CN111205319B - Continuous synthesis method and system of glyphosate - Google Patents

Continuous synthesis method and system of glyphosate Download PDF

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CN111205319B
CN111205319B CN202010182745.XA CN202010182745A CN111205319B CN 111205319 B CN111205319 B CN 111205319B CN 202010182745 A CN202010182745 A CN 202010182745A CN 111205319 B CN111205319 B CN 111205319B
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tower
hydrolysis reaction
gas
rectification
methanol
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CN111205319A (en
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周曙光
胡跃华
屠民海
王瑜钢
杨鸣刚
叶志凤
胡江
陈晓军
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Zhejiang Xinan Chemical Industrial Group Co Ltd
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Zhejiang Xinan Chemical Industrial Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
    • C07F9/3804—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se) not used, see subgroups
    • C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
    • C07F9/3813—N-Phosphonomethylglycine; Salts or complexes thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/48—Preparation of compounds having groups
    • C07C41/50—Preparation of compounds having groups by reactions producing groups
    • C07C41/56—Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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Abstract

The invention relates to the technical field of glyphosate production, in particular to a continuous synthesis method and system of glyphosate. The continuous synthesis method comprises the following steps: under the action of triethylamine, glycine, paraformaldehyde and dialkyl phosphite react in methanol, the obtained synthetic liquid is acidified, the obtained acidified liquid is subjected to primary hydrolysis reaction and secondary hydrolysis reaction, the slurry after the secondary hydrolysis reaction is crystallized to obtain glyphosate, and the gas after the secondary hydrolysis reaction is condensed to obtain condensate and non-condensable gas; mixing gas generated by the primary hydrolysis reaction, non-condensable gas and alkali liquor, carrying out neutralization reaction, stripping the obtained solution and condensate, carrying out first rectification on the obtained gas and the gas obtained by the neutralization reaction, and carrying out second rectification on the obtained tower bottom liquid to obtain methanol; the low-boiling-point substances at the top of the first rectification are subjected to third rectification to obtain chloromethane; and (3) rectifying tower bottom liquid of the third rectification to obtain methylal. The yield of the glyphosate is high, and byproducts can be effectively recovered.

Description

Continuous synthesis method and system of glyphosate
Technical Field
The invention relates to the technical field of glyphosate production, in particular to a continuous synthesis method and system of glyphosate.
Background
Glyphosate is a highly effective, low-toxic, broad-spectrum, biocidal, nonselective herbicide with excellent biological properties. At present, the main production process of the domestic glyphosate has two routes: alkyl ester process (glycine process) and iminodiacetic acid process (IDA process). The foreign production process is mainly the iminodiacetic acid method of Monsanto company in the United states. The method takes methanol as a reaction solvent, in the presence of a catalyst triethylamine, glycine firstly reacts with polyoxymethylene to form N, N-dimethylolglycine, then reacts with dimethyl phosphite and then is hydrolyzed by hydrochloric acid to generate glyphosate, byproduct methylal and chloromethane. The main components of the hydrolysis tail gas of the glycine method glyphosate synthetic solution are water, methylal, methanol, hydrogen chloride and chloromethane mixture, and the recovery process of the tail gas is called solvent recovery for short in the glyphosate industry. The synthetic solution is a mixed solution of raw materials such as methanol, paraformaldehyde (or other formaldehyde sources), glycine (or other raw materials taking chloroacetic acid as a starting point raw material), dimethyl phosphite (or other alkyl phosphate) and the like, and the main components of the mixed solution are organic phosphorus intermediates (glyphosate precursors) such as N-methoxyalkyl ester methyl glycine and the like through depolymerization, condensation and esterification reactions.
The existing glyphosate hydrolysis process is intermittent hydrolysis, after a certain proportion of synthetic solution is mixed with hydrochloric acid in a hydrolysis kettle, steam is introduced to heat up to the reaction end temperature, along with the increase of the hydrolysis temperature, the steam of methylal, methanol, chloromethane, water, hydrogen chloride and the like is distilled out of the reaction kettle, and is treated by a non-condensable gas coarse chloromethane (containing air and acid) chloromethane recovery device and a condensate (diluted methanol) desolventizing recovery device through tertiary condensation.
Patent CN103739625B discloses a continuous hydrolysis process for preparing glyphosate by glycine method, which separates the mixed acid liquid from gas and liquid, the liquid and the condensed gas enter a methylal tower to recover methylal, the bottom liquid of the kettle recovered from methylal enters a methanol recovery tower to recover methanol, and the bottom liquid of the kettle discharged from the methanol recovery tower enters a hydrolysis kettle to complete hydrolysis reaction. The method has low recovery rate of methylal and high energy consumption.
The traditional recovery process is to condense the hydrolysis vapors, wherein the relatively high boiling point methanol, methylal, water and small amounts of hydrogen chloride gas are condensed into a liquid phase, called dilute methanol; the chloromethane is gas phase, and the chloromethane gas is obtained after water washing, alkali washing and sulfuric acid drying to achieve the aim of purification, and the chloromethane product is obtained after compression and condensation. And adding alkali into the diluted methanol obtained by condensation for neutralization, respectively recovering the methanol and methylal in the diluted methanol through two rectifying towers, and recycling the methanol as a solvent to a glyphosate synthesis link, wherein methylal is used as a byproduct.
Patent CN108380029A discloses a system and a process for recovering glyphosate solvent by alkyl ester method, wherein the glyphosate hydrolysis tail gas is subjected to neutralization, pressure control and temperature control and then is sent to a condenser for condensation separation, the condensate is sent to a dilute methanol solution recovery tank, and the non-condensable gas is sent to a chloromethane recovery device.
The two procedures of hydrolysis and solvent recovery in the glyphosate production process are main procedures of steam consumption, a large amount of materials such as methanol, methylal and water are firstly condensed into a liquid state, and then enter the tower again, and a large amount of steam is required to be consumed for heating into a vapor state, so that the heat of hydrolysis steam is wasted, a large amount of raw steam is consumed additionally, and great heat waste is caused.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide a continuous synthesis method and a continuous synthesis system of glyphosate.
The invention provides a continuous synthesis method of glyphosate, which comprises the following steps:
a) Under the action of triethylamine, glycine, paraformaldehyde and dialkyl phosphite are reacted in methanol, and the reacted synthetic solution is acidified to obtain acidified solution;
B) Carrying out primary hydrolysis reaction on the acidizing fluid at the temperature of 90-112 ℃ and the pressure of-5-20 KPa;
c) Carrying out secondary hydrolysis reaction on the product solution of the primary hydrolysis reaction at 115-130 ℃ and-10 KPa, crystallizing slurry after the secondary hydrolysis reaction to obtain glyphosate, and condensing gas after the secondary hydrolysis reaction to obtain condensate and non-condensable gas;
mixing the gas generated by the primary hydrolysis reaction, the non-condensable gas and alkali liquor, and carrying out neutralization reaction;
d) Mixing the solution after the neutralization reaction with condensate, and then carrying out steam stripping, wherein the gas obtained by steam stripping and the gas obtained by the neutralization reaction are subjected to first rectification at-10 KPa and the temperature of a tower kettle of 65-85 ℃, and the tower kettle liquid obtained by the first rectification is subjected to second rectification at 0.1-0.8 MPa and the temperature of the tower kettle of 85-170 ℃ to obtain methanol; the tower top low-boiling-point substances obtained by the first rectification are subjected to third rectification at 0-80 KPa, the tower bottom temperature of 55-70 ℃ and the tower top temperature of minus 10-minus 20 ℃ to obtain chloromethane; and (3) carrying out fourth rectification on the tower bottom liquid obtained by the third rectification at the temperature of between 0 and 30KPa and the temperature of between 65 and 85 ℃ to obtain methylal.
Preferably, in step a), the reaction comprises:
a1 Carrying out depolymerization reaction on methanol, triethylamine and paraformaldehyde at 40-55 ℃;
a2 Carrying out addition reaction on the depolymerization reaction product and glycine at 40-55 ℃;
a3 And (3) carrying out condensation reaction on the product obtained after the addition reaction and dialkyl phosphite at the temperature of 40-55 ℃ to obtain a synthetic solution.
Preferably, in step A), the acidification temperature is between 35 and 55 ℃, and the acidification pressure is between-10 and 10KPa.
Preferably, in the step C), the pH value of the slurry subjected to the secondary hydrolysis reaction is 0.1-3;
the crystallization includes:
first, carrying out primary crystallization under the vacuum degree of 0.083-0.093 MPa and the temperature of 55-65 ℃;
then carrying out secondary crystallization under the vacuum degree of 0.090-0.096 MPa and the temperature of 42-49 ℃;
then carrying out tertiary crystallization under the vacuum degree of 0.097-0.101 MPa and the temperature of 28-32 ℃;
the condensation is vacuum cooling, and the pressure of the vacuum cooling is more than or equal to-70 KPa; or the condensation is water adding cooling or heat exchanger cooling, and the temperature after water adding cooling is 30-90 ℃.
Preferably, in the step C), the temperature of the neutralization reaction is 70-90 ℃ and the pressure is-5-10 KPa.
Preferably, in the step D), the temperature of the stripping tower kettle is 100-108 ℃, and the stripping pressure is-5-30 KPa;
The reflux ratio of the first rectification is 1-4: 1, a step of; the reflux ratio of the second rectification is 1-4: 1, a step of; the reflux ratio of the third rectification is 1 to 3.5:1, a step of; the reflux ratio of the fourth rectification is 0.5-2: 1.
preferably, in step D), the second rectification comprises a low pressure methanol rectification and a high pressure methanol rectification;
the pressure of the low-pressure methanol rectification is 0.1-0.3 MPa, the temperature of the tower kettle is 85-120 ℃, and the reflux ratio is 1-4: 1, a step of;
the pressure of the high-pressure methanol rectification is 0.4-0.8 MPa, the temperature of the tower kettle is 135-170 ℃, and the reflux ratio is 1-4: 1.
the invention also provides a continuous synthesis system of glyphosate, which comprises:
a synthesis kettle;
the first mixing device is connected with the synthesis liquid outlet of the synthesis kettle;
the primary hydrolysis reaction device is connected with the acidification liquid outlet of the first mixing device;
the secondary hydrolysis reaction device is connected with a product solution outlet of the primary hydrolysis reaction device;
a crystallizer connected with a slurry outlet of the secondary hydrolysis reaction device;
a hydrolysis tail gas condenser connected with a gas outlet of the secondary hydrolysis reaction device;
the first gas inlet is connected with the gas outlet of the hydrolysis tail gas condenser; the second gas inlet of the alkaline washing tower is connected with the gas outlet of the first mixing device; the third gas inlet of the alkaline washing tower is connected with the gas outlet of the primary hydrolysis reaction device;
The first liquid inlet is connected with the liquid outlet of the alkaline washing tower; the second liquid inlet of the second mixing device is connected with the liquid outlet of the hydrolysis tail gas condenser;
a stripping column with a first liquid inlet connected with a liquid outlet of the second mixing device;
the first gas inlet is connected with the gas outlet of the alkaline washing tower; the second gas inlet of the separation tower is connected with the gas outlet of the stripping tower;
a methanol column connected to the liquid outlet of the separation column;
a dechlorination methane column connected to the gas outlet of the separation column;
and the methylal tower is connected with the liquid outlet of the dechlorination methane tower.
Preferably, the primary hydrolysis reaction device comprises a primary hydrolysis reaction tower and a primary hydrolysis reaction kettle;
the product solution outlet of the primary hydrolysis reaction tower is connected with the product solution inlet of the primary hydrolysis reaction kettle;
the gas outlet of the primary hydrolysis reaction kettle is connected with the gas inlet of the primary hydrolysis reaction tower;
the secondary hydrolysis reaction device comprises a secondary hydrolysis reaction kettle;
and a product solution inlet of the secondary hydrolysis reaction kettle is connected with a product solution outlet of the primary hydrolysis reaction kettle.
Preferably, the methanol column comprises a low pressure methanol column and a high pressure methanol column;
the liquid inlet of the low-pressure methanol tower is connected with the liquid outlet of the separation tower;
the liquid inlet of the high-pressure methanol tower is connected with the liquid outlet of the low-pressure methanol tower;
the liquid outlet of the high-pressure methanol tower is connected with the second liquid phase inlet of the stripping tower.
The invention provides a continuous synthesis method of glyphosate, which comprises the following steps: a) Under the action of triethylamine, glycine, paraformaldehyde and dialkyl phosphite are reacted in methanol, and the reacted synthetic solution is acidified to obtain acidified solution; b) Carrying out primary hydrolysis reaction on the acidizing fluid at the temperature of 90-112 ℃ and the pressure of-5-20 KPa; c) Carrying out secondary hydrolysis reaction on the product solution of the primary hydrolysis reaction at 115-130 ℃ and-10 KPa, crystallizing slurry after the secondary hydrolysis reaction to obtain glyphosate, and condensing gas after the secondary hydrolysis reaction to obtain condensate and non-condensable gas; mixing the gas generated by the primary hydrolysis reaction, the non-condensable gas and alkali liquor, and carrying out neutralization reaction; d) Mixing the solution after the neutralization reaction with condensate, and then carrying out steam stripping, wherein the gas obtained by steam stripping and the gas obtained by the neutralization reaction are subjected to first rectification under the conditions of-10 MPa and the temperature of a tower kettle of 65-85 ℃, and the tower kettle liquid obtained by the first rectification is subjected to second rectification under the conditions of 0.1-0.8 MPa and the temperature of the tower kettle of 100-165 ℃ to obtain methanol; the tower top low-boiling-point substances obtained by the first rectification are subjected to third rectification at 0-80 KPa, the tower bottom temperature of 55-70 ℃ and the tower top temperature of minus 10-minus 20 ℃ to obtain chloromethane; and (3) carrying out fourth rectification on the tower bottom liquid obtained by the third rectification at the temperature of between 0 and 30KPa and the temperature of between 65 and 85 ℃ to obtain methylal. The continuous synthesis method of the glyphosate has simple process and high yield, and can effectively recycle byproducts.
Drawings
FIG. 1 is a schematic flow diagram of a continuous synthesis system for glyphosate provided in accordance with one embodiment of the present invention;
FIG. 2 is a schematic flow diagram of a system for the continuous synthesis of glyphosate in accordance with another embodiment of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a continuous synthesis method of glyphosate, which comprises the following steps:
a) Under the action of triethylamine, glycine, paraformaldehyde and dialkyl phosphite are reacted in methanol, and the reacted synthetic solution is acidified to obtain acidified solution;
b) Carrying out primary hydrolysis reaction on the acidizing fluid at the temperature of 90-112 ℃ and the pressure of-5-20 KPa;
c) Carrying out secondary hydrolysis reaction on the product solution of the primary hydrolysis reaction at 115-130 ℃ and-10 KPa, crystallizing slurry after the secondary hydrolysis reaction to obtain glyphosate, and condensing gas after the secondary hydrolysis reaction to obtain condensate and non-condensable gas;
Mixing the gas generated by the primary hydrolysis reaction, the non-condensable gas and alkali liquor, and carrying out neutralization reaction;
d) Mixing the solution after the neutralization reaction with condensate, and then carrying out steam stripping, wherein the gas obtained by steam stripping and the gas obtained by the neutralization reaction are subjected to first rectification under the conditions of-10 MPa and the temperature of a tower kettle of 65-85 ℃, and the tower kettle liquid obtained by the first rectification is subjected to second rectification under the conditions of 0.1-0.8 MPa and the temperature of the tower kettle of 100-165 ℃ to obtain methanol; the tower top low-boiling-point substances obtained by the first rectification are subjected to third rectification at 0-80 KPa, the tower bottom temperature of 55-70 ℃ and the tower top temperature of minus 10-minus 20 ℃ to obtain chloromethane; and (3) carrying out fourth rectification on the tower bottom liquid obtained by the third rectification at the temperature of between 0 and 30KPa and the temperature of between 65 and 85 ℃ to obtain methylal.
Under the action of triethylamine, glycine, paraformaldehyde and dialkyl phosphite react in methanol.
In certain embodiments of the invention, the reacting comprises:
a1 Carrying out depolymerization reaction on methanol, triethylamine and paraformaldehyde at 40-55 ℃;
a2 Carrying out addition reaction on the depolymerization reaction product and glycine at 40-55 ℃;
a3 And (3) carrying out condensation reaction on the product obtained after the addition reaction and dialkyl phosphite at the temperature of 40-55 ℃ to obtain a synthetic solution.
In certain embodiments of the invention, the mass ratio of methanol, triethylamine and paraformaldehyde is 4750 to 5700: 1615-1710: 950. in certain embodiments, the mass ratio of methanol, triethylamine, and paraformaldehyde is 5200:1630:950 or 5400:1650:950. in certain embodiments of the invention, the mass ratio of glycine to paraformaldehyde is 1045 to 1250:950. in certain embodiments, the mass ratio of glycine to paraformaldehyde is 1200:950 or 1250:950. in certain embodiments of the invention, the mass ratio of dialkyl phosphite to paraformaldehyde is from 1995 to 2185:950. in certain embodiments, the mass ratio of dialkyl phosphite to paraformaldehyde is 2060:950 or 2100:950. in certain embodiments of the invention, the dialkyl phosphite is dimethyl phosphite.
In certain embodiments of the invention, the depolymerization reaction is at a temperature of 45 ℃ or 50 ℃. In certain embodiments of the invention, the temperature of the addition reaction is 50 ℃ or 45 ℃. In certain embodiments of the invention, the temperature of the condensation reaction is 50 ℃ or 45 ℃.
In certain embodiments of the invention, the reaction in step a) is carried out in a synthesis kettle.
And after the synthetic liquid is obtained, acidifying the synthetic liquid to obtain an acidified liquid.
In certain embodiments of the invention, the acidifying agent employed for the acidification is hydrochloric acid. In certain embodiments of the invention, the acidification temperature is between 35 and 55 ℃ and the acidification pressure is between-10 and 10KPa. In certain embodiments, the acidification temperature is 40 to 55 ℃, 50 ℃ or 40 ℃, and the acidification pressure is-5 to 5KPa or 0KPa or 5KPa.
In certain embodiments of the invention, the acidification is performed in a first mixing device.
After the acidizing fluid is obtained, the acidizing fluid is subjected to primary hydrolysis reaction at the temperature of 90-112 ℃ and the pressure of minus 5-20 KPa.
In certain embodiments of the invention, the acidified solution further comprises, prior to performing the primary hydrolysis reaction: and cooling the acidizing fluid. In certain embodiments of the invention, the temperature after cooling is 30-60 ℃. In certain embodiments of the invention, the cooling is performed in an acidification cooler.
In certain embodiments of the invention, the primary hydrolysis reaction is at a temperature of 100 to 110 ℃, 108 ℃, or 100 ℃ and a pressure of 3 to 12KPa, 10KPa, or 5KPa. In certain embodiments of the invention, the primary hydrolysis reaction is performed in a primary hydrolysis reaction apparatus.
After the primary hydrolysis reaction is finished, carrying out secondary hydrolysis reaction on the product solution of the primary hydrolysis reaction at 115-130 ℃ and minus 10-10 KPa.
In certain embodiments of the invention, the secondary hydrolysis reaction is carried out at a temperature of 115 to 125 ℃, 120 ℃ or 115 ℃ and at a pressure of-5 to 5KPa, -5KPa or 0KPa. In certain embodiments of the invention, the secondary hydrolysis reaction is performed in a secondary hydrolysis reaction apparatus.
And after the secondary hydrolysis reaction is finished, crystallizing the slurry after the secondary hydrolysis reaction to obtain glyphosate, and condensing the gas after the secondary hydrolysis reaction to obtain condensate and non-condensable gas.
In certain embodiments of the invention, the crystallization is preceded by adjusting the pH of the slurry after the secondary hydrolysis reaction to a pH of 0.1 to 3, 0.1 or 2.
In certain embodiments of the invention, the crystallization is carried out at a discharge flow rate of 3 to 20m 3 /h。
In certain embodiments of the invention, the crystallizing comprises:
first, carrying out primary crystallization under the vacuum degree of 0.083-0.093 MPa and the temperature of 55-65 ℃;
then carrying out secondary crystallization under the vacuum degree of 0.090-0.096 MPa and the temperature of 42-49 ℃;
then three-stage crystallization is carried out under the vacuum degree of 0.097-0.101 MPa and the temperature of 28-32 ℃.
The size of the crystals is increased or controlled by stepwise crystallization.
In certain embodiments of the invention, the primary crystallization is at a pressure of 0.084MPa or 0.088MPa and a temperature of 64 ℃ or 55 ℃; the pressure of the secondary crystallization is 0.090MPa or 0.096MPa, and the temperature is 42 ℃; the pressure of the tertiary crystallization is 0.097MPa or 0.101MPa, and the temperature is 32 ℃ or 28 ℃.
In certain embodiments of the invention, the crystallization is performed in a crystallizer. In certain embodiments of the invention, the primary crystallization is performed in a primary crystallizer, the secondary crystallization is performed in a secondary crystallizer, and the tertiary crystallization is performed in a tertiary crystallizer.
In certain embodiments of the invention, the gas resulting from the primary crystallization is subjected to primary condensation. In certain embodiments, the first stage condensation is performed using recycled water. In certain embodiments, the gas temperature after the primary condensation is 30 to 45 ℃. After the condensate liquid is collected into the condensate liquid tank, the condensate liquid can be conveyed to a dilute methanol storage tank by a pump, and the non-condensable gas is discharged after being buffered by the primary vacuum buffer tank.
In certain embodiments of the invention, the gas resulting from the secondary crystallization is subjected to secondary condensation. In certain embodiments, the circulating water is utilized for secondary condensation. In certain embodiments, the gas temperature after the secondary condensation is 30 to 45 ℃. After the condensate liquid is collected into the condensate liquid tank, the condensate liquid can be conveyed to a dilute methanol storage tank by a pump, and non-condensable gas is discharged after being buffered by a secondary vacuum buffer tank.
In certain embodiments of the invention, the gas resulting from the tertiary crystallization is subjected to tertiary condensation. In certain embodiments, the tertiary condensation is performed using recycled water. In certain embodiments, the gas temperature after the three stage condensation is 30 to 45 ℃. After the condensate liquid is collected into the condensate liquid tank, the condensate liquid can be conveyed to a dilute methanol storage tank by a pump, and non-condensable gas is discharged after being buffered by a secondary vacuum buffer tank.
In certain embodiments of the invention, after the tertiary crystallization, centrifugal drying is further included to obtain glyphosate. In certain embodiments of the invention, the centrifugal drying is performed in a centrifugal drying apparatus.
In some embodiments of the invention, the condensation of the gas after the secondary hydrolysis reaction is vacuum cooling, and the pressure of the vacuum cooling is more than or equal to-70 KPa; or the condensation is water adding and cooling, and the temperature after the water adding and cooling is 30-90 ℃. In certain embodiments of the invention, the reduced vacuum pressure is-60 KPa. In certain embodiments of the invention, the condensing is performed in a hydrolysis tail gas condenser. In certain embodiments of the invention, the condensed condensate may be collected into a dilute methanol surge tank.
And mixing the gas generated by the primary hydrolysis reaction, the non-condensable gas and alkali liquor, and carrying out neutralization reaction. In certain embodiments of the invention, the gas produced by the acidification, the gas produced by the primary hydrolysis reaction, the non-condensable gas and the lye are mixed to perform a neutralization reaction. In certain embodiments of the invention, the lye comprises sodium hydroxide solution. In certain embodiments of the invention, the lye has a mass concentration of not more than 48%, preferably not more than 10%, more preferably not more than 5%. In certain embodiments of the invention, the gas produced by the primary hydrolysis reaction comprises methanol, methylal, methyl chloride, water, and hydrogen chloride. In certain embodiments of the invention, the non-condensable gas comprises methanol, methylal, methyl chloride, water and hydrogen chloride.
In certain embodiments of the invention, the neutralization reaction is carried out at a temperature of from 70 to 90℃and a pressure of from-5 to 10KPa. In certain embodiments of the invention, the neutralization reaction is at a temperature of 74 ℃ or 85 ℃ and a pressure of 0KPa or 5KPa.
In certain embodiments of the invention, the neutralization is performed in a caustic wash column.
After the neutralization reaction is completed, the solution after the neutralization reaction and condensate (condensate refers to condensate obtained by condensing gas after the secondary hydrolysis reaction) are mixed and then stripped. In certain embodiments of the invention, the mixing is performed in a second mixing device. In certain embodiments of the invention, the stripper bottoms temperature is 100 to 108 ℃, and the stripping pressure is-5 to 30KPa. In certain embodiments of the invention, the stripper bottoms temperature is 100-105 ℃, 103 ℃ or 100 ℃, and the stripping pressure is 0-10 KPa, 5KPa or 10KPa. In certain embodiments of the invention, the stripping is performed in a stripping column.
In certain embodiments of the invention, the stripped wastewater may enter a wastewater treatment plant.
In the invention, the gas obtained by stripping and the gas obtained by neutralization are subjected to first rectification at-10 KPa and the temperature of a tower kettle of 65-85 ℃. In certain embodiments of the invention, the stripped gas comprises methanol and water. In certain embodiments of the invention, the pressure of the first rectification is 5KPa or 10KPa and the temperature is 65 ℃. In certain embodiments of the invention, the reflux ratio of the first rectification is from 1 to 4:1. in certain embodiments, the reflux ratio of the first rectification is from 2.2 to 2.3:1 or 2.2:1. in certain embodiments of the invention, the first rectification is performed in a separation column. In certain embodiments of the invention, the gas resulting from the first rectification comprises methanol, methylal, and methyl chloride.
In the invention, the tower bottom liquid obtained by the second rectification is subjected to the second rectification under the conditions of 0.1-0.8 MPa and the temperature of the tower bottom of 85-170 ℃ to obtain the methanol. In certain embodiments of the invention, the pressure of the second rectification is 0.5MPa and the bottoms temperature of the second rectification is 150 ℃. In certain embodiments of the invention, the reflux ratio of the second rectification is from 1 to 4:1. in certain embodiments, the reflux ratio of the second rectification is 1.5:1. in certain embodiments of the invention, the second rectification is performed in a methanol column.
In certain embodiments of the invention, the second rectification comprises a low pressure methanol rectification and a high pressure methanol rectification. In some embodiments of the invention, the pressure of the low-pressure methanol rectification is 0.1-0.3 MPa, the temperature of the tower kettle is 85-120 ℃, and the reflux ratio is 1-4: 1 or 1.5:1. in certain embodiments, the pressure of the low-pressure methanol rectification is 0.18MPa or 0.1MPa, the temperature of the tower kettle is 107 ℃ or 115 ℃, and the reflux ratio is 1.5-2: 1 or 1.5:1. in certain embodiments of the invention, the low pressure methanol rectification is performed in a low pressure methanol column. A portion of the methanol may be recovered by low pressure methanol rectification.
In some embodiments of the invention, the pressure of the high-pressure methanol rectification is 0.4-0.8 MPa, the temperature of the tower kettle is 135-170 ℃, and the reflux ratio is 1-4: 1. in certain embodiments of the invention, the pressure of the high pressure methanol rectification is 0.6MPa or 0.7MPa, the tower kettle temperature is 150-165 ℃ or 155 ℃, and the reflux ratio is 2-2.5: 1 or 2.5:1. in certain embodiments of the invention, the high pressure methanol rectification is performed in a high pressure methanol column. In certain embodiments of the invention, the liquid after the high pressure methanol rectification is refluxed to the stripper column. Most of the methanol can be recovered by high pressure methanol rectification.
In the invention, the tower top low-boiling-point substance obtained by the first rectification is subjected to third rectification at 0-80 KPa, the tower bottom temperature is 55-70 ℃ and the tower top temperature is minus 10-minus 20 ℃ to obtain chloromethane. In some embodiments of the invention, the pressure of the third rectification is 55KPa or 40KPa, the temperature of the tower bottom is 60-65 ℃, the temperature of the tower top is-14 to-17 ℃, the temperature of the tower top is-14 ℃ or-17 ℃. In certain embodiments of the invention, the reflux ratio of the third rectification is from 1 to 3.5:1. in certain embodiments, the reflux ratio of the third rectification is from 1.2 to 1.5:1 or 1.5:1. in certain embodiments of the invention, the third rectification is performed in a demethanizer.
And (3) performing fourth rectification on the tower bottom liquid obtained by the third rectification at the temperature of between 0 and 30KPa and the temperature of between 65 and 85 ℃ to obtain methylal and methanol. In certain embodiments of the invention, the fourth rectification is at a pressure of 20KPa or 10KPa and a column bottoms temperature of 73 ℃ or 80 ℃. In certain embodiments of the invention, the reflux ratio of the fourth rectification is from 0.5 to 2:1. in certain embodiments, the fourth rectification has a reflux ratio of 1:1. in certain embodiments of the invention, the fourth rectification is performed in a methylal column.
The source of the raw materials used in the present invention is not particularly limited, and may be generally commercially available.
The continuous synthesis method of the glyphosate has simple process and high yield, and can effectively recycle byproducts.
The invention also provides a continuous synthesis system of glyphosate for implementing the continuous synthesis method, which comprises the following steps:
a synthesis kettle;
the first mixing device is connected with the synthesis liquid outlet of the synthesis kettle;
the primary hydrolysis reaction device is connected with the acidification liquid outlet of the first mixing device;
the secondary hydrolysis reaction device is connected with a product solution outlet of the primary hydrolysis reaction device;
a crystallizer connected with a slurry outlet of the secondary hydrolysis reaction device;
a hydrolysis tail gas condenser connected with a gas outlet of the secondary hydrolysis reaction device;
the first gas inlet is connected with the gas outlet of the hydrolysis tail gas condenser; the second gas inlet of the alkaline washing tower is connected with the gas outlet of the first mixing device; the third gas inlet of the alkaline washing tower is connected with the gas outlet of the primary hydrolysis reaction device;
the first liquid inlet is connected with the liquid outlet of the alkaline washing tower; the second liquid inlet of the second mixing device is connected with the liquid outlet of the hydrolysis tail gas condenser;
A stripping column with a first liquid inlet connected with a liquid outlet of the second mixing device;
the first gas inlet is connected with the gas outlet of the alkaline washing tower; the second gas inlet of the separation tower is connected with the gas outlet of the stripping tower;
a methanol column connected to the liquid outlet of the separation column;
a dechlorination methane column connected to the gas outlet of the separation column;
and the methylal tower is connected with the liquid outlet of the dechlorination methane tower.
See fig. 1. Fig. 1 is a schematic flow diagram of a glyphosate continuous synthesis system according to one embodiment of the present invention.
The continuous synthesis system of glyphosate provided by the invention comprises a synthesis kettle. The synthesis kettle is used for carrying out the reaction of the step A) in the continuous synthesis method. In an embodiment of the invention, the synthesis tank is provided with a raw material inlet and a synthesis liquid outlet. The structure of the synthesis kettle is not particularly limited, and the synthesis kettle can be a conventional synthesis kettle. And discharging the synthetic liquid obtained after the reaction from a synthetic liquid outlet of the synthesis kettle, and entering the first mixing device. In some embodiments of the invention, the synthesis liquid exiting the synthesis tank at the synthesis liquid outlet is fed to the first mixing device by a synthesis liquid feed pump. The structure of the synthetic fluid transfer pump is not particularly limited, and may be a conventional centrifugal pump.
The continuous synthesis system of glyphosate provided by the invention further comprises a first mixing device connected with the synthesis liquid outlet of the synthesis kettle. In certain embodiments of the invention, the first mixing device is provided with a mixed liquor inlet, an acidulant outlet and a gas outlet. In certain embodiments of the invention, the mixed liquor inlet of the first mixing device is connected to the mixed liquor outlet of the synthesis tank. The first mixing device is used for acidifying the synthetic liquid. In certain embodiments of the invention, the first mixing device is a tubular static mixer, the model may be SK, SV or SX, preferably SK.
The continuous synthesis system of glyphosate provided by the invention further comprises a primary hydrolysis reaction device connected with the acidification liquid outlet of the first mixing device. The primary hydrolysis reaction device is used for primary hydrolysis of the acidizing fluid, and simultaneously, light components such as methanol, methylal, chloromethane and the like are separated from the hydrolysis fluid. In certain embodiments of the present invention, the primary hydrolysis reaction apparatus includes a primary hydrolysis reaction column and a primary hydrolysis reaction kettle.
In certain embodiments of the invention, the primary hydrolysis reaction column is provided with an acidified liquid inlet, a product solution outlet, a gas outlet, and a gas inlet. And an acidizing fluid inlet of the primary hydrolysis reaction tower is connected with an acidizing fluid outlet of the first mixing device.
In certain embodiments of the present invention, the primary hydrolysis reaction kettle is provided with a product solution inlet, a product solution outlet, and a gas outlet. And a product solution inlet of the first-stage hydrolysis reaction tower is connected with an acidizing fluid outlet of the first mixing device. And a product solution outlet of the primary hydrolysis reaction tower is connected with a product solution inlet of the primary hydrolysis reaction kettle. And a gas outlet of the primary hydrolysis reaction kettle is connected with a gas inlet of the primary hydrolysis reaction tower. And returning the gas exhausted from the primary hydrolysis reaction kettle to the primary hydrolysis reaction tower.
The structures of the primary hydrolysis reaction tower and the primary hydrolysis reaction kettle are not particularly limited. In certain embodiments of the invention, the primary hydrolysis reaction column is a corrosion resistant packed column. In certain embodiments, the primary hydrolysis reaction column is an open glass lined packed column, a tetrafluoro lined packed column, or a graphite packed column. In certain embodiments of the invention, the primary hydrolysis reaction vessel is an open glass lined reaction vessel.
In certain embodiments of the invention, the continuous synthesis system further comprises a hydrolysis reboiler. The hydrolysis reboiler is used for heating the primary hydrolysis reaction kettle. The connection mode of the hydrolysis reboiler is not particularly limited, and the first-stage hydrolysis reaction kettle can be heated. The present invention is not particularly limited in the structure of the hydrolysis reboiler, and in some embodiments of the present invention, the hydrolysis reboiler is a round block hole type graphite heat exchanger.
In certain embodiments of the invention, the continuous synthesis system further comprises an acidification cooler. See fig. 2. FIG. 2 is a schematic flow diagram of a system for the continuous synthesis of glyphosate in accordance with another embodiment of the present invention. The acidification cooler is used for cooling the acidification liquid. The acidification cooler is characterized in that an acidification liquid inlet is connected with an acidification liquid outlet of the first mixing device, and an acidification liquid outlet of the acidification cooler is connected with an acidification liquid inlet of the primary hydrolysis reaction tower. The structure of the acidizing fluid cooler is not particularly limited, and the acidizing fluid cooler can be a conventional acidizing fluid cooler. In certain embodiments of the invention, the acidified liquid discharged from the acidified liquid outlet of the first mixing means is fed to an acidification cooler by means of an acidification liquid pump. The structure of the acidification liquid pump is not particularly limited, and the acidification liquid pump can be a conventional centrifugal pump or a magnetic pump.
The continuous synthesis system of glyphosate provided by the invention also comprises a secondary hydrolysis reaction device connected with the product solution outlet of the primary hydrolysis reaction device. The secondary hydrolysis reaction device is used for carrying out secondary hydrolysis reaction on the product solution of the primary hydrolysis reaction, and simultaneously separating residual light components, water, hydrogen chloride and the like. In certain embodiments of the invention, the secondary hydrolysis reaction apparatus is a secondary hydrolysis reaction kettle.
In certain embodiments of the invention, the secondary hydrolysis reactor is provided with a product solution inlet, a slurry outlet, and a gas outlet. And a product solution inlet of the secondary hydrolysis reaction kettle is connected with a product solution outlet of the primary hydrolysis reaction kettle.
The structure of the secondary hydrolysis reaction kettle is not particularly limited in the invention, and in some embodiments of the invention, the secondary hydrolysis reaction kettle is an open glass lining reaction kettle.
The continuous synthesis system of glyphosate provided by the invention also comprises a crystallizer connected with the slurry outlet of the secondary hydrolysis reaction device. The crystallizer is used for separating out glyphosate crystals in slurry discharged from the secondary hydrolysis reaction device. In certain embodiments of the invention, the continuous synthesis system further comprises a buffer tank. The buffer tank is used for adjusting the pH value of the slurry discharged from the slurry outlet of the secondary hydrolysis reaction device and then enters the crystallizer. In certain embodiments of the invention, the slurry inlet of the surge tank is connected to the slurry outlet of the secondary hydrolysis reaction device.
In certain embodiments of the invention, the crystallizer comprises a primary crystallizer, a secondary crystallizer, and a tertiary crystallizer.
In certain embodiments of the invention, the slurry inlet of the primary crystallizer is connected to the slurry outlet of the secondary hydrolysis reactor. And the slurry inlet of the secondary crystallizer is connected with the slurry outlet of the primary crystallizer. And the slurry inlet of the third-stage crystallizer is connected with the slurry outlet of the second-stage crystallizer. And the slurry discharged from the slurry outlet of the three-stage crystallizer is glyphosate. In certain embodiments, the slurry inlet of the primary crystallizer is connected to the liquid outlet of the surge tank.
The structure of each stage of the crystallizer is not particularly limited in the present invention, and in some embodiments of the present invention, each stage of the crystallizer may be a DTB crystallizer.
In certain embodiments of the invention, the slurry exiting the secondary hydrolysis reaction column enters the primary crystallizer via a primary crystallization feed pump. The structure of the primary crystallization feed pump is not particularly limited, and may be a conventional centrifugal pump or magnetic pump. In certain embodiments of the invention, the slurry exiting the primary crystallizer enters the secondary crystallizer via a secondary crystallization feed pump. The structure of the secondary crystallization feed pump is not particularly limited, and may be a conventional centrifugal pump or magnetic pump. In certain embodiments of the present invention, the slurry exiting the secondary crystallizer is fed into the tertiary crystallizer by a tertiary crystallization feed pump. The structure of the three-stage crystallization feed pump is not particularly limited, and the three-stage crystallization feed pump can be a conventional centrifugal pump or a magnetic pump.
In certain embodiments of the invention, the continuous synthesis system further comprises a primary condenser, a primary vacuum buffer tank, and a condensate tank. In certain embodiments of the invention, the gas inlet of the primary condenser is connected to the gas outlet of the primary crystallizer, and the liquid outlet of the primary condenser is connected to the first liquid inlet of the condensate tank. And a gas outlet of the primary condenser is connected with a gas inlet of the primary vacuum buffer tank. And condensing the gas from the primary crystallizer in the primary condenser, enabling the condensate to enter a condensate tank, and discharging the non-condensable gas after buffering the non-condensable gas by the primary vacuum buffer tank. The invention is not particularly limited to the structures of the primary condenser, the primary vacuum buffer tank and the condensate tank, and can be a conventional condenser, a vacuum buffer tank and a condensate tank.
In certain embodiments of the invention, the continuous synthesis system further comprises a secondary condenser and a secondary vacuum buffer tank. In some embodiments of the invention, the gas inlet of the secondary condenser is connected to the gas outlet of the secondary crystallizer, the liquid outlet of the secondary condenser is connected to the second liquid inlet of the condensate tank, and the gas outlet of the secondary condenser is connected to the gas inlet of the secondary vacuum buffer tank. The gas from the secondary crystallizer is condensed in a secondary condenser, the condensate enters a condensate tank, and the non-condensed gas is discharged after being buffered by a secondary vacuum buffer tank. The structure of the secondary condenser and the secondary vacuum buffer tank is not particularly limited, and the secondary condenser, the vacuum buffer tank and the condensate tank can be conventional condensers.
In certain embodiments of the invention, the continuous synthesis system further comprises a three stage condenser and a three stage vacuum buffer tank. In certain embodiments of the invention, the gas inlet of the three-stage condenser is connected to the gas outlet of the three-stage crystallizer, the liquid outlet of the three-stage condenser is connected to the third liquid inlet of the condensate tank, and the gas outlet of the three-stage condenser is connected to the gas inlet of the three-stage vacuum buffer tank. The gas from the three-stage crystallizer is condensed in a three-stage condenser, the condensate enters a condensate tank, and the non-condensed gas is discharged after being buffered by a three-stage vacuum buffer tank. The invention is not particularly limited to the structures of the three-stage condenser and the three-stage vacuum buffer tank, and can be a conventional condenser, vacuum buffer tank and condensate tank.
In some embodiments of the invention, after the liquid entering the condensate tank is cooled in the condensate tank, the liquid can be pumped to a dilute methanol storage tank and can flow back to the three crystallizers.
In certain embodiments of the invention, the continuous synthesis system of glyphosate further comprises a centrifugal drying apparatus. And the inlet of the centrifugal drying device is connected with the glyphosate outlet of the three-stage crystallizer. The centrifugal drying device is used for drying the glyphosate obtained by the three-stage crystallizer. The structure of the centrifugal drying device is not particularly limited, and a centrifugal drying device well known to those skilled in the art may be used.
The continuous synthesis system of glyphosate provided by the invention further comprises a hydrolysis tail gas condenser connected with the gas outlet of the secondary hydrolysis reaction device. The hydrolysis tail gas condenser is used for cooling the tail gas after the secondary hydrolysis reaction. In certain embodiments of the invention, the hydrolysis tail gas condenser is provided with a gas inlet, a gas outlet, and a condensate outlet. In certain embodiments of the invention, the gas inlet of the hydrolysis tail gas condenser is connected to the gas outlet of the secondary hydrolysis reaction device. In certain embodiments, the gas inlet of the hydrolysis tail gas condenser is connected to the gas outlet of the secondary hydrolysis reactor. The structure of the hydrolysis tail gas condenser is not particularly limited in the present invention, and in some embodiments of the present invention, the hydrolysis tail gas condenser may be an acid-resistant heat exchanger.
The continuous synthesis system of glyphosate provided by the invention also comprises an alkaline washing tower. The hydrolyzed tail gas is acid gas, and the gas is alkalescent through acid-base neutralization of an alkaline washing tower, so that the equipment material selection range of a rear system is wide, and the cost is lower. The alkaline washing tower is provided with a first gas inlet, a second gas inlet, a third gas inlet, a liquid outlet and a gas outlet. In certain embodiments of the invention, the first gas inlet of the caustic scrubber is connected to the gas outlet of the hydrolysis tail gas condenser, the second gas inlet of the caustic scrubber is connected to the gas outlet of the first mixing device, and the third gas inlet of the caustic scrubber is connected to the gas outlet of the primary hydrolysis reaction device. In certain embodiments of the invention, the third gas inlet of the caustic scrubber is connected to the gas outlet of the primary hydrolysis reaction column. The structure of the caustic tower is not particularly limited in the present invention, and in some embodiments of the present invention, the caustic tower may be a packed tower.
The continuous synthesis system of glyphosate provided by the invention also comprises a second mixing device connected with the liquid outlet of the alkaline washing tower. In an embodiment of the invention, the second mixing device is provided with a first liquid inlet, a second liquid inlet and a liquid outlet. The first liquid inlet of the second mixing device is connected with the liquid outlet of the alkaline washing tower. And a second liquid inlet of the second mixing device is connected with a liquid outlet of the hydrolysis tail gas condenser. In certain embodiments of the invention, the second mixing device is a tubular static mixer, model number may be SK, SV or SX, preferably SK.
The continuous synthesis system of glyphosate provided by the invention also comprises a stripping tower connected with the liquid outlet of the second mixing device. The stripping tower is used for extracting low components in the feed in a steam stripping mode, so that raw material consumption is reduced, and product yield is improved. In certain embodiments of the invention, the stripper is provided with a first liquid inlet, a second liquid inlet, a gas outlet and a liquid outlet. The first liquid inlet of the stripping tower is connected with the liquid outlet of the second mixing device. In certain embodiments of the invention, the second liquid inlet of the stripper column is connected to the liquid outlet of the high pressure methanol column. The structure of the stripping column is not particularly limited in the present invention, and may be a conventional stripping column.
The continuous synthesis system of glyphosate provided by the invention also comprises a separation tower connected with the gas outlet of the alkaline washing tower. The separation tower is used for carrying out the first rectification, and dilute methanol at the tower bottom and low-boiling-point substances at the tower top can be obtained through the first rectification. In certain embodiments of the invention, the separation column is provided with a first gas inlet, a second gas inlet, a liquid outlet and a gas outlet. In certain embodiments of the invention, the first gas inlet of the separation column is connected to the gas outlet of the caustic scrubber and the second gas inlet of the separation column is connected to the gas outlet of the stripper. The present invention is not particularly limited in the structure of the separation column, and in some embodiments of the present invention, the separation column may be a conventional packed rectifying column.
The continuous synthesis system of glyphosate provided by the invention also comprises a methanol tower connected with the liquid outlet of the separation tower. And the dilute methanol at the tower bottom in the separation tower is discharged through a liquid outlet of the separation tower and enters the methanol tower. In certain embodiments of the invention, the methanol column is provided with a liquid inlet and a liquid outlet. The liquid inlet of the methanol tower is connected with the liquid outlet of the separation tower. The structure of the methanol column is not particularly limited in the present invention, and in some embodiments of the present invention, the methanol column may be a conventional packed rectifying column.
In certain embodiments of the invention, the methanol column comprises a low pressure methanol column and a high pressure methanol column. The low-pressure methanol tower is provided with a liquid inlet, a liquid outlet and a methanol outlet. The high-pressure methanol tower is provided with a liquid inlet, a liquid outlet and a methanol outlet. The liquid inlet of the low-pressure methanol tower is connected with the liquid outlet of the separation tower; the liquid inlet of the high-pressure methanol tower is connected with the liquid outlet of the low-pressure methanol tower. The liquid outlet of the high-pressure methanol tower is connected with the second liquid phase inlet of the stripping tower. The structures of the low pressure methanol column and the high pressure methanol column are not particularly limited in the present invention, and in some embodiments of the present invention, the low pressure methanol column may be a conventional packed rectifying column. In certain embodiments of the invention, the high pressure methanol column may be a conventional packed rectification column.
The continuous synthesis system of glyphosate provided by the invention also comprises a dechlorination methane tower connected with the gas outlet of the separation tower. And methyl chloride is refined through rectification of the chloromethane removal tower, so that the treatment cost of a post-system is reduced, methanol and methylal are recovered, and the consumption of the methanol is reduced. In certain embodiments of the invention, the de-chloromethane column is provided with a gas inlet, a column bottoms outlet, and a chloromethane outlet. In certain embodiments of the invention, the gas inlet of the demethanizer is connected to the gas outlet of the separation column. The structure of the demethanizer is not particularly limited in the present invention, and in some embodiments of the present invention, the demethanizer may be a conventional packed rectifying column.
The continuous synthesis system of glyphosate provided by the invention also comprises a methylal tower connected with the liquid outlet of the dechlorination methane tower. The methylal tower is used for recovering methylal and methanol. The methylal tower is provided with a liquid inlet and a gas outlet. The liquid inlet of the methylal tower is connected with the tower bottom liquid outlet of the methane dechlorination tower. The structure of the methylal column is not particularly limited in the present invention, and in some embodiments of the present invention, the methylal column may be a conventional packed rectifying column.
The continuous synthesis method and system of the glyphosate provided by the invention have the advantages of simple process and high glyphosate yield, and can effectively recycle byproducts.
In order to further illustrate the present invention, the following examples are provided to illustrate a method and system for the continuous synthesis of glyphosate, but they should not be construed as limiting the scope of the invention.
The raw materials used in the following examples are all generally commercially available.
Example 1
Experiments were performed on the continuous synthesis system of glyphosate depicted in figure 2:
synthesizing glyphosate synthetic solution in a synthesis kettle:
the raw materials comprise: 5200 parts by weight of methanol, 1630 parts by weight of triethylamine, 950 parts by weight of paraformaldehyde, 1200 parts by weight of glycine and 2060 parts by weight of dimethyl phosphite.
a1 Depolymerizing methanol, triethylamine and paraformaldehyde at 45 ℃;
a2 Carrying out addition reaction on the depolymerization reaction product and glycine at 50 ℃;
a3 And (3) carrying out condensation reaction on the product obtained after the addition reaction and dialkyl phosphite at 50 ℃ to obtain a synthetic solution.
The synthesis solution and hydrochloric acid were mixed in a first mixing device (static mixer) and acidified at 50℃and at a pressure of 0KPa. After acidification is complete, cool to 40 ℃ in an acidification cooler. The cooled acidizing fluid enters a first-stage hydrolysis reaction tower and a first-stage hydrolysis kettle to carry out a first-stage hydrolysis reaction, wherein the temperature of the first-stage hydrolysis reaction is 108 ℃, and the pressure is 10KPa. And carrying out secondary hydrolysis reaction on the product solution of the primary hydrolysis reaction in a secondary hydrolysis kettle, wherein the temperature of the secondary hydrolysis reaction is 120 ℃, and the pressure is-5 KPa.
The pH value of the slurry after the secondary hydrolysis reaction is regulated to be 0.1 in a buffer tank, the slurry enters a primary crystallizer, primary crystallization is carried out under the vacuum degree of 0.084MPa and the temperature of 64 ℃, the slurry after the primary crystallization enters the secondary crystallizer, secondary crystallization is carried out under the vacuum degree of 0.090MPa and the temperature of 49 ℃, the slurry after the secondary crystallization enters a tertiary crystallizer, tertiary crystallization is carried out under the vacuum degree of 0.097MPa and the temperature of 32 ℃, and the product after the tertiary crystallization is centrifugally dried, thus obtaining the glyphosate. The yield of glyphosate was 74% and the purity was 97% as measured. The gas obtained by crystallization at each stage is condensed to 40 ℃ by circulating water, the obtained condensate is collected to a condensate tank and can be conveyed to a dilute methanol storage tank by a pump, and the non-condensable gas is discharged after being buffered by a primary vacuum buffer tank.
And carrying out vacuum cooling on the gas after the secondary hydrolysis reaction in a hydrolysis tail gas condenser, wherein the pressure of the vacuum cooling is-60 KPa. The gas discharged from the hydrolysis tail gas condenser (comprising methanol, methylal, chloromethane, water and hydrogen chloride), the gas discharged from the primary hydrolysis reaction tower (comprising methanol, methylal, chloromethane, water and hydrogen chloride) and the gas discharged from the static mixer enter an alkaline washing tower, and are subjected to neutralization reaction with 5% sodium hydroxide solution in the alkaline washing tower, wherein the neutralization reaction temperature is 74 ℃, and the pressure is 0KPa.
And (3) mixing the solution after the neutralization reaction with condensate (condensate refers to condensate obtained by condensing gas after the secondary hydrolysis reaction), and then stripping in a stripping tower, wherein the temperature of the stripping tower kettle is 103 ℃, and the stripping pressure is 5KPa. The gas (including methanol and water) separated from the top of the stripping tower and the gas discharged from the top of the alkaline washing tower enter a separating tower for first rectifying separation, the temperature of the bottom of the separating tower is 76 ℃, the pressure of the top of the separating tower is 5KPa, and the reflux ratio of the top of the separating tower is 2.2: and 1, feeding the wastewater at the bottom of the stripping tower into a wastewater treatment device.
The gas (comprising methanol, methylal and chloromethane) distilled from the top of the separation tower enters a chloromethane removal tower to recycle chloromethane, the temperature of the top of the chloromethane removal tower is-14 ℃, the pressure of the top of the chloromethane removal tower is 55KPa, and the reflux ratio is 1.5:1, a step of; feeding the tower bottom liquid of the dechlorination methane tower into a methylal tower, recovering methylal, wherein the temperature of the tower bottom of the methylal tower is 73 ℃, the pressure is 20KPa, and the reflux ratio is 1:1.
The components at the bottom of the separation tower sequentially enter a low-pressure methanol tower and a high-pressure methanol tower to recycle methanol, the pressure of the low-pressure methanol tower is 0.18MPa, the temperature of a tower kettle is 107 ℃, and the reflux ratio is 1.5:1, the pressure of the high-pressure methanol tower is 0.6MPa, the temperature of the tower kettle is 155 ℃, and the reflux ratio is 2.5:1. and the liquid after rectification of the high-pressure methanol tower flows back to the stripping tower.
The detection shows that the recovery rate of the chloromethane is more than 99 percent, the purity (without air) is about 97.5 percent, and the dimethyl ether is about 2.5 percent; recovery rate of methylal is >99%, purity is >85%; the recovery rate of the methanol is more than 99 percent, and the purity is more than 99.5 percent; 260kg of methanol is consumed per ton of glyphosate, 5.6t of steam is consumed per ton of glyphosate, and 55kg of sulfuric acid is consumed per ton of chloromethane.
Example 2
Experiments were performed on the continuous synthesis system of glyphosate depicted in figure 2:
synthesizing glyphosate synthetic solution in a synthesis kettle:
the raw materials comprise: 5400 parts by weight of methanol, 1650 parts by weight of triethylamine, 950 parts by weight of paraformaldehyde, 1250 parts by weight of glycine and 2100 parts by weight of dimethyl phosphite.
a1 Depolymerizing methanol, triethylamine and paraformaldehyde at 50 ℃;
a2 Carrying out addition reaction on the depolymerization reaction product and glycine at 45 ℃;
a3 And (3) carrying out condensation reaction on the product obtained after the addition reaction and dialkyl phosphite at 45 ℃ to obtain a synthetic solution.
The synthesis solution and hydrochloric acid were mixed in a first mixing device (static mixer) and acidified at a temperature of 40℃and a pressure of 5KPa. After acidification is complete, it is cooled to 30 ℃ in an acidification cooler. The cooled acidizing fluid enters a first-stage hydrolysis reaction tower and a first-stage hydrolysis kettle to carry out a first-stage hydrolysis reaction, wherein the temperature of the first-stage hydrolysis reaction is 100 ℃, and the pressure is 5KPa. And carrying out secondary hydrolysis reaction on the product solution of the primary hydrolysis reaction in a secondary hydrolysis kettle, wherein the temperature of the secondary hydrolysis reaction is 115 ℃, and the pressure is-5 KPa.
And (3) regulating the pH value of the slurry after the secondary hydrolysis reaction to be 2 in a buffer tank, entering a primary crystallizer, carrying out primary crystallization at the vacuum degree of 0.088MPa and the temperature of 55 ℃, entering a secondary crystallizer, carrying out secondary crystallization at the vacuum degree of 0.096MPa and the temperature of 42 ℃, entering a tertiary crystallizer, carrying out tertiary crystallization at the vacuum degree of 0.101MPa and the temperature of 28 ℃, and centrifugally drying the product after the tertiary crystallization to obtain the glyphosate. The yield of the glyphosate is 76% and the purity is 95% through detection. The gas obtained by crystallization at each stage is condensed to 40 ℃ by circulating water, the obtained condensate is collected to a condensate tank and can be conveyed to a dilute methanol storage tank by a pump, and the non-condensable gas is discharged after being buffered by a primary vacuum buffer tank.
And carrying out vacuum cooling on the gas after the secondary hydrolysis reaction in a hydrolysis tail gas condenser, wherein the pressure of the vacuum cooling is-60 KPa. The gas discharged from the hydrolysis tail gas condenser (comprising methanol, methylal, chloromethane, water and hydrogen chloride), the gas discharged from the primary hydrolysis reaction tower (comprising methanol, methylal, chloromethane, water and hydrogen chloride) and the gas discharged from the static mixer enter an alkaline washing tower, and are subjected to neutralization reaction with 5% sodium hydroxide solution in mass concentration in the alkaline washing tower, wherein the neutralization reaction temperature is 85 ℃, and the pressure is 5KPa.
And (3) mixing the solution after the neutralization reaction with condensate (condensate refers to condensate obtained by condensing gas after the secondary hydrolysis reaction), and then stripping in a stripping tower, wherein the temperature of the stripping tower kettle is 100 ℃, and the stripping pressure is 10KPa. The gas (including methanol and water) separated from the top of the stripping tower and the gas discharged from the top of the alkaline washing tower enter a separating tower for first rectifying separation, the temperature of the bottom of the separating tower is 65 ℃, the pressure of the top of the separating tower is 10KPa, and the reflux ratio of the top of the separating tower is 2.2: and 1, feeding the wastewater at the bottom of the stripping tower into a wastewater treatment device.
The gas (comprising methanol, methylal and chloromethane) distilled from the top of the separation tower enters a chloromethane removal tower to recycle chloromethane, the temperature of the top of the chloromethane removal tower is minus 17 ℃, the pressure of the top of the chloromethane removal tower is 40KPa, and the reflux ratio is 1.5:1, a step of; feeding the tower bottom liquid of the dechlorination methane tower into a methylal tower, recovering methylal, wherein the temperature of the tower bottom of the methylal tower is 80 ℃, the pressure is 10KPa, and the reflux ratio is 1:1.
The components at the bottom of the separation tower sequentially enter a low-pressure methanol tower and a high-pressure methanol tower to recycle methanol, the pressure of the low-pressure methanol tower is 0.1MPa, the temperature of a tower kettle is 115 ℃, and the reflux ratio is 1.5:1, the pressure of the high-pressure methanol tower is 0.7MPa, the temperature of the tower kettle is 155 ℃, and the reflux ratio is 2.5:1. and the liquid after rectification of the high-pressure methanol tower flows back to the stripping tower.
The detection shows that the recovery rate of the chloromethane is more than 99 percent, the purity (without air) is about 97.5 percent, and the dimethyl ether is about 2.5 percent; recovery rate of methylal is >99%, purity is >85%; the recovery rate of the methanol is more than 99 percent, and the purity is more than 99.5 percent; 265kg of methanol is consumed per ton of glyphosate, 5.5t of steam is consumed per ton of glyphosate, and 55kg of sulfuric acid is consumed per ton of chloromethane.
Comparative example 1
Synthesizing glyphosate synthetic solution in a synthesis kettle:
the raw materials comprise: 5200 parts by weight of methanol, 1630 parts by weight of triethylamine, 950 parts by weight of paraformaldehyde, 1200 parts by weight of glycine and 2060 parts by weight of dimethyl phosphite.
a1 Depolymerizing methanol, triethylamine and paraformaldehyde at 45 ℃;
a2 Carrying out addition reaction on the depolymerization reaction product and glycine at 50 ℃;
a3 And (3) carrying out condensation reaction on the product obtained after the addition reaction and dialkyl phosphite at 50 ℃ to obtain a synthetic solution.
The synthetic liquid and the hydrochloric acid are respectively measured in a measuring tank, then are sequentially put into a hydrolysis kettle, are stirred and slowly heated, are subjected to hydrolysis reaction (intermittent reaction), gas phases generated by the reaction are condensed in a first stage, a second stage and a third stage, condensate is collected into a dilute methanol tank, and noncondensable gas (crude chloromethane) is conveyed to a chloromethane recovery device by a fan. The end temperature of the hydrolysis reaction is controlled between 110 ℃ and 135 ℃ and the system pressure is controlled between 5KPa and 5KPa below zero.
After the neutralization reaction of dilute methanol and 40% liquid caustic soda by mass concentration in a static mixer, preheating to 60-80 ℃ by using recovered methanol and steam condensate water, then rectifying by feeding gas-liquid two phases into a partition wall tower, controlling the temperature of the top of the methylal side at 42 ℃ and normal pressure, controlling the reflux ratio at 5, condensing the gas phase extracted from the top of the tower to obtain methylal product, and removing chloromethane from non-condensable gas (crude chloromethane); the temperature of the top of the tower at the methanol side is controlled at 64 ℃, the normal pressure, the reflux ratio is 1.5, the methanol product is extracted from the top of the tower, and the mixture of the methanol and the water is extracted from the middle lower side of the tower to a high-pressure methanol tower; the waste water at the tower kettle is subjected to heat exchange and then goes to an environmental protection station; the temperature of the top of the high-pressure methanol tower is controlled to 120 ℃, the pressure is controlled to 0.55MPa, the reflux ratio is 3.5, the gas phase at the top of the tower is used as a heat source for a partition wall tower, condensate is methanol product, and the waste water at the tower bottom is subjected to heat exchange and then goes to an environmental protection station.
The recovery rate of methanol in the process is more than 98%, the purity is more than 99.5%, 330kg of methanol is consumed per ton of glyphosate, 7.3t of steam is consumed per ton of glyphosate, and 130kg of sulfuric acid is consumed per ton of chloromethane.
The mass comparison results of methyl chloride and methylal obtained in examples 1 to 2 and comparative example 1 are shown in tables 1 and 2:
table 1 comparison of the quality of chloromethane obtained in examples 1 and 2 and comparative example 1
Chloromethane Dimethyl ether Methylal (methylal) Methanol Water and its preparation method
Example 1 97.5 2.5 Not detected Not detected Not detected
Implementation of the embodimentsExample 2 97.5 2.5 Not detected Not detected Not detected
Comparative example 1 93.3 2.5 2.5 1.5 0.2
Table 2 comparative mass results of methylal obtained in examples 1 to 2 and comparative example 1
Chloromethane Methylal (methylal) Methanol Water and its preparation method
Example 1 <0.1 85 14.8 0.1
Example 2 <0.1 86 13.8 0.1
Comparative example 1 ≈3 85 11.9 0.1
The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core ideas. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. A continuous synthesis method of glyphosate comprises the following steps:
a) Under the action of triethylamine, glycine, paraformaldehyde and dialkyl phosphite are reacted in methanol, and the reacted synthetic solution is acidified to obtain acidified solution;
b) Carrying out primary hydrolysis reaction on the acidizing fluid at the temperature of 90-112 ℃ and the pressure of-5-20 KPa;
c) Carrying out secondary hydrolysis reaction on the product solution of the primary hydrolysis reaction at 115-130 ℃ and-10 KPa, crystallizing slurry after the secondary hydrolysis reaction to obtain glyphosate, and condensing gas after the secondary hydrolysis reaction to obtain condensate and non-condensable gas;
mixing the gas generated by the primary hydrolysis reaction, the non-condensable gas and alkali liquor, and carrying out neutralization reaction;
d) Mixing the solution after the neutralization reaction with condensate, and then carrying out steam stripping, wherein the gas obtained by steam stripping and the gas obtained by the neutralization reaction are subjected to first rectification at-10 KPa and a tower bottom temperature of 65-85 ℃, and the tower bottom liquid obtained by the first rectification is subjected to second rectification at 0.1-0.8 MPa and a tower bottom temperature of 85-170 ℃ to obtain methanol; performing third rectification on the tower top low-boiling-point substances obtained by the first rectification at the temperature of 0-80 KPa, the temperature of a tower bottom of 55-70 ℃ and the temperature of the tower top of-10 to-20 ℃ to obtain chloromethane; and (3) carrying out fourth rectification on the tower bottom liquid obtained by the third rectification at the temperature of 0-30 KPa and the temperature of 65-85 ℃ to obtain methylal.
2. The continuous synthesis process according to claim 1, wherein in step a), the reaction comprises:
a1 Carrying out depolymerization reaction on methanol, triethylamine and paraformaldehyde at 40-55 ℃;
a2 Carrying out addition reaction on the depolymerization reaction product and glycine at 40-55 ℃;
a3 And (3) carrying out condensation reaction on the product obtained after the addition reaction and dialkyl phosphite at the temperature of 40-55 ℃ to obtain a synthetic solution.
3. The continuous synthesis method according to claim 1, wherein in the step a), the acidification temperature is 35-55 ℃, and the acidification pressure is-10 kpa.
4. The continuous synthesis method according to claim 1, wherein in the step C), the pH value of the slurry after the secondary hydrolysis reaction is 0.1 to 3;
the crystallization includes:
first performing primary crystallization under the vacuum degree of 0.083-0.093 MPa and the temperature of 55-65 ℃;
performing secondary crystallization at the vacuum degree of 0.090-0.096 MPa and the temperature of 42-49 ℃;
then performing tertiary crystallization at 28-32 ℃ under the vacuum degree of 0.097-0.101 MPa;
the condensation is vacuum cooling, and the pressure of the vacuum cooling is more than or equal to-70 KPa; or the condensation is water adding cooling or heat exchanger cooling, and the temperature after water adding cooling is 30-90 ℃.
5. The continuous synthesis method according to claim 1, wherein in the step C), the neutralization reaction is performed at a temperature of 70 to 90 ℃ and a pressure of-5 to 10kpa.
6. The continuous synthesis method according to claim 1, wherein in the step D), the temperature of the stripping tower kettle is 100-108 ℃, and the stripping pressure is-5-30 kpa;
the reflux ratio of the first rectification is 1-4: 1, a step of; the reflux ratio of the second rectification is 1-4: 1, a step of; the reflux ratio of the third rectification is 1-3.5: 1, a step of; the reflux ratio of the fourth rectification is 0.5-2: 1.
7. the continuous synthesis process according to claim 1, wherein in step D), the second rectification comprises a low pressure methanol rectification and a high pressure methanol rectification;
the pressure of the low-pressure methanol rectification is 0.1-0.3 MPa, the temperature of a tower kettle is 85-120 ℃, and the reflux ratio is 1-4: 1, a step of;
the pressure of the high-pressure methanol rectification is 0.4-0.8 MPa, the temperature of a tower kettle is 135-170 ℃, and the reflux ratio is 1-4: 1.
8. a continuous synthesis system for use in the continuous synthesis method of glyphosate according to any one of claims 1 to 7, comprising:
a synthesis kettle;
the first mixing device is connected with the synthesis liquid outlet of the synthesis kettle;
The primary hydrolysis reaction device is connected with the acidification liquid outlet of the first mixing device;
the secondary hydrolysis reaction device is connected with a product solution outlet of the primary hydrolysis reaction device;
a crystallizer connected with a slurry outlet of the secondary hydrolysis reaction device;
a hydrolysis tail gas condenser connected with a gas outlet of the secondary hydrolysis reaction device;
the first gas inlet is connected with the gas outlet of the hydrolysis tail gas condenser; the second gas inlet of the alkaline washing tower is connected with the gas outlet of the first mixing device; the third gas inlet of the alkaline washing tower is connected with the gas outlet of the primary hydrolysis reaction device;
the first liquid inlet is connected with the liquid outlet of the alkaline washing tower; the second liquid inlet of the second mixing device is connected with the liquid outlet of the hydrolysis tail gas condenser;
a stripping column with a first liquid inlet connected with a liquid outlet of the second mixing device;
the first gas inlet is connected with the gas outlet of the alkaline washing tower; the second gas inlet of the separation tower is connected with the gas outlet of the stripping tower;
a methanol column connected to the liquid outlet of the separation column;
A dechlorination methane column connected to the gas outlet of the separation column;
and the methylal tower is connected with the liquid outlet of the dechlorination methane tower.
9. The continuous synthesis system according to claim 8, wherein the primary hydrolysis reaction apparatus comprises a primary hydrolysis reaction column and a primary hydrolysis reaction kettle;
the product solution outlet of the primary hydrolysis reaction tower is connected with the product solution inlet of the primary hydrolysis reaction kettle;
the gas outlet of the primary hydrolysis reaction kettle is connected with the gas inlet of the primary hydrolysis reaction tower;
the secondary hydrolysis reaction device comprises a secondary hydrolysis reaction kettle;
and a product solution inlet of the secondary hydrolysis reaction kettle is connected with a product solution outlet of the primary hydrolysis reaction kettle.
10. The continuous synthesis system according to claim 8, wherein the methanol column comprises a low pressure methanol column and a high pressure methanol column;
the liquid inlet of the low-pressure methanol tower is connected with the liquid outlet of the separation tower;
the liquid inlet of the high-pressure methanol tower is connected with the liquid outlet of the low-pressure methanol tower;
the liquid outlet of the high-pressure methanol tower is connected with the second liquid phase inlet of the stripping tower.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1939927A (en) * 2006-09-19 2007-04-04 浙江新安化工集团股份有限公司 Continuous synthesis of glyphosate by dimethyl ester
CN102757462A (en) * 2012-07-30 2012-10-31 浙江金帆达生化股份有限公司 Continuous production method of glyphosate crystal
CN103736384A (en) * 2014-01-27 2014-04-23 山东潍坊润丰化工股份有限公司 Treatment process of glyphosate hydrolyzing tail gas
CN103752158A (en) * 2014-01-27 2014-04-30 山东潍坊润丰化工股份有限公司 Method for treating glyphosate hydrolyzing tail gas
CN108404637A (en) * 2018-04-20 2018-08-17 湖北泰盛化工有限公司 A kind of alkyl esterification method glyphosate hydrolyzing tail gas reclaimer and technique
CN211814218U (en) * 2020-03-16 2020-10-30 浙江新安化工集团股份有限公司 Continuous synthesis system of glyphosate

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101786938A (en) * 2010-03-15 2010-07-28 衡阳莱德生物药业有限公司 Method for recycling chloromethane during production of glyphosate by using glycine method

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1939927A (en) * 2006-09-19 2007-04-04 浙江新安化工集团股份有限公司 Continuous synthesis of glyphosate by dimethyl ester
CN102757462A (en) * 2012-07-30 2012-10-31 浙江金帆达生化股份有限公司 Continuous production method of glyphosate crystal
CN103736384A (en) * 2014-01-27 2014-04-23 山东潍坊润丰化工股份有限公司 Treatment process of glyphosate hydrolyzing tail gas
CN103752158A (en) * 2014-01-27 2014-04-30 山东潍坊润丰化工股份有限公司 Method for treating glyphosate hydrolyzing tail gas
CN108404637A (en) * 2018-04-20 2018-08-17 湖北泰盛化工有限公司 A kind of alkyl esterification method glyphosate hydrolyzing tail gas reclaimer and technique
CN211814218U (en) * 2020-03-16 2020-10-30 浙江新安化工集团股份有限公司 Continuous synthesis system of glyphosate

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