CN211753889U - Recovery system of tail gas is hydrolysised to glyphosate synthetic liquid - Google Patents
Recovery system of tail gas is hydrolysised to glyphosate synthetic liquid Download PDFInfo
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- CN211753889U CN211753889U CN202020324082.6U CN202020324082U CN211753889U CN 211753889 U CN211753889 U CN 211753889U CN 202020324082 U CN202020324082 U CN 202020324082U CN 211753889 U CN211753889 U CN 211753889U
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Abstract
The utility model relates to a glyphosate production technical field especially relates to a recovery system of tail gas is hydrolysised to glyphosate synthetic liquid, include: a hydrolysis reaction device; the first gas inlet is connected with the gas outlet of the hydrolysis reaction device; the first liquid inlet is connected with the liquid outlet of the alkaline tower; 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 methane-removing column connected to the gas outlet of the separation column; and the formaldehyde condensation tower is connected with a liquid outlet of the methane-removing tower. The utility model provides a recovery system simple process of glyphosate synthetic fluid hydrolysis tail gas can effectively retrieve the accessory substance, and the cost is lower.
Description
Technical Field
The utility model relates to a glyphosate production technical field especially relates to a recovery system of tail gas is hydrolysised to glyphosate synthetic liquid.
Background
Glyphosate is a highly effective, low toxicity, broad spectrum, biocidal, non-selective herbicide with excellent biological properties. At present, the domestic main stream production process of 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 in America. The glyphosate in China is mainly produced by an alkyl ester method taking glycine and dimethyl phosphite as main raw materials, the method takes methanol as a reaction solvent, the glycine firstly reacts with polyformaldehyde in the presence of a catalyst triethylamine to form N, N-dimethylolglycine, then the N, N-dimethylolglycine reacts with dimethyl phosphite, and hydrochloric acid is added to hydrolyze the N, N-dimethylolglycine to generate the glyphosate and byproducts methylal and methyl chloride. The main components of the tail gas generated by hydrolyzing the glyphosate synthetic liquid by the glycine method are a mixture of water, methylal, methanol, hydrogen chloride and chloromethane, and the recovery process of the tail gas is referred to as solvent recovery in the glyphosate industry. The synthetic solution is a mixed solution of an organophosphorus intermediate (glyphosate precursor) such as N-methoxyalkyl ester methylglycine as a main component, which is obtained by depolymerizing, condensing and esterifying raw materials such as methanol, paraformaldehyde (or other formaldehyde sources), glycine (or other raw materials starting from chloroacetic acid), dimethyl phosphite (or other alkyl phosphates).
The existing glyphosate hydrolysis process is intermittent hydrolysis, after a synthetic solution and hydrochloric acid in a certain proportion are mixed in a hydrolysis kettle, steam is introduced to raise the temperature to the reaction end point, the hydrolysis reaction is carried out along with the raising of the hydrolysis temperature, the steam of methylal, methanol, chloromethane, water, hydrogen chloride and the like is evaporated out from the reaction kettle, three-stage condensation is carried out, the non-condensable gas of crude chloromethane (containing air and acidity) is treated by a chloromethane recovery device, and a condensate (diluted methanol) is treated by a solvent recovery device.
Patent CN103739625B discloses a continuous hydrolysis process for preparing glyphosate by a glycine method, which comprises the steps of separating gas from liquid of mixed acid, respectively feeding the liquid and the condensed gas into a methylal tower to recover methylal, feeding kettle bottom liquid recovered from the methylal into a methanol recovery tower to recover methanol, and feeding kettle bottom liquid discharged from the methanol recovery tower into a hydrolysis kettle to complete hydrolysis reaction. The method has the advantages of low recovery rate of methylal and high energy consumption.
The traditional recovery process is to condense hydrolysis steam, wherein methanol, methylal, water and a small amount of hydrogen chloride gas with relatively high boiling points are condensed into a liquid phase, which is called dilute methanol; the chloromethane is in gas phase, and is purified by water washing, alkali washing and sulfuric acid drying to obtain chloromethane gas, and the chloromethane product is obtained by compression and condensation. Adding alkali into the condensed dilute methanol for neutralization, respectively recovering methanol and methylal in the dilute methanol by two rectifying towers, recycling the methanol as a solvent to a glyphosate synthesis link, and taking the methylal as a byproduct.
Patent CN108380029A discloses a system and a process for recovering glyphosate solvent by alkyl ester method, the tail gas of glyphosate hydrolysis is sent to a condenser for condensation and separation after neutralization, pressure control and temperature control, the condensate is sent to a diluted methanol solution recovery tank, and the non-condensable gas is sent to a methyl chloride recovery device.
SUMMERY OF THE UTILITY MODEL
In view of this, the to-be-solved technical problem of the utility model lies in providing a recovery system of glyphosate synthetic fluid hydrolysis tail gas, the utility model provides a recovery system of glyphosate synthetic fluid hydrolysis tail gas simple process can effectively retrieve the accessory substance, and the cost is lower.
The utility model provides a recovery system of tail gas is hydrolysised to glyphosate synthetic liquid, include:
a hydrolysis reaction device;
the first gas inlet is connected with the gas outlet of the hydrolysis reaction device;
the first liquid inlet is connected with the liquid outlet of the alkaline tower;
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 methane-removing column connected to the gas outlet of the separation column;
and the formaldehyde condensation tower is connected with a liquid outlet of the methane-removing tower.
Preferably, the hydrolysis reaction device comprises a hydrolysis reaction tower and a hydrolysis reaction kettle;
a product solution outlet of the hydrolysis reaction tower is connected with a product solution inlet of the hydrolysis reaction kettle; and a gas outlet of the hydrolysis reaction kettle is connected with a gas inlet of the hydrolysis reaction tower.
Preferably, the hydrolysis reaction device comprises 1 hydrolysis reaction tower and 1 hydrolysis reaction kettle.
Preferably, the recovery system further comprises a hydrolysis reboiler;
the hydrolysis reboiler is used for heating the hydrolysis reaction kettle.
Preferably, the methanol tower comprises a low pressure methanol tower and a high pressure methanol tower;
the liquid phase inlet of the low-pressure methanol tower is connected with the liquid outlet of the separation tower;
and the liquid phase inlet of the high-pressure methanol tower is connected with the liquid outlet of the low-pressure methanol tower.
Preferably, the liquid outlet of the high-pressure methanol column is connected with the second liquid inlet of the stripping column.
The utility model provides a recovery system of tail gas is hydrolysised to glyphosate synthetic liquid, include: a hydrolysis reaction device; the first gas inlet is connected with the gas outlet of the hydrolysis reaction device; the first liquid inlet is connected with the liquid outlet of the alkaline tower; 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 methane-removing column connected to the gas outlet of the separation column; and the formaldehyde condensation tower is connected with a liquid outlet of the methane-removing tower. The utility model provides a recovery system simple process of glyphosate synthetic fluid hydrolysis tail gas can effectively retrieve the accessory substance, and the cost is lower.
Drawings
Fig. 1 is a schematic flow chart of a recovery system for hydrolysis tail gas of glyphosate synthetic fluid according to an embodiment of the present invention;
fig. 2 is a schematic flow chart of a recovery system of glyphosate synthesis solution hydrolysis tail gas according to another embodiment of the present invention.
Detailed Description
The technical solution of the present invention will be described clearly and completely below with reference to the embodiments of the present invention, and it should be understood that the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments in the present invention, all other embodiments obtained by a person skilled in the art without creative work belong to the protection scope of the present invention.
The utility model provides a recovery system of tail gas is hydrolysised to glyphosate synthetic liquid, include:
a hydrolysis reaction device;
the first gas inlet is connected with the gas outlet of the hydrolysis reaction device;
the first liquid inlet is connected with the liquid outlet of the alkaline tower;
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 methane-removing column connected to the gas outlet of the separation column;
and the formaldehyde condensation tower is connected with a liquid outlet of the methane-removing tower.
See fig. 1. Fig. 1 is a schematic flow chart of a recovery system for hydrolysis tail gas of glyphosate synthetic fluid according to an embodiment of the present invention.
In some embodiments of the present invention, the recovery system of the glyphosate synthetic fluid hydrolysis tail gas further comprises a synthesis kettle. The synthesis kettle is used for synthesizing glyphosate synthesis liquid. In the embodiment of the utility model, the synthesis cauldron is provided with raw materials import and synthetic liquid export. The utility model discloses it is right the structure of synthetic cauldron does not have special restriction, can be conventional synthetic cauldron.
In certain embodiments of the present invention, the recovery system for the hydrolysis tail gas of glyphosate synthetic fluid further comprises an acidification device. In certain embodiments of the present invention, the acidification device is provided with a mixed liquid inlet, an acidulant inlet, an acidification liquid outlet, and a gas outlet. In certain embodiments of the present invention, the mixed liquid inlet of the acidification device is connected to the mixed liquid outlet of the synthesis kettle. The acidizing device is used for acidizing the synthetic fluid. In certain embodiments of the present invention, the acidification device is a tubular static mixer, model SK, SV or SX, preferably SK.
In certain embodiments of the present invention, the synthetic fluid discharged from the synthetic fluid outlet of the synthesis kettle enters the acidification device through the synthetic fluid delivery pump. The utility model discloses it is right the structure of synthetic liquid delivery pump does not have special restriction, can be conventional centrifugal pump.
The utility model provides a recovery system of glyphosate synthetic fluid hydrolysis tail gas includes hydrolysis reaction unit. The hydrolysis reaction device is used for hydrolyzing the acidizing fluid and simultaneously separating light components such as methanol, methylal, methyl chloride and the like from the hydrolysis fluid. In certain embodiments of the present invention, the acidification liquid inlet of the hydrolysis reaction device is connected to the acidification liquid outlet of the acidification device. In certain embodiments of the present invention, the hydrolysis reaction device comprises a hydrolysis reaction tower and a hydrolysis reaction kettle. See fig. 2. Fig. 2 is a schematic flow chart of a recovery system of glyphosate synthesis solution hydrolysis tail gas according to another embodiment of the present invention. In certain embodiments of the present invention, the hydrolysis reaction apparatus comprises 1 hydrolysis reaction tower and 1 hydrolysis reaction kettle.
In certain embodiments of the present invention, the hydrolysis reaction tower is provided with an acidification liquid inlet, a product solution outlet, a gas outlet, and a gas inlet. And an acidizing fluid inlet of the hydrolysis reaction tower is connected with an acidizing fluid outlet of the acidizing device.
In certain embodiments of the present invention, the hydrolysis reactor is provided with a product solution inlet, a product solution outlet, and a gas outlet. And a product solution inlet of the hydrolysis reaction tower is connected with an acidizing fluid outlet of the acidizing device. And a product solution outlet of the hydrolysis reaction tower is connected with a product solution inlet of the hydrolysis reaction kettle. And a gas outlet of the hydrolysis reaction kettle is connected with a gas inlet of the hydrolysis reaction tower. And returning the gas discharged from the hydrolysis reaction kettle to the hydrolysis reaction tower.
The utility model discloses it is right hydrolysis reaction tower and hydrolysis reaction cauldron's structure does not have special restriction. In certain embodiments of the present invention, the hydrolysis reaction tower is a corrosion-resistant packed tower. In certain embodiments, the 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 present invention, the hydrolysis reactor is an open glass lined reactor.
In certain embodiments of the present invention, the recovery system for the hydrolysis tail gas of the glyphosate synthetic fluid further comprises a hydrolysis reboiler. The hydrolysis reboiler is used for heating the hydrolysis reaction kettle. The utility model discloses it is right hydrolysis reboiler's connected mode does not have special restriction, can realize hydrolysis reaction cauldron the heating can. The utility model discloses it is right the structure of hydrolysis reboiler does not have special restriction the utility model discloses an in some embodiments, the hydrolysis reboiler is round block cellular type graphite heat exchanger.
In certain embodiments of the present invention, the system for recovering the tail gas from the hydrolysis of the glyphosate synthetic fluid further comprises an acidification cooler. The acidification cooler is used for cooling the acidification liquid. And an acidizing fluid inlet of the acidizing cooler is connected with an acidizing fluid outlet of the mixing device, and an acidizing fluid outlet of the acidizing cooler is connected with an acidizing fluid inlet of the hydrolysis reaction tower. The utility model discloses it is right the structure of acidizing fluid cooler does not have special restriction the utility model discloses an in some embodiments, follow mixing arrangement's acidizing fluid outlet exhaust acidizing fluid passes through the acidizing fluid pump and gets into the acidizing cooler. The utility model discloses it is right the structure of acidizing fluid pump does not have special restriction, can be conventional centrifugal pump or magnetic drive pump.
The utility model provides a recovery system of glyphosate synthetic liquid tail gas of hydrolysising still include with the caustic wash tower that hydrolysis reaction unit's gas outlet links to each other. The hydrolysis tail gas is acid gas, and the acid and alkali in the alkaline washing tower neutralize the acid and alkali, so that the range of equipment material selection of the rear system is wide, and the cost is lower. The alkaline tower is provided with a first gas inlet, a second gas inlet, a liquid outlet and a gas outlet. And a first gas inlet of the alkaline tower is connected with a gas outlet of the hydrolysis reaction device. In certain embodiments of the present invention, the second gas inlet of the caustic tower is connected to the gas outlet of the acidifying device. The utility model discloses it is right the structure of caustic wash tower does not have special restriction, in the certain embodiments of the utility model, the caustic wash tower can be for the packed tower.
The utility model provides a recovery system of glyphosate synthetic liquid tail gas of hydrolysising still include with the strip tower that the liquid outlet of alkali wash tower links to each other. In certain embodiments of the present invention, the stripper is provided with a first liquid inlet, a second liquid inlet, a gas outlet, and a liquid outlet. And a first liquid inlet of the stripping tower is connected with a liquid outlet of the alkaline washing tower. The utility model discloses it is right the structure of strip tower does not have special restriction, can be conventional strip tower.
The utility model provides a recovery system of glyphosate synthetic liquid tail gas of hydrolysising still include with the knockout tower that the gas outlet of caustic wash tower links to each other. The separation tower is used for carrying out the first rectification, and the tower kettle diluted methanol and the tower top low-boiling-point substance can be obtained through the first rectification. In certain embodiments of the present 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 present invention, the first gas inlet of the separation tower is connected to the gas outlet of the caustic tower, and the second gas inlet of the separation tower is connected to the gas outlet of the stripping tower. The utility model discloses it does not have special restriction to be right the structure of knockout tower, in the certain embodiments of the utility model, the knockout tower can be conventional filler rectifying column.
The utility model provides a recovery system of glyphosate synthetic liquid tail gas of hydrolysising still include with the methanol tower that the liquid outlet of knockout tower links to each other. And the dilute methanol in the tower kettle in the separation tower is discharged from a liquid outlet of the separation tower and enters a methanol tower. In certain embodiments of the present invention, the methanol column is provided with a liquid inlet and a liquid outlet. And the liquid inlet of the methanol tower is connected with the liquid outlet of the separation tower. The utility model discloses it is right the structure of methanol tower does not have special restriction the utility model discloses an in some embodiments, the methanol tower can be conventional filler rectifying column.
In certain embodiments of the present invention, the methanol tower comprises a low pressure methanol tower and a high pressure methanol tower. 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; and the liquid inlet of the high-pressure methanol tower is connected with the liquid outlet of the low-pressure methanol tower. And a liquid outlet of the high-pressure methanol tower is connected with a second liquid phase inlet of the stripping tower. The utility model discloses it is right the structure of low pressure methanol tower and high pressure methanol tower does not have special restriction. In certain embodiments of the present invention, the low pressure methanol column may be a conventional packed rectification column. In certain embodiments of the present invention, the high pressure methanol column can be a conventional packed rectification column.
The utility model provides a recovery system of glyphosate synthetic liquid tail gas of hydrolysising still include with the dechlorination methane tower that the gas outlet of knockout tower links to each other. The chloromethane is refined by rectification of a chloromethane removing tower, so that the post-system treatment cost is reduced, and simultaneously, the methanol and methylal are recovered, and the consumption of the methanol is reduced. In certain embodiments of the present invention, the methyl chloride removal column is provided with a gas inlet, a bottoms outlet, and a methyl chloride outlet. In certain embodiments of the present invention, the gas inlet of the demethanizer is connected to the gas outlet of the separation column. The utility model discloses it is right the structure of dechlorination methane tower does not have special restriction the utility model discloses an in some embodiments, the dechlorination methane tower can be conventional filler rectifying column.
The utility model provides a recovery system of glyphosate synthetic fluid tail gas of hydrolysising still include with the methylal tower that the liquid export of dechlorination methane tower links to each other. The methylal tower is used for recovering methylal and methanol. The formaldehyde column is provided with a liquid inlet and a gas outlet. And a liquid inlet of the formaldehyde condensation tower is connected with a tower bottom liquid outlet of the methane-removing tower. The utility model discloses it is right the structure of formaldehyde tower does not have special restriction, can be conventional filler rectifying column.
The utility model also provides a method for retrieve glyphosate synthetic fluid hydrolysis tail gas in recovery system above, including the following steps:
A) carrying out hydrolysis reaction on the acidified glyphosate synthetic solution at 120-130 ℃ and 70-100 KPa;
B) mixing gas generated by the hydrolysis reaction with alkali liquor to perform neutralization reaction;
C) carrying out steam stripping on the solution after the neutralization reaction, carrying out first rectification on gas obtained by the steam stripping and gas obtained by the neutralization reaction at-5-30 KPa and the temperature of a tower kettle of 65-85 ℃, and carrying out second rectification on tower kettle liquid obtained by the first rectification at 0.1-0.8 MPa and the temperature of the tower kettle 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 tower kettle temperature of 55-70 ℃ and the tower top temperature of-10-20 ℃ to obtain methyl chloride; and performing fourth rectification on the tower bottom liquid obtained by the third rectification at the temperature of 65-85 ℃ at 0-30 KPa to obtain methylal.
In certain embodiments of the present invention, the glyphosate synthesis solution is prepared according to the following method:
under the action of triethylamine, glycine, paraformaldehyde and dialkyl phosphite are reacted in methanol to obtain glyphosate synthetic solution.
Preferably, the method specifically comprises the following steps:
a1) carrying out depolymerization reaction on methanol, triethylamine and paraformaldehyde at 40-55 ℃;
a2) performing addition reaction on the product after the depolymerization reaction and glycine at the temperature of 40-55 ℃;
a3) and carrying out condensation reaction on the product after the addition reaction and dialkyl phosphite at the temperature of 40-55 ℃ to obtain synthetic liquid.
In certain embodiments of the present invention, the mass ratio of methanol, triethylamine and paraformaldehyde is 4750-5700: 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 present invention, the mass ratio of glycine to paraformaldehyde is 1045-1250: 950. in certain embodiments, the mass ratio of glycine to paraformaldehyde is 1200: 950 or 1250: 950. in certain embodiments of the present invention, the mass ratio of the dialkyl phosphite to the paraformaldehyde is 1995-2185: 950. in certain embodiments, the mass ratio of dialkyl phosphite to paraformaldehyde is 2060: 950 or 2100: 950. in certain embodiments of the present invention, the dialkyl phosphite is dimethyl phosphite.
In certain embodiments of the present invention, the temperature of the depolymerization reaction is 45 ℃ or 50 ℃. In certain embodiments of the present invention, the temperature of the addition reaction is 50 ℃ or 45 ℃. In certain embodiments of the present invention, the temperature of the condensation reaction is 50 ℃ or 45 ℃.
In certain embodiments of the present invention, the reaction in step a) is carried out in a synthesis kettle.
And after the synthetic solution is obtained, acidifying the synthetic solution to obtain acidified glyphosate synthetic solution.
In certain embodiments of the present invention, the acidifying agent used for the acidification is hydrochloric acid. In some embodiments of the present invention, the temperature of the acidification is 35 to 55 ℃, and the pressure of the acidification is-10 to 10 KPa. In some embodiments, the acidification temperature is 40-55 ℃, 50 ℃ or 40 ℃, and the acidification pressure is-5 KPa or 0KPa or 5 KPa.
In certain embodiments of the present invention, the acidification is performed in an acidification device.
And (3) after obtaining the acidified glyphosate synthetic solution, carrying out hydrolysis reaction on the acidified glyphosate synthetic solution at the temperature of 120-130 ℃ and under the pressure of 70-100 KPa.
The hydrolysis reaction in the recovery method of the glyphosate synthetic fluid hydrolysis tail gas provided by the utility model is a one-step hydrolysis reaction.
In certain embodiments of the present invention, the acidizing fluid further comprises, prior to performing the hydrolysis reaction: and cooling the acidizing fluid. In certain embodiments of the present invention, the temperature of the cooling is 15 to 30 ℃. In certain embodiments of the present invention, the cooling is performed in an acidification cooler.
In certain embodiments of the present invention, the hydrolysis reaction is carried out at a temperature of 128 ℃ or 120 ℃ and a pressure of 80KPa or 90 KPa. In certain embodiments of the present invention, the hydrolysis reaction is carried out in a hydrolysis reaction apparatus. In certain embodiments of the present invention, the slurry after the hydrolysis reaction is subjected to a subsequent crystallization process to prepare glyphosate.
And after the hydrolysis reaction is finished, mixing gas generated by the hydrolysis reaction with alkali liquor to perform a neutralization reaction. In some embodiments of the present invention, the gas generated by the acidification, the gas generated by the hydrolysis reaction and the alkali solution are mixed to perform a neutralization reaction. In certain embodiments of the present invention, the lye comprises a sodium hydroxide solution. In certain embodiments of the present invention, the concentration of the lye is not higher than 48% by mass, preferably not higher than 10% by mass, more preferably not higher than 5% by mass. In certain embodiments of the present invention, the gas produced by the hydrolysis reaction comprises methanol, methylal, methyl chloride, water, and hydrogen chloride.
In some embodiments of the present invention, the temperature of the neutralization reaction is 70 to 90 ℃ and the pressure is-5 to 10 KPa. In certain embodiments of the present invention, the temperature of the neutralization reaction is 74 ℃ or 85 ℃ and the pressure is 0KPa or 5 KPa.
In certain embodiments of the present invention, the neutralization is performed in a caustic tower.
After the neutralization reaction is completed, the solution after the neutralization reaction is subjected to steam stripping. In some embodiments of the present invention, the temperature of the stripped tower is 100-108 ℃, and the pressure of the stripping is-5-30 KPa. In some embodiments of the present invention, the temperature of the stripped tower is 100-105 ℃, 103 ℃ or 100 ℃, and the pressure of the stripping is 0-10 KPa, 5KPa or 10 KPa. In certain embodiments of the present invention, the stripping is performed in a stripper. In certain embodiments of the present invention, the stripped wastewater may enter a wastewater treatment plant.
The utility model discloses in, the gas that the strip obtained and the gas that neutralization reaction obtained carry out first rectification under-10 ~ 10KPa, tower cauldron temperature 65 ~ 85 ℃. In certain embodiments of the present invention, the stripping gas comprises methanol and water. In certain embodiments of the present invention, the pressure of the first rectification is 5KPa or 10KPa and the temperature is 65 ℃. In certain embodiments of the present invention, the reflux ratio of the first rectification is 1-4: 1. in certain embodiments, the reflux ratio of the first rectification is 2.2 to 2.3: 1 or 2.2: 1. in certain embodiments of the present invention, the first rectification is performed in a separation column. In certain embodiments of the present invention, the gas obtained by the first rectification comprises methanol, methylal and methyl chloride.
The utility model discloses in, the tower bottom liquid that first rectification obtained carries out the second rectification under 0.1 ~ 0.8MPa, tower bottom temperature 85 ~ 170 ℃ to obtain methyl alcohol. In certain embodiments of the present invention, the pressure of the second distillation is 0.5MPa, and the temperature of the column bottom of the second distillation is 150 ℃. In some embodiments of the present invention, the reflux ratio of the second rectification is 1-4: 1. in certain embodiments, the reflux ratio of the second rectification is 1.5 to 2.5: 1. in certain embodiments of the present invention, the second rectification is performed in a methanol column.
In certain embodiments of the present invention, the second rectification comprises low pressure methanol rectification and high pressure methanol rectification. In some embodiments of the present invention, the pressure of the low-pressure methanol distillation 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 a tower kettle is 107 ℃ or 115 ℃, and the reflux ratio is 1.5-2: 1 or 1.5: 1. in certain embodiments of the present invention, the low pressure methanol rectification is performed in a low pressure methanol column.
In some embodiments of the present invention, the pressure of the high pressure methanol distillation is 0.4-0.8 MPa, the temperature of the tower kettle is 135-170 ℃, and the reflux ratio is 1-4: 1. in some embodiments of the present invention, the pressure of the high pressure methanol distillation is 0.6MPa or 0.7MPa, the temperature of the column bottom is 150-165 ℃ or 155 ℃, and the reflux ratio is 2-2.5: 1 or 2.5: 1. in certain embodiments of the present invention, the high pressure methanol rectification is performed in a high pressure methanol column. In certain embodiments of the present invention, the liquid after the high pressure methanol rectification is refluxed to the stripping column.
The utility model discloses in, the top of the tower low boiling residue that first rectification obtained carries out the third rectification under 0 ~ 80KPa, tower cauldron temperature 55 ~ 70 ℃, top of the tower temperature-10 ~ 20 ℃, obtains methyl chloride. In some embodiments of the present invention, the pressure of the third distillation is 55KPa or 40KPa, the temperature of the column bottom is 60-65 ℃, the temperature of the column top is-14 to-17 ℃, -14 ℃ or-17 ℃. In some embodiments of the present invention, the reflux ratio of the third distillation is 1-3.5: 1. in certain embodiments, the reflux ratio of the third rectification is 1.2 to 1.5: 1 or 1.5: 1. in certain embodiments of the present invention, the third rectification is performed in a demethanizer.
And performing fourth rectification on the tower bottom liquid obtained by the third rectification at the temperature of 65-85 ℃ at 0-30 KPa to obtain methylal. In certain embodiments of the present invention, the pressure of the fourth distillation is 20KPa or 10KPa, and the temperature of the column bottom is 73 ℃ or 80 ℃. In some embodiments of the present invention, the reflux ratio of the fourth rectification is 0.5-2: 1. in certain embodiments, the fourth rectification has a reflux ratio of 1: 1. in certain embodiments of the present invention, the fourth rectification is performed in a formal column.
The utility model has no special limitation to the source of the raw materials adopted above, and can be sold in general markets.
The utility model provides a recovery system simple process of glyphosate synthetic fluid hydrolysis tail gas can effectively retrieve the accessory substance, and the cost is lower.
For further illustration of the present invention, the following detailed description will be made with reference to the examples for the recovery system of the tail gas from the hydrolysis of glyphosate synthetic fluid, but they should not be construed as limiting the scope of the present invention.
The starting materials used in the following examples are all generally commercially available.
Example 1
Experiments were conducted on the recovery system for the tail gas from the hydrolysis of glyphosate synthesis solution as described 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) Carrying out depolymerization reaction on methanol, triethylamine and paraformaldehyde at 45 ℃;
a2) performing addition reaction on the product after the depolymerization reaction and glycine at 50 ℃;
a3) and carrying out condensation reaction on the product after the addition reaction and dialkyl phosphite at 50 ℃ to obtain synthetic liquid.
The synthetic solution and hydrochloric acid were mixed in an acidification device (static mixer) and acidified at 50 ℃ under 0 KPa. After acidification is completed, the mixture is cooled in an acidification cooler. And (3) feeding the cooled acidified liquid into a hydrolysis reaction tower and a hydrolysis kettle for hydrolysis reaction, wherein the temperature of the hydrolysis reaction is 128 ℃, and the pressure is 80 KPa.
The gas discharged from the hydrolysis reaction tower (comprising methanol, methylal, methyl chloride, water and hydrogen chloride) and the gas discharged from the static mixer enter a caustic washing tower (the total flow of the gas in the caustic washing tower is 28 m)3And h), performing neutralization reaction with a sodium hydroxide solution with the mass concentration of 5% in an alkaline tower, wherein the temperature of the neutralization reaction is 74 ℃, and the pressure is 0 KPa.
And (3) stripping the solution after the neutralization reaction in a stripping tower, wherein the temperature of a kettle of the stripping tower is 103 ℃, and the stripping pressure is 5 KPa. And (2) introducing gas (comprising methanol and water) separated from the top of the stripping tower and gas discharged from the top of the alkaline washing tower into a separation tower for first rectification separation, wherein the tower kettle temperature of the separation tower is 76 ℃, the tower top pressure is 5KPa, and the tower top reflux ratio of the separation tower is 2.2: and 1, enabling the wastewater at the bottom of the stripping tower to enter a wastewater treatment device.
And (2) introducing gas (comprising methanol, methylal and methyl chloride) evaporated from the top of the separation tower into a methane-dechlorinating tower, recovering the methyl chloride, wherein the temperature of the top of the methane-dechlorinating tower is-14 ℃, the pressure of the top of the methane-dechlorinating tower is 55KPa, the temperature of the bottom of the methane-dechlorinating tower is 60 ℃, and the reflux ratio is 1.5: 1; and (3) enabling tower bottom liquid of the methane-removing tower to enter a methylal tower, recovering methylal, wherein the tower bottom temperature of the methylal tower is 73 ℃, the pressure is 20KPa, and the reflux ratio is 1: 1.
the tower bottom components of the separation tower sequentially enter a low-pressure methanol tower and a high-pressure methanol tower to recover 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 a high-pressure methanol tower is 0.6MPa, the temperature of a tower kettle is 155 ℃, and the reflux ratio is 2.5: 1. and liquid rectified by 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; the recovery rate of methylal is more than 99 percent, and the purity is more than 85 percent; 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 by each ton of glyphosate, 5.0t of steam is consumed by each ton of glyphosate, and 55kg of sulfuric acid is consumed by each ton of chloromethane.
Example 2
Experiments were conducted on the recovery system for the tail gas from the hydrolysis of glyphosate synthesis solution as described 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) Carrying out depolymerization reaction on methanol, triethylamine and paraformaldehyde at 50 ℃;
a2) performing addition reaction on the product after the depolymerization reaction and glycine at the temperature of 45 ℃;
a3) and carrying out condensation reaction on the product after the addition reaction and dialkyl phosphite at the temperature of 45 ℃ to obtain synthetic liquid.
The synthetic solution and hydrochloric acid were mixed in an acidification device (static mixer) and acidified at 40 ℃ under a pressure of 5 KPa. After acidification is completed, the mixture is cooled in an acidification cooler. And (3) feeding the cooled acidified liquid into a hydrolysis reaction tower and a hydrolysis kettle for hydrolysis reaction, wherein the temperature of the hydrolysis reaction is 120 ℃, and the pressure is 90 KPa.
The gas discharged from the hydrolysis reaction tower (comprising methanol, methylal, methyl chloride, water and hydrogen chloride) and the gas discharged from the static mixer enter a caustic washing tower (the total flow of the gas in the caustic washing tower is 28 m)3And h), performing neutralization reaction with a sodium hydroxide solution with the mass concentration of 5% in an alkaline tower, wherein the temperature of the neutralization reaction is 85 ℃, and the pressure is 5 KPa.
And (3) stripping the solution after the neutralization reaction in a stripping tower, wherein the temperature of a kettle of the stripping tower is 100 ℃, and the stripping pressure is 10 KPa. And (2) introducing gas (comprising methanol and water) separated from the top of the stripping tower and gas discharged from the top of the alkaline washing tower into a separation tower for first rectification separation, wherein the tower kettle temperature of the separation tower is 65 ℃, the tower top pressure is 10KPa, and the tower top reflux ratio of the separation tower is 2.2: and 1, enabling the wastewater at the bottom of the stripping tower to enter a wastewater treatment device.
And (2) introducing gas (comprising methanol, methylal and methyl chloride) evaporated from the top of the separation tower into a methane-dechlorinating tower, recovering the methyl chloride, wherein the top temperature of the methane-dechlorinating tower is-17 ℃, the temperature of a tower kettle is 65 ℃, the pressure of the top of the tower is 40KPa, and the reflux ratio is 1.5: 1; and (3) enabling tower bottom liquid of the methane-removing tower to enter a methylal tower, recovering methylal, wherein the tower bottom temperature of the methylal tower is 80 ℃, the pressure is 10KPa, and the reflux ratio is 1: 1.
the tower bottom components of the separation tower sequentially enter a low-pressure methanol tower and a high-pressure methanol tower to recover 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 a high-pressure methanol tower is 0.7MPa, the temperature of a tower kettle is 155 ℃, and the reflux ratio is 2.5: 1. and liquid rectified by 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; the recovery rate of methylal is more than 99 percent, and the purity is more than 85 percent; 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 by each ton of glyphosate, 4.9t of steam is consumed by each ton of glyphosate, and 55kg of sulfuric acid is consumed by each ton of methyl chloride.
Comparative example 1
The synthetic liquid and the hydrochloric acid are respectively metered in a metering tank, then are successively put into a hydrolysis kettle, the stirring is started, the temperature is slowly raised, the hydrolysis reaction (batch reaction) is carried out, the gas phase generated by the reaction is condensed through a first-stage, a second-stage and a third-stage, the condensate is collected into a dilute methanol tank, and the non-condensable gas (crude chloromethane) is conveyed to a chloromethane recovery device by a fan. The temperature of the hydrolysis reaction end point is controlled to be 110-135 ℃, and the system pressure is controlled to be 5-5 KPa.
After carrying out neutralization reaction on dilute methanol and liquid caustic soda with the mass concentration of 40% in a static mixer, preheating to 60-80 ℃ by using recovered methanol and steam condensate water, rectifying in a partition wall tower through gas-liquid two phases, controlling the temperature of the top of the methylal side tower at 42 ℃, controlling the pressure at normal pressure, controlling the reflux ratio at 5, condensing the gas phase extracted from the top of the tower to obtain a methylal product, and removing chloromethane from non-condensable gas (crude chloromethane) by using a chloromethane recovery device; the temperature of the top of the methanol side tower is controlled at 64 ℃, the pressure is normal, the reflux ratio is 1.5, the methanol product is extracted from the top of the tower, and the mixture of methanol and water is extracted from the middle lower side of the tower to the high-pressure methanol tower; removing the tower kettle waste water to an environment-friendly station after heat exchange; the temperature at the top of the high-pressure methanol tower is controlled at 120 ℃, the pressure is controlled at 0.55MPa, the reflux ratio is 3.5, the gas phase at the top of the high-pressure methanol tower is used as a heat source for the partition wall tower, the condensate is a methanol product, and the waste water at the bottom of the tower is subjected to heat exchange and then is discharged to an environmental protection station.
The recovery rate of methanol is more than 98%, the purity is more than 99.5%, 330kg of methanol is consumed by each ton of glyphosate, 7.0t of steam is consumed by each ton of glyphosate, and 130kg of sulfuric acid is consumed by each ton of methyl chloride.
The results of comparing the quality of methyl chloride and methylal obtained in example 1 with those obtained in comparative example 1 are shown in tables 1 and 2:
TABLE 1 comparison of the quality of the methyl chloride obtained in example 1 with that of comparative example 1
| Methyl chloride | Dimethyl ether | Methylal | Methanol | Water (W) | |
| Example 1 | 97.5 | 2.5 | Not detected out | Not detected out | Not detected out |
| Comparative example 1 | 93.3 | 2.5 | 2.5 | 1.5 | 0.2 |
TABLE 2 comparison of the qualities of the formals obtained in example 1 and comparative example 1
| Methyl chloride | Methylal | Methanol | Water (W) | |
| Example 1 | <0.1 | 85 | 14.8 | 0.1 |
| Comparative example 1 | ≈3 | 85 | 11.9 | 0.1 |
The above description of the embodiments is only intended to help understand 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 (6)
1. A recovery system of glyphosate synthetic fluid hydrolysis tail gas includes:
a hydrolysis reaction device;
the first gas inlet is connected with the gas outlet of the hydrolysis reaction device;
the first liquid inlet is connected with the liquid outlet of the alkaline tower;
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 methane-removing column connected to the gas outlet of the separation column;
and the formaldehyde condensation tower is connected with a liquid outlet of the methane-removing tower.
2. The recycling system according to claim 1, wherein the hydrolysis reaction device comprises a hydrolysis reaction tower and a hydrolysis reaction kettle;
a product solution outlet of the hydrolysis reaction tower is connected with a product solution inlet of the hydrolysis reaction kettle; and a gas outlet of the hydrolysis reaction kettle is connected with a gas inlet of the hydrolysis reaction tower.
3. The recycling system according to claim 1, wherein the hydrolysis reaction device comprises 1 hydrolysis reaction tower and 1 hydrolysis reaction kettle.
4. The recovery system of claim 3, further comprising a hydrolysis reboiler;
the hydrolysis reboiler is used for heating the hydrolysis reaction kettle.
5. A recovery system as claimed in claim 1, in which the methanol column comprises a low pressure methanol column and a high pressure methanol column;
the liquid phase inlet of the low-pressure methanol tower is connected with the liquid outlet of the separation tower;
and the liquid phase inlet of the high-pressure methanol tower is connected with the liquid outlet of the low-pressure methanol tower.
6. The recovery system of claim 5, wherein the liquid outlet of the high pressure methanol column is connected to the second liquid inlet of the stripping column.
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