CN211753890U - 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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- CN211753890U CN211753890U CN202020324951.5U CN202020324951U CN211753890U CN 211753890 U CN211753890 U CN 211753890U CN 202020324951 U CN202020324951 U CN 202020324951U CN 211753890 U CN211753890 U CN 211753890U
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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 first-stage hydrolysis reaction device; a secondary hydrolysis reaction device; a hydrolysis tail gas condenser; the first gas inlet is connected with a gas outlet of the hydrolysis tail gas condenser; a second gas inlet of the alkaline tower is connected with a gas outlet of the primary hydrolysis reaction device; the first liquid inlet is connected with a liquid outlet of the alkaline tower; a second liquid inlet of the mixing device is connected with a liquid outlet of the hydrolysis tail gas condenser; a vapor-liquid separator connected to the liquid outlet of the mixing device; the gas inlet of the gas-liquid separator is connected with the gas outlet of the alkaline washing tower; a dividing wall column; a methylal condenser; high pressure methanol tower. The recovery system has simple process, can effectively recover byproducts, and has low steam consumption and low cost.
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 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).
Patent CN104163832B discloses a continuous production device and method for glyphosate, wherein the method comprises mixing a condensation liquid with hydrochloric acid in a high-level hydrochloric acid tank through a heat-preservation pipeline, feeding the mixture into a mixer, mixing uniformly, and feeding the mixed liquid into a mixing kettle for hydrolysis reaction to obtain a hydrolysate; the hydrolysate is injected into a deacidification kettle for desolventizing, deacidification tail gas enters an alkaline tower and a two-stage condenser for condensation, the condensed tail gas is sent to a gas-liquid separator, the condensate separated by the gas-liquid separator enters a methylal storage tank, the tail gas enters a methanol tower, the tail gas is distilled in the methanol tower and then enters the two-stage condenser for condensation, the condensed tail gas is sent to a chloromethane recovery system, and the condensate enters a methanol storage tank. The method can realize uninterrupted continuous production through the connection of the continuous devices, so that more equipment is needed and the occupied area is larger. In addition, the recovery rate of methylal is low, methylal needs to be condensed into liquid, and then enters the tower again, and a large amount of steam is consumed to heat the methylal into vapor, so that not only is the heat of hydrolysis steam wasted, but also a large amount of raw steam is additionally consumed, and great heat waste is caused.
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 tail gas of hydrolysising, the utility model provides a recovery system obtains the methylal rate of recovery higher, and the steam consumption is few.
The utility model provides a recovery system of tail gas is hydrolysised to glyphosate synthetic liquid, include:
a first-stage hydrolysis reaction device;
the second-stage hydrolysis reaction device is connected with a product solution outlet of the first-stage hydrolysis reaction device;
the hydrolysis tail gas condenser is 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; a second gas inlet of the alkaline tower is connected with a gas outlet of the primary hydrolysis reaction device;
the first liquid inlet is connected with the liquid outlet of the alkaline tower; a second liquid inlet of the mixing device is connected with a liquid outlet of the hydrolysis tail gas condenser;
the gas-liquid separator is connected with the liquid outlet of the mixing device; the gas inlet of the gas-liquid separator is connected with the gas outlet of the alkaline washing tower;
a dividing wall column having a liquid inlet connected to the liquid outlet of the vapor-liquid separator; the gas inlet of the partition wall tower is connected with the gas outlet of the gas-liquid separator;
a methylal condenser connected to the methylal side column of the divided wall column;
and the high-pressure methanol tower is connected with the methanol side tower of the partition wall tower.
Preferably, the first-stage hydrolysis reaction device comprises a first-stage hydrolysis reaction tower and a first-stage hydrolysis reaction kettle;
the product solution outlet of the first-stage hydrolysis reaction tower is connected with the product solution inlet of the first-stage 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.
Preferably, the first-stage hydrolysis reaction tower is a corrosion-resistant packed tower;
the first-stage hydrolysis reaction kettle is an open glass lining reaction kettle, a tetrafluoro lining reaction kettle or a graphite reaction kettle.
Preferably, the secondary hydrolysis reaction device is a secondary hydrolysis reaction kettle;
and a product solution inlet of the second-stage hydrolysis reaction kettle is connected with a product solution outlet of the first-stage hydrolysis reaction kettle.
Preferably, the second-stage hydrolysis reaction kettle is an open glass lining reaction kettle, a tetrafluoro lining reaction kettle or a graphite reaction kettle.
Preferably, the hydrolysis tail gas condenser is an acid-proof heat exchanger.
Preferably, the mixing device is a tubular static mixer.
Preferably, the recovery system does not contain a stripper.
The utility model provides a recovery system of tail gas is hydrolysised to glyphosate synthetic liquid, include: a first-stage hydrolysis reaction device; the second-stage hydrolysis reaction device is connected with a product solution outlet of the first-stage hydrolysis reaction device; the hydrolysis tail gas condenser is 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; a second gas inlet of the alkaline tower is connected with a gas outlet of the primary hydrolysis reaction device; the first liquid inlet is connected with the liquid outlet of the alkaline tower; a second liquid inlet of the mixing device is connected with a liquid outlet of the hydrolysis tail gas condenser; the gas-liquid separator is connected with the liquid outlet of the mixing device; the gas inlet of the gas-liquid separator is connected with the gas outlet of the alkaline washing tower; a dividing wall column having a liquid inlet connected to the liquid outlet of the vapor-liquid separator; the gas inlet of the partition wall tower is connected with the gas outlet of the gas-liquid separator; a methylal condenser connected to the methylal side column of the divided wall column; and the high-pressure methanol tower is connected with the methanol side tower of the partition wall tower. The utility model provides a recovery system simple process of glyphosate synthetic fluid hydrolysis tail gas can effectively retrieve the accessory substance, and steam consumption is few, 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 first-stage hydrolysis reaction device;
the second-stage hydrolysis reaction device is connected with a product solution outlet of the first-stage hydrolysis reaction device;
the hydrolysis tail gas condenser is 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; a second gas inlet of the alkaline tower is connected with a gas outlet of the primary hydrolysis reaction device;
the first liquid inlet is connected with the liquid outlet of the alkaline tower; a second liquid inlet of the mixing device is connected with a liquid outlet of the hydrolysis tail gas condenser;
the gas-liquid separator is connected with the liquid outlet of the mixing device; the gas inlet of the gas-liquid separator is connected with the gas outlet of the alkaline washing tower;
a dividing wall column having a liquid inlet connected to the liquid outlet of the vapor-liquid separator; the gas inlet of the partition wall tower is connected with the gas outlet of the gas-liquid separator;
a methylal condenser connected to the methylal side column of the divided wall column;
and the high-pressure methanol tower is connected with the methanol side tower of the partition wall 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 certain embodiments of the present invention, the recovery system of glyphosate synthetic fluid hydrolysis tail gas provided by the present invention 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 one-level hydrolysis reaction unit. The first-stage hydrolysis reaction device is used for first-stage hydrolysis of the acidizing fluid. In some embodiments of the present invention, the acidification liquid inlet of the first-stage hydrolysis reaction device is connected to the acidification liquid outlet of the acidification device. In some embodiments of the present invention, the first stage hydrolysis reaction device comprises a first stage hydrolysis reaction tower and a first stage hydrolysis reaction kettle.
In certain embodiments of the present invention, the first-stage 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 primary hydrolysis reaction tower is connected with an acidizing fluid outlet of the mixing device.
In certain embodiments of the present invention, the first stage hydrolysis reactor is provided with a product solution inlet, a product solution outlet, and a gas outlet. And a product solution inlet of the primary hydrolysis reaction tower is connected with an acidizing fluid outlet of the 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 discharged from the first-stage hydrolysis reaction kettle to the first-stage hydrolysis reaction tower.
The utility model discloses it is right the structure of one-level hydrolysis reaction tower and one-level hydrolysis reaction cauldron does not have special restriction. In certain embodiments of the present invention, the first stage hydrolysis reaction tower is a corrosion-resistant packed tower. In certain embodiments, the first stage hydrolysis reaction tower is an open glass lined packed tower, a tetrafluoro-lined packed tower, or a graphite packed tower. In certain embodiments of the present invention, the first stage 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 first-stage hydrolysis reaction kettle. The utility model discloses it is right the connected mode of hydrolysis reboiler does not have special restriction, can realize that one-level hydrolysis reaction cauldron's 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. 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. 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 primary 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 fluid tail gas of hydrolysising still include with the second grade hydrolysis reaction device that one-level hydrolysis reaction device's product solution export links to each other. 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 present invention, the second stage hydrolysis reaction device is a second stage hydrolysis reaction kettle.
In certain embodiments of the present invention, the second stage hydrolysis reactor is provided with a product solution inlet, a slurry outlet, and a gas outlet. And a product solution inlet of the second-stage hydrolysis reaction kettle is connected with a product solution outlet of the first-stage hydrolysis reaction kettle.
The utility model discloses it is right second grade hydrolysis reaction kettle's structure does not have special restriction the utility model discloses an in some embodiments, second grade hydrolysis reaction kettle is open glass-lined reation kettle.
The utility model provides a recovery system of glyphosate synthetic liquid tail gas of hydrolysising still include with the tail gas condenser of hydrolysising that the gas outlet of second grade hydrolysis reaction unit links to each other. And the hydrolysis tail gas condenser is used for cooling tail gas after the secondary hydrolysis reaction. In certain embodiments of the present invention, the hydrolysis tail gas condenser is provided with a gas inlet, a gas outlet, and a condensate outlet. In certain embodiments of the present invention, the gas inlet of the hydrolysis tail gas condenser is connected to the gas outlet of the second stage hydrolysis reaction device. In certain embodiments, the gas inlet of the hydrolysis tail gas condenser is connected with the gas outlet of the secondary hydrolysis reaction kettle. The utility model discloses it is right the structure of tail gas condenser of hydrolysising does not have special restriction. In certain embodiments of the present invention, the hydrolysis tail gas condenser may be an acid-resistant heat exchanger.
The utility model provides a recovery system of glyphosate synthetic solution tail gas of hydrolysising still includes the caustic wash tower. 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 third gas inlet, a liquid outlet and a gas outlet. And a first gas inlet of the alkaline washing tower is connected with a gas outlet of the hydrolysis tail gas condenser. In certain embodiments of the present invention, the second gas inlet of the caustic tower is connected to the gas outlet of the primary hydrolysis reaction device. In certain embodiments of the present invention, the third 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 mixing arrangement that the liquid outlet of caustic wash tower links to each other. In an embodiment of the invention, the mixing device is provided with a first liquid inlet, a second liquid inlet and a liquid outlet. And a first liquid inlet of the mixing device is connected with a liquid outlet of the alkaline washing tower. And a second liquid inlet of the mixing device is connected with a liquid outlet of the hydrolysis tail gas condenser. In certain embodiments of the present invention, the mixing device is a tubular static mixer, and the model may be SK, SV or SX, preferably SK.
The utility model provides a recovery system of glyphosate synthetic fluid tail gas of hydrolysising still include with the vapour and liquid separator that mixing arrangement's liquid outlet links to each other. In certain embodiments of the present invention, the vapor-liquid separator is provided with a gas inlet, a liquid inlet and a liquid outlet. The utility model discloses in, vapour and liquid separator's liquid inlet with mixing arrangement's liquid outlet links to each other, vapour and liquid separator's gas inlet with the gas outlet of alkaline wash tower links to each other. The utility model discloses it is right vapor-liquid separator's structure does not have special restriction, can be conventional vapor-liquid separator.
The utility model provides a recovery system of glyphosate synthetic fluid tail gas of hydrolysising still include with the spacer tower that vapour and liquid separator links to each other. In certain embodiments of the present invention, the divided wall column comprises a methylal side column and a methanol side column. After gas-liquid separation, the solution and the gas after the gas-liquid separation respectively enter a partition wall tower and are rectified in the partition wall tower. In the utility model, the liquid inlet of the partition wall tower is connected with the liquid outlet of the vapor-liquid separator; and the gas inlet of the partition wall tower is connected with the gas outlet of the gas-liquid separator. Rectifying by a partition wall tower, discharging methylal gas from the top of a methylal side tower, condensing to obtain methylal, wherein the non-condensable gas is a crude product of methyl chloride; discharging methanol from the top of the methanol side column; the column side of the methanol side column withdraws a mixture of methanol and water. And discharging the wastewater from the tower kettle of the partition wall tower, and allowing the wastewater to enter a wastewater treatment device. The utility model discloses it is right the structure of dividing wall tower does not have special restriction, can be conventional dividing wall tower.
The utility model provides a recovery system of glyphosate synthetic fluid tail gas of hydrolysising still include with the methylal condenser that the methylal side tower of partition wall tower links to each other. In certain embodiments of the present invention, the methylal condenser is provided with a gas inlet, a methylal outlet and a gas outlet. In certain embodiments of the present invention, the gas inlet of the methylal condenser is connected to the top of the methylal side column of the dividing wall column. And condensing the gas discharged from the top of the methylal side tower in a methylal condenser, wherein the liquid obtained by condensation is methylal. The non-condensable gas discharged from the gas outlet of the methylal condenser is a crude product of methyl chloride, and can enter a methyl chloride recovery device. The utility model discloses it is right the structure of methylal condenser does not have special restriction, can be conventional methylal condenser.
The utility model provides a recovery system of glyphosate synthetic liquid tail gas of hydrolysising still include with the high-pressure methanol tower that the methyl alcohol side tower of spacer tower links to each other. In some embodiments of the present invention, the high pressure methanol column is provided with a liquid inlet, a methanol outlet and a column bottom outlet. In certain embodiments of the present invention, the liquid inlet of the high pressure methanol column is connected to the side of the methanol side column of the dividing wall column. The mixture (methanol and water) discharged from the methanol side column is rectified in a high-pressure methanol column to obtain methanol. And the wastewater discharged from the tower kettle outlet of the high-pressure methanol tower can enter a wastewater treatment device. The utility model discloses it is right the structure of high pressure methanol tower does not have special restriction the utility model discloses an in some embodiments, high pressure methanol tower 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 primary hydrolysis reaction on the acidified glyphosate synthetic solution at 90-112 ℃ and-5-20 KPa;
B) performing secondary hydrolysis reaction on the product solution of the primary hydrolysis reaction at 115-130 ℃ and-10 KPa, and condensing the gas after the secondary hydrolysis reaction to obtain a condensate and a non-condensable gas;
mixing the gas generated by the primary hydrolysis reaction, the non-condensable gas and alkali liquor, and performing neutralization reaction;
C) mixing the condensate with the solution after the neutralization reaction, and adjusting the pH value to 7.5-12;
D) carrying out gas-liquid separation on the solution after the pH value is adjusted and the gas obtained by the neutralization reaction;
E) the solution and the gas after the gas-liquid separation respectively enter a partition wall tower; the tower top temperature of a methylal side tower in the partition wall tower is 35-50 ℃, and the pressure in the methylal side tower is normal pressure; the top temperature of a methanol side tower in the partition wall tower is 55-70 ℃, and the pressure in the methanol side tower is normal pressure;
condensing gas discharged from the top of the methylal side tower to obtain methylal;
condensing gas discharged from the top of the methanol side tower to obtain methanol; and rectifying the mixture discharged from the tower side of the methanol side tower to obtain the methanol.
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 synthesis of the glyphosate synthesis solution is performed in a synthesis kettle.
And after the synthetic liquid is obtained, acidifying the synthetic liquid to obtain acidified liquid.
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.
After obtaining the acidizing fluid, carrying out primary hydrolysis reaction on the acidizing fluid at the temperature of 90-112 ℃ and under the pressure of-5-20 KPa.
In certain embodiments of the present invention, the acidizing fluid further comprises, before the first stage 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 some embodiments of the present invention, the temperature of the first-stage hydrolysis reaction is 100-110 ℃, 108 ℃ or 100 ℃, and the pressure is 3-12 KPa, 10KPa or 5 KPa. In certain embodiments of the present invention, the primary hydrolysis reaction is carried out in a primary hydrolysis reaction apparatus.
And after the first-stage hydrolysis reaction is finished, performing a second-stage hydrolysis reaction on the product solution of the first-stage hydrolysis reaction at 115-130 ℃ and-10 KPa.
In some embodiments of the present invention, the temperature of the second stage hydrolysis reaction is 115-125 ℃, 120 ℃ or 115 ℃, and the pressure is-5 KPa, -5KPa or 0 KPa. In certain embodiments of the present invention, the second hydrolysis reaction is performed in a second 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 some embodiments of the present invention, the condensation of the gas after the second-stage hydrolysis reaction is a vacuum cooling, wherein the pressure of the vacuum cooling is greater than or equal to-70 KPa; or the condensation is water adding and cooling, and the temperature after water adding and cooling is 30-90 ℃. In certain embodiments of the present invention, the vacuum lowering pressure is-60 KPa. In certain embodiments of the present invention, the condensation is performed in a hydrolysis tail gas condenser. In some embodiments of the present invention, the condensed condensate may be collected to a dilute methanol buffer tank.
Mixing the gas generated by the primary hydrolysis reaction, the non-condensable gas and alkali liquor, and carrying out neutralization reaction. In some embodiments of the present invention, the gas generated by the acidification, the gas generated by the primary hydrolysis reaction, the non-condensable gas 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 primary hydrolysis reaction comprises methanol, methylal, methyl chloride, water, and hydrogen chloride. In certain embodiments of the present invention, the non-condensable gas 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.
The utility model discloses in, will condensate and the solution after the neutralization reaction mix, adjust pH value to 7.5 ~ 12.
In some embodiments of the present invention, the mixing of the condensate with the solution after the neutralization reaction, and the adjustment of the pH value are performed in a mixing device.
In certain embodiments of the present invention, the condensate is mixed with the solution after the neutralization reaction to adjust the pH to 8 or 11.
And after the pH value is adjusted, carrying out gas-liquid separation on the solution after the pH value is adjusted and the gas obtained by the neutralization reaction.
In some embodiments of the present invention, the gas-liquid separation temperature is 60 to 80 ℃. In certain embodiments, the temperature of the gas-liquid separation is 65 ℃ or 75 ℃.
In certain embodiments of the present invention, the gas-liquid separation is performed in a vapor-liquid separator.
And after gas-liquid separation, the solution and the gas after the gas-liquid separation respectively enter the partition wall tower. Specifically, the solution after gas-liquid separation enters the dividing wall tower from a liquid inlet of the dividing wall tower, and the gas after gas-liquid separation enters the dividing wall tower from a gas inlet of the dividing wall tower.
The utility model discloses in, the partition wall tower includes methylal side tower and methyl alcohol side tower.
The tower top temperature of a methylal side tower in the partition wall tower is 35-50 ℃, and the pressure in the methylal side tower is normal pressure. In certain embodiments of the present invention, the top temperature of the methylal sidecar column in the divided wall column is 42 ℃. In certain embodiments of the present invention, the reflux ratio in the methylal side column is 0.5-2: 1. in certain embodiments, the reflux ratio in the methylal sidedraw column is 1: 1.
the top temperature of the methanol side tower in the partition wall tower is 55-70 ℃, and the pressure in the methanol side tower is normal pressure. In certain embodiments of the present invention, the overhead temperature of the methanol side column in the divided wall column is 64 ℃. In certain embodiments of the present invention, the reflux ratio in the methanol side column is 0.5-2: 1. in certain embodiments, the reflux ratio in the methanol side column is 1: 1.
and condensing the gas discharged from the top of the methylal side tower to obtain methylal. In certain embodiments of the present invention, the temperature of the condensation is 30-35 ℃. In certain embodiments, the temperature of the condensation is 32 ℃. In certain embodiments of the present invention, the condensation is carried out in a methylal condenser. In some embodiments of the present invention, the non-condensable gas obtained by the condensation is a crude product of methyl chloride, and enters the methyl chloride recovery device. The utility model discloses it is right the structure of methylal condenser does not have special restriction, adopt conventional methylal condenser can.
And condensing the gas discharged from the top of the methanol side tower to obtain methanol. In certain embodiments of the present invention, the temperature of the condensation is 50-65 ℃. In certain embodiments, the temperature of the condensation is 55 ℃. In certain embodiments of the present invention, the condensation is performed in a methanol condenser. The utility model discloses it is right methanol condenser's structure does not have special restriction, adopts conventional methanol condenser can.
The mixture discharged from the column side of the methanol side column comprises methanol and water. And rectifying the mixture discharged from the tower side of the methanol side tower to obtain the methanol. In some embodiments of the present invention, the top temperature of the rectification column is 100 to 130 ℃ or 120 ℃. In some embodiments of the present invention, the pressure of the rectification is 0.3 to 0.6MPa, 0.55MPa or 0.5 MPa. In some embodiments of the present invention, the reflux ratio of the rectification is 1-6: 1. 3.5: 1 or 4: 1. in certain embodiments of the present invention, the rectification is performed in a high pressure methanol column. In some embodiments of the present invention, the rectified wastewater may enter a wastewater treatment device. In some embodiments of the present invention, the wastewater discharged from the tower bottom of the partition wall tower can enter the wastewater treatment device.
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 steam consumption is few, 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 first-stage hydrolysis reaction tower and a first-stage hydrolysis kettle to perform a first-stage hydrolysis reaction, wherein the temperature of the first-stage hydrolysis reaction is 108 ℃, and the pressure is 10 KPa. And performing 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.
And (3) 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. And (2) gas (comprising methanol, methylal, methyl chloride, water and hydrogen chloride) discharged from the hydrolysis tail gas condenser, gas (comprising methanol, methylal, methyl chloride, water and hydrogen chloride) discharged from the primary hydrolysis reaction tower and gas discharged from the static mixer enter an alkaline tower, and are subjected to neutralization reaction with a sodium hydroxide solution with the mass concentration of 5% in the alkaline tower, wherein the temperature of the neutralization reaction is 74 ℃ and the pressure is 0 KPa.
And mixing the condensate discharged from the hydrolysis tail gas condenser and the solution after the neutralization reaction in a mixing device, adjusting the pH value to 8, and then carrying out gas-liquid separation on the condensate and the gas obtained by the neutralization reaction in a gas-liquid separator. The temperature of the gas-liquid separation was 65 ℃.
After gas-liquid separation, the solution and the gas after the gas-liquid separation respectively enter a partition wall tower, the tower top temperature of a methylal side tower in the partition wall tower is 42 ℃, the pressure in the methylal side tower is normal pressure, and the reflux ratio in the methylal side tower is 1: 1; the top temperature of the methanol side tower in the partition wall tower is 64 ℃, the pressure in the methanol side tower is normal pressure, and the reflux ratio in the methanol side tower is 1: 1.
condensing the gas discharged from the top of the methylal side column in a methylal condenser to obtain methylal; the temperature of the condensation is 32 ℃; the non-condensable gas obtained by condensation is methyl chloride and enters a methyl chloride recovery device.
The gas discharged from the top of the methanol side column was condensed in a methanol condenser to obtain methanol. The temperature of the condensation was 55 ℃.
And the mixture discharged from the tower side of the methanol side tower is rectified at the tower top temperature of 120 ℃ and the tower top temperature of 0.55MPa in the high-pressure methanol tower, and the reflux ratio of the rectification is 3.5: 1, obtaining the methanol.
The detection shows that the recovery rate of the chloromethane is more than 95%, the purity (without air) is about 92%, and the dimethyl ether is about 2.5%; the recovery rate of methylal is more than 98 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; the consumption of methanol per ton of glyphosate is 330kg, the consumption of steam per ton of glyphosate is 6.4t, and the consumption of sulfuric acid per ton of methyl chloride is 130 kg.
Example 2
Experiments were performed on a continuous synthesis system for glyphosate 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 first-stage hydrolysis reaction tower and a first-stage hydrolysis kettle to perform a first-stage hydrolysis reaction, wherein the temperature of the first-stage hydrolysis reaction is 100 ℃, and the pressure is 5 KPa. And performing 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) 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. And (2) gas (comprising methanol, methylal, methyl chloride, water and hydrogen chloride) discharged from the hydrolysis tail gas condenser, gas (comprising methanol, methylal, methyl chloride, water and hydrogen chloride) discharged from the primary hydrolysis reaction tower and gas discharged from the static mixer enter an alkaline tower, and are subjected to neutralization reaction with a sodium hydroxide solution with the mass concentration of 5% in the alkaline tower, wherein the temperature of the neutralization reaction is 85 ℃, and the pressure is 5 KPa.
And mixing the condensate discharged from the hydrolysis tail gas condenser and the solution after the neutralization reaction in a mixing device, adjusting the pH value to 11, and then carrying out gas-liquid separation on the condensate and the gas obtained by the neutralization reaction in a gas-liquid separator. The temperature of the gas-liquid separation was 75 ℃.
After gas-liquid separation, the solution and the gas after the gas-liquid separation respectively enter a partition wall tower, the tower top temperature of a methylal side tower in the partition wall tower is 42 ℃, the pressure in the methylal side tower is normal pressure, and the reflux ratio in the methylal side tower is 1: 1; the top temperature of the methanol side tower in the partition wall tower is 64 ℃, the pressure in the methanol side tower is normal pressure, and the reflux ratio in the methanol side tower is 1: 1.
condensing the gas discharged from the top of the methylal side column in a methylal condenser to obtain methylal; the temperature of the condensation is 32 ℃; the non-condensable gas obtained by condensation is methyl chloride and enters a methyl chloride recovery device.
The gas discharged from the top of the methanol side column was condensed in a methanol condenser to obtain methanol. The temperature of the condensation was 55 ℃.
And the mixture discharged from the tower side of the methanol side tower is rectified at the tower top temperature of 120 ℃ and the tower top pressure of 0.5MPa in the high-pressure methanol tower, and the reflux ratio of the rectification is 4: 1, obtaining the methanol.
The detection shows that the recovery rate of the chloromethane is more than 95%, the purity (without air) is about 92%, and the dimethyl ether is about 2.5%; the recovery rate of methylal is more than 98 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; the consumption of methanol per ton of glyphosate is 330kg, the consumption of steam per ton of glyphosate is 6.5t, and the consumption of sulfuric acid per ton of chloromethane is 125 kg.
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 (8)
1. A recovery system of glyphosate synthetic fluid hydrolysis tail gas includes:
a first-stage hydrolysis reaction device;
the second-stage hydrolysis reaction device is connected with a product solution outlet of the first-stage hydrolysis reaction device;
the hydrolysis tail gas condenser is 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; a second gas inlet of the alkaline tower is connected with a gas outlet of the primary hydrolysis reaction device;
the first liquid inlet is connected with the liquid outlet of the alkaline tower; a second liquid inlet of the mixing device is connected with a liquid outlet of the hydrolysis tail gas condenser;
the gas-liquid separator is connected with the liquid outlet of the mixing device; the gas inlet of the gas-liquid separator is connected with the gas outlet of the alkaline washing tower;
a dividing wall column having a liquid inlet connected to the liquid outlet of the vapor-liquid separator; the gas inlet of the partition wall tower is connected with the gas outlet of the gas-liquid separator;
a methylal condenser connected to the methylal side column of the divided wall column;
and the high-pressure methanol tower is connected with the methanol side tower of the partition wall tower.
2. The recycling system according to claim 1, wherein the primary hydrolysis reaction device comprises a primary hydrolysis reaction tower and a primary hydrolysis reaction kettle;
the product solution outlet of the first-stage hydrolysis reaction tower is connected with the product solution inlet of the first-stage 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.
3. The recovery system of claim 2, wherein the primary hydrolysis reaction tower is a corrosion-resistant packed tower;
the first-stage hydrolysis reaction kettle is an open glass lining reaction kettle, a tetrafluoro lining reaction kettle or a graphite reaction kettle.
4. The recycling system according to claim 2, wherein the secondary hydrolysis reaction device is a secondary hydrolysis reaction kettle;
and a product solution inlet of the second-stage hydrolysis reaction kettle is connected with a product solution outlet of the first-stage hydrolysis reaction kettle.
5. The recycling system according to claim 4, wherein the secondary hydrolysis reaction kettle is an open glass lined reaction kettle, a tetrafluoro lined reaction kettle or a graphite reaction kettle.
6. The recovery system of claim 1, wherein the hydrolysis tail gas condenser is an acid-tolerant heat exchanger.
7. A recovery system in accordance with claim 1, characterized in that said mixing device is a tubular static mixer.
8. The recovery system of claim 1, wherein the recovery system does not contain a stripper.
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