SUMMERY OF THE UTILITY MODEL
In view of this, the present invention provides a system for recovering tail gas from hydrolysis of glyphosate-phosphonated synthetic liquid, so as to solve the problem of energy waste caused by condensing methanol, methylal and water, and then heating, rectifying and recovering methanol, methylal and the like in the prior art; and simultaneously, the utility model provides a recovery system can effectively reduce methyl alcohol consumption, improve the methyl chloride rate of recovery through the refining to methyl chloride, and can reduce the consumption of low reaches methyl chloride recovery process sulphuric acid and the processing of waste sulphuric acid.
The utility model provides a grass phosphonic acid synthetic liquid hydrolysis tail gas recovery system, include:
an alkaline washing tower;
the tower bottom liquid outlet of the alkaline tower and a connecting pipeline of the stripping tower are provided with a hydrolysis condensate liquid inlet;
the separation tower is respectively connected with the air outlet of the alkaline tower and the air outlet of the stripping tower;
the chloromethane refining tower is connected with a discharge port at the top of the separation tower;
a methylal rectifying tower connected with a tower bottom liquid outlet of the chloromethane refining tower;
and the methanol rectification system is connected with a tower bottom liquid outlet of the separation tower, and the tower bottom liquid outlet of the methanol rectification system is connected with the stripping tower.
Preferably, the methanol rectification system comprises a first methanol rectification column and a second methanol rectification column;
the first methanol rectifying tower adopts low-pressure rectification, and a feed inlet of the first methanol rectifying tower is connected with a tower bottom liquid outlet of the separation tower;
the second methanol rectifying tower adopts high-pressure rectification, a feed inlet of the second methanol rectifying tower is connected with a tower bottom liquid outlet of the first methanol rectifying tower, and a tower bottom liquid outlet of the second methanol rectifying tower is connected with the stripping tower.
Preferably, the alkaline washing tower is a spray tower, and the spray tower is provided with a tower bottom liquid circulating spray pipeline.
The utility model provides a tail gas recovery technology of grass glycine phosphonic acid synthetic liquid hydrolysis, which comprises the following steps:
a) mixing the tail gas from the hydrolysis of the glyphosate acidification synthetic solution with alkali liquor in an alkaline tower for reaction to obtain alkaline tower bottom liquid and neutralized tail gas;
b) mixing the alkaline tower bottom liquid and the glyphosate acidification synthetic liquid hydrolysis condensate, and then carrying out steam stripping in a stripping tower to obtain a gas phase product and a stripping tower bottom liquid;
c) rectifying and separating the neutralized tail gas and the gas-phase product in a separation tower to obtain a gas phase at the top of the separation tower and a tower bottom liquid of the separation tower;
d) rectifying and separating the gas phase at the top of the separation tower in a methyl chloride refining tower to obtain methyl chloride and a methyl chloride refining tower kettle solution;
rectifying and separating the tower bottom liquid of the methyl chloride refining tower in a methylal rectifying tower to obtain tower top methylal and tower bottom methanol;
e) rectifying and separating the tower bottom liquid of the separation tower in a methanol rectification system to obtain methanol and tower bottom liquid of the methanol rectification system, and returning the tower bottom liquid of the methanol rectification system to the stripping tower;
step d) and step e) are not in sequence.
Preferably, in the step a), the temperature of the mixing reaction is 70-90 ℃; the pressure of the mixing reaction is-10 to 10 KPa; the residence time of the tail gas of the hydrolysis of the glyphosate acidification synthetic liquid in the alkaline washing tower is 5-20 s.
Preferably, in the step b), the temperature of a tower kettle of the stripping tower is 100-108 ℃; the tower top temperature of the stripping tower is 70-100 ℃; the pressure of the stripping tower is-10-20 KPa.
Preferably, in the step c), the reflux ratio of the separation tower is 1-4; the temperature of a tower kettle of the separation tower is 65-80 ℃; the tower top temperature of the separation tower is 50-70 ℃; the pressure of the separation tower is-10 to 10 KPa.
Preferably, in the step d), the reflux ratio of the chloromethane refining tower is 1-3.5; the temperature of a tower kettle of the chloromethane refining tower is 55-70 ℃; the tower top temperature of the chloromethane refining tower is-10 to-20 ℃; the pressure of the chloromethane refining tower is 0-80 KPa.
Preferably, in the step d), the reflux ratio of the methylal rectifying tower is 0.5-2; the tower kettle temperature of the methylal rectifying tower is 65-85 ℃; the tower top temperature of the methylal rectifying tower is 35-45 ℃; the pressure of the methylal rectifying tower is 0-30 KPa.
Preferably, step e) specifically comprises:
e1) rectifying the tower bottom liquid of the separation tower in a low-pressure methanol rectification system to obtain methanol and tower bottom liquid of the low-pressure methanol rectification system;
the reflux ratio of the low-pressure methanol rectification system is 1-4; the tower kettle temperature of the low-pressure methanol rectification system is 90-120 ℃; the tower top temperature of the low-pressure methanol rectification system is 80-100 ℃; the pressure of the low-pressure methanol rectification system is 0-0.3 MPa;
e2) rectifying the tower bottom liquid of the low-pressure methanol rectification system in a high-pressure methanol rectification system to obtain methanol and tower bottom liquid of a high-pressure methanol rectification system, and returning the tower bottom liquid of the high-pressure methanol rectification system to the stripping tower;
the reflux ratio of the high-pressure methanol rectification system is 1-4; the tower kettle temperature of the high-pressure methanol rectification system is 135-170 ℃; the tower top temperature of the high-pressure methanol rectification system is 100-120 ℃; the pressure of the high-pressure methanol rectification system is 0.3-0.8 MPa.
Compared with the prior art, the utility model provides a hydrolysis tail gas recovery system of synthetic fluid of glyphosate. The utility model provides a recovery system includes: an alkaline washing tower; the tower bottom liquid outlet of the alkaline tower and a connecting pipeline of the stripping tower are provided with a hydrolysis condensate liquid inlet; the separation tower is respectively connected with the air outlet of the alkaline tower and the air outlet of the stripping tower; the chloromethane refining tower is connected with a discharge port at the top of the separation tower; a methylal rectifying tower connected with a tower bottom liquid outlet of the chloromethane refining tower; and the methanol rectification system is connected with a tower bottom liquid outlet of the separation tower, and the tower bottom liquid outlet of the methanol rectification system is connected with the stripping tower. In the utility model, the tail gas of the hydrolysis of the glyphosate acidification synthetic solution is firstly mixed and reacted with alkali liquor in the alkaline washing tower to obtain the tower bottom liquid and the neutralized tail gas of the alkaline washing tower; then, carrying out pH value adjustment (the pH value is controlled to be 6-14) on the tower bottom liquid discharged from the alkaline washing tower by using a glyphosate acidification synthetic liquid hydrolysis condensate (diluted methanol), and carrying out steam stripping on the alkaline washing tower bottom liquid subjected to pH value adjustment in a steam stripping tower to obtain a gas phase product and the tower bottom liquid of the steam stripping tower; then, rectifying and separating the neutralized tail gas and the gas-phase product in a separation tower to obtain a gas phase at the top of the separation tower and a tower bottom liquid of the separation tower; then, rectifying and separating the gas phase at the top of the separation tower in a methyl chloride refining tower to obtain methyl chloride and a methyl chloride refining tower bottom liquid, and rectifying and separating the methyl chloride refining tower bottom liquid in a methylal rectifying tower to obtain methylal and methanol; and rectifying and separating the tower bottom liquid of the separation tower in a methanol rectifying system to obtain methanol and the tower bottom liquid of the methanol rectifying system, and returning the tower bottom liquid of the methanol rectifying system to the stripping tower. The utility model provides a recovery system carries out neutralization, strip and multiple-effect rectification through hydrolysising tail gas to glyphosate acidizing synthetic liquid, has not only reduced tail gas recovery's heat energy consumption by a wide margin, has still saved the use amount of refrigerant, has reduced the emission of waste water, waste gas simultaneously, has reduced the methyl alcohol loss, has improved the quality and the rate of recovery of the methylal, the chloromethane that retrieve and obtain. In addition, the refined methyl chloride gas does not contain other components except methyl chloride, dimethyl ether and air basically, the quality of the methyl chloride is improved, the problem that sulfuric acid consumption is high when the methyl chloride product is subsequently dried by sulfuric acid due to the fact that low-boiling-point substances such as methanol and methylal are mixed into the methyl chloride gas can be solved, the refined methyl chloride does not need water washing and alkali washing processes any more, the amount of waste water can be reduced, the investment of equipment and electrometers in corresponding processes can be reduced, and the investment cost can be reduced.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings in the embodiments of the present invention, and it is obvious 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 grass phosphonic acid synthetic liquid hydrolysis tail gas recovery system, include:
an alkaline washing tower;
the tower bottom liquid outlet of the alkaline tower and a connecting pipeline of the stripping tower are provided with a hydrolysis condensate liquid inlet;
the separation tower is respectively connected with the air outlet of the alkaline tower and the air outlet of the stripping tower;
the chloromethane refining tower is connected with a discharge port at the top of the separation tower;
a methylal rectifying tower connected with a tower bottom liquid outlet of the chloromethane refining tower;
and the methanol rectification system is connected with a tower bottom liquid outlet of the separation tower, and the tower bottom liquid outlet of the methanol rectification system is connected with the stripping tower.
Referring to fig. 1, fig. 1 is a schematic flow chart of a recovery system for hydrolysis tail gas of glyphosate acidification synthetic solution provided by the embodiment of the present invention. Wherein 1 represents an alkaline washing tower, 2 represents a stripping tower, 3 represents a separation tower, 4 represents a methyl chloride refining tower, 5 represents a methylal rectifying tower, 6 represents a first methanol rectifying tower, and 7 represents a second methanol rectifying tower.
The utility model provides a recovery system includes alkaline tower 1, strip tower 2, knockout tower 3, methyl chloride refining tower 4, methylal rectifying column 5 and methyl alcohol rectification system. Wherein, the alkaline washing tower 1 is used for removing hydrogen chloride in the hydrolyzed tail gas of the glyphosate acidified synthetic solution, and is provided with a hydrolyzed tail gas inlet, an alkali liquor inlet, an air outlet and a tower bottom liquid outlet. In an embodiment provided by the present invention, the alkaline washing tower 1 is a spray tower, and the spray tower is provided with a tower bottom liquid circulating spray pipeline, so that the tower bottom liquid can circularly absorb the hydrolysis tail gas.
The utility model discloses in, strip tower 2 is used for carrying out the strip separation to the outer tower bottom liquid of arranging of glyphosate acidizing synthetic fluid condensate (rare methyl alcohol) and alkaline tower 1 that upstream process produced, is provided with inlet, steam inlet, gas outlet, waste water outlet and methyl alcohol rectification system tower bottom liquid backward flow mouth on it, and strip tower 2's inlet is connected with alkaline tower 1's tower bottom liquid outlet, is provided with the condensate inlet of hydrolysising on its connecting tube. The utility model discloses in, the glyphosate acidizing synthetic fluid condensate accessible that upstream process produced hydrolysis condensate inlet enters into the system, mixes with the outer tower bottom liquid of arranging of alkaline tower 1 to the realization is adjusted the pH value of alkaline tower 1 tower bottom liquid (pH value control is 6 ~ 14).
The utility model discloses in, knockout tower 3 is arranged in carrying out the rectification separation to the neutralization tail gas among the alkaline tower 1 discharge and the 2 combustion gas phase products of strip tower 2, is provided with air inlet, top of the tower discharge gate and tower bottom liquid export on it, and the air inlet of knockout tower 3 is connected with the gas outlet of alkaline tower 1 and the gas outlet of strip tower 2 respectively.
The utility model discloses in, methyl chloride refining tower 4 is used for carrying out the rectification separation to the top of the tower gaseous phase that knockout tower 3 separated, retrieves methyl chloride wherein. The chloromethane refining tower 4 is provided with a feed inlet, a discharge outlet at the top of the tower and a tower bottom liquid outlet, and the feed inlet of the chloromethane refining tower 4 is connected with the discharge outlet at the top of the tower of the separation tower 3.
The utility model discloses in, methylal rectifying column 5 is used for carrying out the rectification separation to 4 exhaust tower bottoms of methyl chloride refining tower, retrieves methylal wherein. The methylal rectifying tower 5 is provided with a feed inlet, a tower top discharge port and a tower bottom liquid outlet, and the feed inlet of the methylal rectifying tower 5 is connected with the tower bottom liquid outlet of the methyl chloride refining tower 4.
The utility model discloses in, methyl alcohol rectification system is used for carrying out the rectification separation to 3 exhaust tower bottoms of knockout tower, retrieves methyl alcohol wherein. The methanol rectifying system is provided with a feed inlet, a tower top discharge hole and a tower bottom liquid outlet, the feed inlet of the methanol rectifying system is connected with the tower bottom liquid outlet of the separation tower 3, and the tower bottom liquid outlet of the methanol rectifying system is connected with the tower bottom liquid reflux port of the methanol rectifying system of the stripping tower 2.
In one embodiment provided by the present invention, the methanol rectification system comprises a first methanol rectification column 6 and a second methanol rectification column 7; the first methanol rectifying tower 6 adopts low-pressure rectification and is provided with a feed inlet, a tower top discharge port and a tower bottom liquid outlet, and the feed inlet of the first methanol rectifying tower 6 is connected with the tower bottom liquid outlet of the separation tower 3; the second methanol rectifying tower 7 adopts high-pressure rectification and is provided with a feed inlet, a tower top discharge outlet and a tower bottom liquid outlet, the feed inlet of the second methanol rectifying tower 7 is connected with the tower bottom liquid outlet of the first methanol rectifying tower 6, and the tower bottom liquid outlet of the second methanol rectifying tower 7 is connected with the tower bottom liquid reflux opening of the methanol rectifying system of the stripping tower 2.
Referring to fig. 2, fig. 2 is a flow chart of a recovery system for hydrolysis tail gas of glyphosate acidification synthetic fluid provided by the embodiment of the present invention. Wherein 1 represents an alkaline tower, 2 represents a stripping tower, 2-1 represents a stripping tower first-stage preheater, 2-2 represents a stripping tower second-stage preheater, 2-3 represents a stripping tower third-stage preheater, 2-4 represents a stripping tower cooler, 3 represents a separation tower, 3-1 represents a separation tower condenser, 3-2 represents a separation tower reflux tank, 3-3 represents a low-boiling-point blower, 3-4 represents a blower post-condenser, 3-5 represents a low-boiling-point substance intermediate tank, 3-6 represents a separation tower reboiler, 4 represents a methyl chloride refining tower, 4-1 represents a methyl chloride compressor, 4-2 represents a methyl chloride refining tower condenser, 4-3 represents a methyl chloride refining tower reflux tank, 4-4 represents a methyl chloride refining tower, 5 represents a methylal rectifying tower, 5-1 represents a methylal rectifying tower condenser, 5-2 denotes a methylal intermediate tank, 5-3 denotes a methylal rectifying tower reboiler, 5-4 denotes a methylal rectifying tower cooler, 6 denotes a first methanol rectifying tower, 6-1 denotes a first methanol rectifying tower preheater, 6-2 denotes a first methanol rectifying tower reflux tank, 6-3 denotes a first methanol rectifying tower cooler, 6-4 denotes a first methanol rectifying tower reboiler, 7 denotes a second methanol rectifying tower, 7-1 denotes a second methanol rectifying tower feed preheater, 7-2 denotes a second methanol rectifying tower reflux tank, 7-3 denotes a second methanol rectifying tower cooler, 7-4 denotes a second methanol rectifying tower reboiler, ls (lowpressure steam) denotes low pressure steam, and ms (medium pressure steam) denotes medium pressure steam.
In an embodiment of the present invention, the recycling system further comprises a stripper first-stage preheater 2-1, a stripper second-stage preheater 2-2, and a stripper third-stage preheater 2-3. The utility model discloses in, the outer tower bottom liquid of arranging of caustic wash tower 1 mixes the back through stripper one-level preheater 2-1, stripper second grade preheater 2-2 and stripper tertiary preheater 2-3 in proper order after with the hydrolytic condensate of glyphosate acidizing synthetic fluid, reenters into stripper 2 and carries out the strip separation. Wherein, the heat source of the first-stage preheater 2-1 of the stripping tower is preferably the methanol product separated from the first methanol rectifying tower 6, the heat source of the second-stage preheater 2-2 of the stripping tower is preferably the methanol product separated from the second methanol rectifying tower 7, and the heat source of the third-stage preheater 2-3 of the stripping tower is preferably steam condensate water.
In an embodiment provided by the utility model, the recovery system further comprises a stripping tower cooler 2-4, and the tower bottom liquid (wastewater) discharged from the stripping tower 2 is cooled by the stripping tower cooler 2-4 and then conveyed to a downstream wastewater treatment device by a pump.
In one embodiment provided by the utility model, the recovery system further comprises a separation tower condenser 3-1, a separation tower reflux tank 3-2, a low-boiling fan 3-3, a fan post-condenser 3-4 and a low-boiling substance intermediate tank 3-5. In the utility model, the gas phase at the top of the separation tower 3 is partially condensed by a separation tower condenser 3-1, the condensate is collected to a separation tower reflux tank 3-2 and then is conveyed by a pump, and the condensate partially refluxes and partially enters a chloromethane refining tower 4; the gas phase which is not condensed by the condenser 3-1 of the separation tower is pressurized by a low-boiling fan 3-3 and then is conveyed to a fan rear condenser 3-4, and the condensate is collected to a low-boiling substance intermediate tank 3-5; the gas phase which is not condensed by the fan rear condenser 3-4 is conveyed to the methyl chloride refining tower 4, and the condensate in the low-boiling-point substance intermediate tank 3-5 is also conveyed to the methyl chloride refining tower 4 by a pump.
In an embodiment of the present invention, the recycling system further includes a separation tower reboiler 3-6 for heating the tower bottoms of the separation tower 3 to heat and gasify the tower bottoms. The heat source of the separation tower reboiler 3-6 is preferably methanol steam discharged from the top of the first methanol rectifying tower 6.
In one embodiment provided by the utility model, the recovery system further comprises a methyl chloride compressor 4-1, a methyl chloride refining tower condenser 4-2 and a methyl chloride refining tower reflux tank 4-3. In the utility model, the gas at the top part of the methyl chloride refining tower 4 is conveyed to a methyl chloride compressor 4-1 through a pipeline for compression, the compressed methyl chloride enters a methyl chloride refining tower condenser 4-2 for condensation, the condensate generated by condensation is recovered to a methyl chloride refining tower reflux tank 4-3 and then reflows to the methyl chloride refining tower 4; the uncondensed noncondensable gas and the gas phase extracted from the top of the methyl chloride refining tower 4 are conveyed to a downstream methyl chloride recovery device as methyl chloride products.
In an embodiment provided by the present invention, the recycling system further comprises a reboiler 4-4 for heating the bottom liquid of the chloromethane refining tower 4 to heat and gasify the bottom liquid. The heat source of the methyl chloride refining tower reboiler 4-4 is preferably steam condensate water.
In one embodiment provided by the utility model, the recovery system further comprises a methylal rectifying tower condenser 5-1 and a methylal intermediate tank 5-2. In the utility model, after the gas phase at the top of the methylal rectifying tower 5 is condensed by a methylal rectifying tower condenser 5-1, the condensate is collected to a methylal intermediate tank 5-2, part of the condensate flows back, and part of the condensate is conveyed to a downstream methylal recovery device as a methylal product; the uncondensed gas phase (methylal rectification column vent gas) is sent to a low-boiling fan 3-3 and treated together with the gas phase which is not condensed by the separation column condenser 3-1.
In an embodiment provided by the utility model, the recovery system still includes chloromethyl acetal rectifying column reboiler 5-3 for the tower bottom liquid to methylal rectifying column 5 heats, makes the tower bottom liquid intensification gasification. The heat source of the chloromethyl acetal rectifying tower reboiler 5-3 is preferably methanol steam discharged from the top of the first methanol rectifying tower 6.
In an embodiment provided by the utility model, the recovery system further comprises a methylal rectifying tower cooler 5-4 for cooling the tower bottom liquid (methanol) discharged from the methylal rectifying tower 5.
In an embodiment provided by the present invention, the recycling system further includes a first methanol rectifying tower preheater 6-1, and the tower bottom liquid discharged from the separation tower 3 enters the first methanol rectifying tower 6 for rectification and separation after being preheated by the first methanol rectifying tower preheater 6-1. The heat source of the first methanol rectifying tower preheater 6-1 is preferably tower bottom liquid discharged out of the second methanol rectifying tower 7.
In one embodiment provided by the present invention, the recovery system further comprises a first methanol rectification column reflux drum 6-2. The utility model discloses in, 6 top of the tower methanol steam of first methanol rectifying tower are as the heat source of knockout tower reboiler 3-6 and/or methylal rectifying tower reboiler 5-3, after above-mentioned reboiler heat transfer condensation, the condensate that obtains is collected to first methanol rectifying tower reflux tank 6-2, later through the pump delivery, and partial reflux is to first methanol rectifying tower 6, and the remainder outwards carries as the methanol product. In one embodiment provided by the present invention, the recovery system further comprises a first methanol rectification tower cooler 6-3, and the methanol product is cooled by the first methanol rectification tower cooler 6-3 and then transported to a downstream methanol recovery device. In one embodiment provided by the present invention, the methanol product is used as a heat source to exchange heat with the first-stage preheater 2-1 of the stripping tower before entering the first methanol rectifying tower cooler 6-3.
In an embodiment provided by the present invention, the recycling system further comprises a first methanol rectifying tower reboiler 6-4 for heating the tower bottoms of the first methanol rectifying tower 6 to heat and gasify the tower bottoms. The heat source of the first methanol rectifying tower reboiler 6-4 is preferably methanol steam discharged from the top of the second methanol rectifying tower 7.
In an embodiment provided by the present invention, the recycling system further comprises a second methanol rectifying tower feed preheater 7-1, the second methanol rectifying tower feed preheater 7-1 is disposed between the outlet of the tower bottom liquid of the first methanol rectifying tower 6 and the feed inlet of the second methanol rectifying tower 7, and is used for preheating the tower bottom liquid of the first methanol rectifying tower 6 to be fed into the second methanol rectifying tower 7.
In one embodiment provided by the present invention, the recovery system further comprises a second methanol distillation column reflux drum 7-2. The utility model discloses in, second methyl alcohol rectifying column 7 top of the tower methanol steam is as the heat source of first methyl alcohol rectifying column reboiler 6-4, after above-mentioned reboiler heat transfer condensation, the condensate that obtains is collected to second methyl alcohol rectifying column reflux tank 7-2, later through the pump delivery, and partial reflux is to second methyl alcohol rectifying column 7, and the surplus is outwards carried as the methanol product. In one embodiment provided by the present invention, the recovery system further comprises a second methanol distillation tower cooler 7-3, and the methanol product is cooled by the second methanol distillation tower cooler 7-3 and then transported to a downstream methanol recovery device. In one embodiment provided by the present invention, the methanol product is first used as a heat source to exchange heat with the second pre-heater 2-2 of the stripping tower before entering the second methanol rectifying tower cooler 7-3.
In an embodiment provided by the present invention, the recycling system further comprises a second methanol distillation column reboiler 7-4, for heating the tower bottoms of the second methanol distillation column 7, so as to heat and gasify the tower bottoms.
In one embodiment provided by the utility model, the tower bottom liquid discharged from the second methanol rectifying tower 7 is used as the heat source of the first methanol rectifying tower preheater 6-1, and enters the stripping tower 2 after exchanging heat with the tower bottom liquid; part is passed directly into stripping column 2.
For the sake of clarity, taking the glyphosate acidified synthesis solution hydrolysis tail gas recovery system shown in fig. 2 as an example, the first methanol rectification tower 6 adopts low-pressure rectification, and the second methanol rectification tower 7 adopts high-pressure rectification, and the specific working processes of the recovery system are as follows:
the gas phase from the hydrolysis procedure is conveyed to an alkaline washing tower 1 through a pipeline, gas-liquid neutralization reaction is carried out on the gas phase, fresh liquid caustic soda and circulating lye in the tower, the gas phase at the top of the tower is conveyed to a separation tower 3 through a pipeline, and the tower bottom liquid is conveyed to a stripping tower 2.
Mixing tower bottom liquid from an alkaline tower 1 and hydrolysis condensate of glyphosate acidification synthetic liquid, conveying the mixture to a first-stage preheater 2-1 of a stripping tower by a pump, preheating the mixture by a methanol product of a low-pressure methanol rectification system (a first methanol rectification tower 6), conveying the mixture to a second-stage preheater 2-2 of the stripping tower by a pipeline, preheating the mixture by a methanol product of a high-pressure methanol rectification system (a second methanol rectification tower 7), conveying the mixture to a third-stage preheater 2-3 of the stripping tower by a pipeline, preheating by steam condensate, and conveying the mixture to the stripping tower 2 by a pipeline. The lower side of the stripping tower 2 is connected with high-pressure methanol rectification system tower kettle wastewater, the tower kettle is connected with low-pressure steam (LS), materials in the tower are stripped, the gas phase at the top of the tower is conveyed to the separation tower 3 through a pipeline, and the tower kettle wastewater is conveyed to a downstream wastewater treatment device through a pump after being cooled by a stripping tower cooler 2-4.
Gas phases from the alkaline tower 1 and the stripping tower 2 are separated in a separation tower 3, the gas phase at the top of the tower is partially condensed by a separation tower condenser 3-1, condensate is collected to a separation tower reflux tank 3-2 and then is conveyed by a pump, partial reflux is carried out, and partial reflux enters a methyl chloride refining tower 4; the uncondensed gas phase and the vent gas of the methylal rectifying tower 5 enter a low-boiling fan 3-3 together for pressure increase, then are conveyed to a fan rear condenser 3-4 by a pipeline, the condensate is collected to a low-boiling substance intermediate tank 3-5, the gas phase is conveyed to a methyl chloride refining tower 4 by a pipeline, and the collected condensate in the low-boiling substance intermediate tank 3-5 is also conveyed to the methyl chloride refining tower 4 by a pump. The tower kettle dilute methanol of the separation tower 3 is heated by methanol steam discharged from the top of the low-pressure methanol rectification system in a reboiler 3-6 of the separation tower, and then is conveyed to the low-pressure methanol rectification system by a pump.
Dilute methanol from the tower bottom of a separation tower 3 is preheated by high-pressure methanol rectification system tower bottom wastewater in a first methanol rectification tower preheater 6-1, then enters a low-pressure methanol rectification system (a first methanol rectification tower 6) for rectification, tower top methanol steam is used as a heat source of a separation tower reboiler 3-6 and a methylal rectification tower reboiler 5-3, condensed methanol is collected to a first methanol rectification tower reflux tank 6-2 and is conveyed by a pump, part of the condensed methanol is refluxed to the low-pressure methanol rectification system, the rest part of the condensed methanol is used as a methanol product to exchange heat with a first-stage preheater 2-1 of a stripping tower, and the methanol product is cooled by a first methanol rectification tower cooler 6-3 and then is conveyed to a downstream methanol recovery device; the dilute methanol in the tower bottom is heated by steam at the top of a high-pressure methanol rectification system in a first methanol rectification tower reboiler 6-4, and then is conveyed to the high-pressure methanol rectification system by a pump.
Dilute methanol from the tower bottom of the low-pressure methanol rectification system is preheated by a second methanol rectification tower feeding preheater 7-1 and then enters a high-pressure methanol rectification system (a second methanol rectification tower 7) for rectification, methanol steam at the tower top is used as a heat source of a first methanol rectification tower reboiler 6-4, condensed methanol is collected to a reflux tank 7-2 of the second methanol rectification tower, part of the condensed methanol is delivered by a pump and then reflows to the high-pressure methanol rectification system, and the rest part of the condensed methanol is used as a methanol product to exchange heat with a second preheater 2-2 of a stripping tower, and then is delivered to a downstream methanol recovery device after being cooled by a second methanol rectification tower cooler 7-3; the tower bottom waste water part exchanges heat with a first methanol rectifying tower preheater 6-1 and then enters a stripping tower 2, and the part directly enters the stripping tower 2.
Non-condensable gas and low-boiling-point substances from a separation tower 3 are rectified in a methyl chloride refining tower 4, part of the gas at the top of the tower is conveyed to a methyl chloride compressor 4-1, the compressed gas enters a methyl chloride refining tower condenser 4-2, condensate is recovered to a methyl chloride refining tower reflux tank 4-3, and the non-condensable gas and gas phase extracted from the top of the tower are conveyed to a downstream methyl chloride recovery device together by a pipeline; and the condensate collected by the reflux tank 4-3 of the chloromethane refining tower refluxes to the chloromethane refining tower 4. The tower bottom liquid is heated by steam condensate water in a methyl chloride refining tower reboiler 4-4 and then is conveyed to a methylal rectifying tower 5 by a pump.
Rectifying tower bottoms from a methyl chloride refining tower 4 in a methylal rectifying tower 5, condensing tower top gas phase through a methylal rectifying tower condenser 5-1, conveying vent gas to a low-boiling fan 3-3 through a pipeline, collecting condensate to a methylal intermediate tank 5-2, conveying the condensate by a pump, partially refluxing, and conveying part of the condensate serving as a methylal product to a downstream methylal recovery device. The methanol in the tower bottom is heated by methanol steam discharged by a low-pressure methanol rectification system in a reboiler 5-3 of the methylal rectification tower, and then is conveyed to a cooler 5-4 of the methylal rectification tower by a pump for cooling, and then is conveyed to a downstream methanol recovery device by a pipeline.
The utility model also provides a grass phosphonic acid synthetic liquid tail gas recovery technology of hydrolysising, including following step:
a) mixing the tail gas from the hydrolysis of the glyphosate acidification synthetic solution with alkali liquor in an alkaline tower for reaction to obtain alkaline tower bottom liquid and neutralized tail gas;
b) mixing the alkaline tower bottom liquid and the glyphosate acidification synthetic liquid hydrolysis condensate, and then carrying out steam stripping in a stripping tower to obtain a gas phase product and a stripping tower bottom liquid;
c) rectifying and separating the neutralized tail gas and the gas-phase product in a separation tower to obtain a gas phase at the top of the separation tower and a tower bottom liquid of the separation tower;
d) rectifying and separating the gas phase at the top of the separation tower in a methyl chloride refining tower to obtain methyl chloride and a methyl chloride refining tower kettle solution;
rectifying and separating the tower bottom liquid of the methyl chloride refining tower in a methylal rectifying tower to obtain tower top methylal and tower bottom methanol;
e) rectifying and separating the tower bottom liquid of the separation tower in a methanol rectification system to obtain methanol and tower bottom liquid of the methanol rectification system, and returning the tower bottom liquid of the methanol rectification system to the stripping tower;
step d) and step e) are not in sequence.
The utility model provides an among the recovery technology, glyphosate acidizing synthetic liquid hydrolysis tail gas at first in the caustic wash tower with alkali lye mixed reaction, obtain caustic wash tower bottom liquid and neutralization tail gas. Wherein, the alkaline washing tower is preferably the alkaline washing tower in the recovery system introduced in the technical scheme of the utility model; the temperature of the mixing reaction is preferably 70 to 90 ℃, more preferably 74 ℃, and specifically 70 ℃, 71 ℃, 72 ℃, 73 ℃, 74 ℃, 75 ℃, 76 ℃, 77 ℃, 78 ℃, 79 ℃, 80 ℃, 81 ℃, 82 ℃, 83 ℃, 84 ℃, 85 ℃, 86 ℃, 87 ℃, 88 ℃, 89 ℃ or 90 ℃; the pressure of the mixing reaction is preferably-10 KPa, more preferably 0KPa, and specifically can be-10 KPa, -5KPa, -4KPa, -3KPa, -2KPa, -1KPa, 0KPa, 1KPa, 2KPa, 3KPa, 4KPa, 5KPa, 6KPa, 7KPa, 8KPa, 9KPa or 10 KPa; the circulation flow of the alkali liquor is preferably 20-40 m3H, more preferably 28m3H, in particular 20m3/h、21m3/h、22m3/h、23m3/h、24m3/h、25m3/h、26m3/h、27m3/h、28m3/h、29m3/h、30m3/h、31m3/h、32m3/h、33m3/h、34m3/h、35m3/h、36m3/h、37m3/h、38m3/h、39m3H or 40m3H; the residence time of the hydrolyzed tail gas of the glyphosate acidified synthetic liquid in the alkaline washing tower is preferably 5-20 s, and specifically can be 5s, 6s, 7s, 8s, 9s, 10s, 11s, 12s, 13s, 14s, 15s, 16s, 17s, 18s, 19s or 20 s.
The utility model provides an among the recovery process, follow the exhaust tower bottom liquid of caustic wash tower mixes with glyphosate acidizing synthetic liquid condensate of hydrolysising (rare methyl alcohol), and later mixed liquid strips in the strip tower, obtains gaseous phase product and strip tower bottom liquid. The purpose of mixing is to adjust the pH value of tower bottom liquid discharged from the alkaline washing tower by using a glyphosate acidification synthetic liquid hydrolysis condensate, wherein the pH value is preferably controlled to be 6-14; the stripping tower is preferably the stripping tower in the recovery system introduced in the technical scheme of the utility model; the temperature of the tower kettle of the stripping tower is preferably 100-108 ℃, more preferably 100-105 ℃, most preferably 103 ℃, and specifically 100 ℃, 101 ℃, 102 ℃, 103 ℃, 104 ℃, 105 ℃, 106 ℃, 107 ℃ or 108 ℃; the tower top temperature of the stripping tower is preferably 70-100 ℃, and specifically can be 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃; the pressure of the stripping tower is preferably-10-20 KPa, more preferably 0-10 KPa, most preferably 5KPa, and specifically can be-10 KPa, -5KPa, 0KPa, 5KPa, 10KPa, 15KPa or 20 KPa.
The utility model provides an among the recovery technology, the neutralization tail gas with the gas phase result carries out the rectification separation in the knockout tower, obtains knockout tower top gas phase and knockout tower cauldron liquid. Wherein, the separation tower is preferably the separation tower in the recovery system introduced in the technical scheme of the utility model; the reflux ratio of the separation tower is preferably 1-4, more preferably 2.2-2.3, and specifically can be 1, 1.2, 1.5, 1.8, 2, 2.2, 2.3, 2.5, 2.8, 3, 3.2, 3.5, 3.7 or 4; the temperature of the tower kettle of the separation tower is preferably 65-80 ℃, and specifically can be 65 ℃, 70 ℃, 75 ℃ or 80 ℃; the temperature of the top of the separation tower is 50-70 ℃, and specifically can be 50 ℃, 55 ℃, 60 ℃, 65 ℃ or 70 ℃; the pressure of the separation tower is preferably-10 KPa, more preferably 5KPa, and specifically can be-10 KPa, -5KPa, 0KPa, 5KPa or 10 KPa.
The utility model provides an among the recovery technology, the gas phase carries out the rectification separation in methyl chloride refining tower in the knockout tower top of the tower, obtains methyl chloride and methyl chloride refining tower bottom liquid. Wherein, the methyl chloride refining tower is preferably the methyl chloride refining tower in the recovery system introduced in the technical scheme of the utility model; the reflux ratio of the chloromethane refining tower is preferably 1-3.5, more preferably 1.2-1.5, and specifically can be 1, 1.2, 1.5, 1.7, 2, 2.3, 2.5, 2.7, 3, 3.2 or 3.5; the temperature of a tower kettle of the chloromethane refining tower is preferably 55-70 ℃, more preferably 60-65 ℃, and specifically can be 55 ℃, 58 ℃, 60 ℃, 62 ℃, 65 ℃, 67 ℃ or 70 ℃; the top temperature of the chloromethane refining tower is preferably-10 to-20 ℃, more preferably-15 to-17 ℃, and specifically can be-10 ℃, 11 ℃, 12 ℃, 13 ℃, 14 ℃, 15 ℃, 16 ℃, 17 ℃, 18 ℃, 19 ℃ or-20 ℃; the pressure of the methyl chloride refining tower is preferably 0-80 KPa, more preferably 55KPa, and specifically can be 0KPa, 5KPa, 10KPa, 15KPa, 20KPa, 25KPa, 30KPa, 35KPa, 40KPa, 45KPa, 50KPa, 55KPa, 60KPa, 65KPa, 70KPa, 75KPa or 80 KPa.
In the recovery process provided by the utility model, the tower bottom liquid of the methyl chloride refining tower is rectified and separated in the methylal rectifying tower to obtain the methylal at the top of the tower and the methanol in the tower bottom. Wherein, the methylal rectifying tower is preferably the methylal rectifying tower in the recovery system introduced in the technical scheme of the utility model; the reflux ratio of the methylal rectifying tower is preferably 0.5-2, more preferably 1, and specifically can be 0.5, 1, 1.5 or 2; the tower kettle temperature of the methylal rectification tower is preferably 65-85 ℃, more preferably 73 ℃, and specifically can be 65 ℃, 67 ℃, 70 ℃, 73 ℃, 75 ℃, 78 ℃, 80 ℃, 83 ℃ or 85 ℃; the top temperature of the methylal rectifying tower is preferably 35-45 ℃, and specifically can be 35 ℃, 36 ℃, 37 ℃, 38 ℃, 39 ℃, 40 ℃, 41 ℃, 42 ℃, 43 ℃, 44 ℃ or 45 ℃; the pressure of the methylal rectifying tower is preferably 0-30 KPa, more preferably 20KPa, and specifically can be 0KPa, 5KPa, 10KPa, 15KPa, 20KPa, 25KPa or 30 KPa.
The utility model provides an among the recovery technology, the fractionating tower bottom liquid carries out the rectification separation in methyl alcohol rectification system, obtains methyl alcohol and methyl alcohol rectification system tower bottom liquid, methyl alcohol rectification system tower bottom liquid returns in the strip tower. In an embodiment of the present invention, the above process specifically includes:
e1) rectifying the tower bottom liquid of the separation tower in a low-pressure methanol rectification system to obtain methanol and tower bottom liquid of the low-pressure methanol rectification system;
e2) rectifying the tower bottom liquid of the low-pressure methanol rectifying system in a high-pressure methanol rectifying system to obtain methanol and tower bottom liquid of the high-pressure methanol rectifying system, and returning the tower bottom liquid of the high-pressure methanol rectifying system to the stripping tower.
In the above methanol rectification process provided by the present invention, in step e1), the low-pressure methanol rectification system is preferably the first methanol rectification tower in the recovery system introduced in the above technical solution of the present invention; the reflux ratio of the low-pressure methanol rectification system is preferably 1-4, more preferably 1.5-2, and specifically can be 1, 1.5, 2, 2.5, 3, 3.5 or 4; the temperature of a tower kettle of the low-pressure methanol rectification system is preferably 90-120 ℃, more preferably 100-110 ℃, and specifically can be 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃ or 120 ℃; the tower top temperature of the low-pressure methanol rectification system is preferably 80-100 ℃, and specifically can be 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃; the pressure of the low-pressure methanol rectification system is preferably 0-0.3 MPa, and specifically can be 0MPa, 0.1MPa, 0.15MPa, 0.2MPa, 0.25MPa or 0.3 MPa.
In the above methanol rectification process provided by the present invention, in step e2), the high pressure methanol rectification system is preferably the second methanol rectification column in the recovery system introduced in the above technical solution of the present invention; the reflux ratio of the high-pressure methanol rectification system is preferably 1-4, more preferably 2-2.5, and specifically can be 1, 1.5, 2, 2.5, 3, 3.5 or 4; the temperature of a tower kettle of the high-pressure methanol rectification system is preferably 135-170 ℃, more preferably 150-165 ℃, and specifically can be 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃, 160 ℃, 165 ℃ or 170 ℃; the tower top temperature of the high-pressure methanol rectification system is preferably 100-120 ℃, and specifically can be 100 ℃, 105 ℃, 110 ℃, 115 ℃ or 120 ℃; the pressure of the high-pressure methanol rectification system is preferably 0.3-0.8 MPa, more preferably 0.6MPa, and specifically can be 0.3MPa, 0.4MPa, 0.5MPa, 0.6MPa, 0.7MPa or 0.8 MPa.
The utility model provides a recovery system and recovery process through to glyphosate acidizing synthetic liquid tail gas hydrolysis carry out neutralization, strip and multiple-effect rectification, have not only reduced tail gas recovery's heat energy consumption by a wide margin, have still saved the use amount of refrigerant, have reduced the emission of waste water, waste gas simultaneously, have reduced the methyl alcohol loss, have improved the quality and the rate of recovery of the methylal that the recovery obtained, chloromethane, have good economy and environmental protection benefit. Particularly, the utility model provides a recovery system and recovery process have following advantage at least:
1) by adopting a multi-effect rectification and heat integration process, the heat energy (steam) consumption and the refrigerant consumption of tail gas recovery are greatly reduced, the system energy consumption is reduced by 15-18%, and the energy cost is reduced;
2) the chloromethane refining tower is adopted to refine the chloromethane, so that the methanol and methylal in the chloromethane are recovered, and the loss of the methanol can be reduced by about 20%; the refined methyl chloride gas crude product basically does not contain other components except methyl chloride, dimethyl ether and air, the quality of the methyl chloride is improved, the problem that the consumption of sulfuric acid is high when the sulfuric acid is dried subsequently due to the fact that low-boiling-point substances such as methanol and methylal are mixed into the methyl chloride gas can be solved, and the usage amount of the sulfuric acid in a downstream sulfuric acid drying process and the treatment amount of waste sulfuric acid can be reduced by more than 55%; meanwhile, the refined chloromethane does not need water washing and alkali washing processes, so that the wastewater amount can be reduced, the equipment and electric instrument investment of the corresponding process can be reduced, and the investment cost can be reduced;
3) the methylal is recovered by adopting the methylal rectifying tower, so that the recovery rate of the methylal is improved, the methyl chloride component in the obtained methylal product is greatly reduced, and the quality of the methylal product is improved;
4) the stripping tower is adopted to carry out stripping on the wastewater, beneficial components in the three wastes are recovered, the total amount of the wastewater and the COD of the wastewater are reduced, the amount of the three wastes and the treatment cost are reduced, and the social benefit is obvious.
For the sake of clarity, the following examples are given in detail.