CN100567311C - The continuous synthetic method of a kind of glyphosate by dimethyl ester - Google Patents
The continuous synthetic method of a kind of glyphosate by dimethyl ester Download PDFInfo
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- CN100567311C CN100567311C CNB2006100534610A CN200610053461A CN100567311C CN 100567311 C CN100567311 C CN 100567311C CN B2006100534610 A CNB2006100534610 A CN B2006100534610A CN 200610053461 A CN200610053461 A CN 200610053461A CN 100567311 C CN100567311 C CN 100567311C
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Abstract
The invention provides the continuous synthetic method of a kind of glyphosate by dimethyl ester, comprise being that the synthetic liquid of feedstock production mixes the laggard hydrolysis reaction zone of going into hcl acidifying with Paraformaldehyde 96, glycine, dimethyl ester, reaction mass keeps continuous regime in hydrolysis reactor; Acidizing synthetic liquid is continuous hydrolysis in hydrolysis reaction zone, forms glyphosate salt, obtains the former powder of glyphosate with crystallization in the discharging also continuously.Wherein the preferred embodiment of hydrolysis reaction zone has " tower two stills " and forms such as " series connection of three stills ".The present invention has realized glyphosate hydrolysis serialization, and has simplified technology, can realize scale operation.
Description
Technical field
The present invention relates to the research field that the glyphosate by dimethyl ester serialization is produced.
Background technology
Glyphosate is the steriland herbicide of a kind of low toxicity, efficient, wide spectrum, at first succeeded in developing by U.S. Monsanto Company in 1974, and in the many national applications in the whole world patent protection.The nineties middle and later periods, along with its patent protection the expiring successively and the extensive plantation of resistance glyphosate transgenic crop of countries in the world, glyphosate is used has been obtained fast development, become the maximum and fastest-rising pesticide species of output.
The synthetic method of glyphosate is a lot, but industrialized operational path is present only with two, i.e. IDA technology and alkyl esterification method technology.Alkyl esterification method technology is the operational path that the most of manufacturing enterprises of China adopt.Alkyl esterification method technology is divided into dimethyl ester method and trimethyl method again.China substantially all is the still formula dimethyl ester method at intermittence that adopts band to stir at present, its level of automation is low, and single covering device ability is little, long reaction time, front and back produce and lack continuity, produce and be subject to artificial factor and the wild effect that occurs now and then, and production efficiency is low, energy utilization is unreasonable.
The reaction of dimethyl ester method hydrolysing step:
Summary of the invention
At above deficiency, the invention provides the continuous production method that a kind of dimethyl ester legal system is equipped with glyphosate.
The production process of the dimethylphosphite method glyphosate that is provided is: add Paraformaldehyde 96 in containing the methanol solution of triethylamine, be heated to 40-50 ℃ of dissolving, add glycine then, at room temperature the dissolving back adds dimethylphosphite, 60-70 ℃ of following condensation, form synthetic liquid, synthetic liquid and hcl acidifying also carry out hydrolysis reaction, obtain glyphosphonic acid with crystallization in then.
The objective of the invention is to realize glyphosate hydrolysis serialization, simplify technology and realize the scale operation of glyphosate.
Another object of the present invention is to obtain methyl chloride gas stably.
The object of the invention is achieved by following concrete technical scheme: will be that the synthetic liquid of feedstock production mixes the laggard hydrolysis reaction zone of going into hcl acidifying with Paraformaldehyde 96, glycine, dimethyl ester, reaction mass keeps continuous regime in hydrolysis reactor; Acidizing synthetic liquid is continuous hydrolysis in hydrolysis reaction zone, forms glyphosate salt, obtains the former powder of glyphosate with crystallization in the discharging also continuously.
Hydrolysis reactor is the plug flow hydrolysis reactor or mixes hydrolysis reactor entirely among the present invention, can certainly be both arbitrary combination.
The plug flow hydrolysis reactor comprises tubular reactor, tower reactor, thin-film evaporator etc., and wherein tower hydrolysis reactor comprises packing tower, tray column or void tower etc.So-called plug flow hydrolysis reactor, promptly material along with spatial displacement, constantly reacts in reactor, and reactant concn reduces gradually, and resultant concentration increases gradually, and the parameter of materials of each locus is inconsistent, and the discharge port material is a resultant.The residence time of material in reactor is identical.
The full hydrolysis reactor that mixes comprises tank reactor, mixing tank etc.The so-called full hydrolysis reactor that mixes, promptly in perfectly mixed reactor, the various parameter unanimities of the material of all locus, and also the discharge port material properties is interior identical with reactor.The residence time of material in reactor is not necessarily identical.
Hydrolysis reactor can be that a kind of in the plug flow hydrolysis reactor also can be multiple combination among the present invention; It can be one or more the combination in one or more and the perfectly mixed reactor in the plug flow hydrolysis reactor; Also can be exactly that the series connection of one-level perfectly mixed reactor or multistage perfectly mixed reactor is as hydrolysis reactor.
When hydrolysis reactor was a plurality of combination, built-up sequence was without a fixed pattern, and can be designed voluntarily by the technician according to through engineering approaches needs and reaction effect.
When adopting a kind of plug flow hydrolysis reactor among the present invention, it can be one or by a plurality of combinations as hydrolysis reactor.
The plug flow hydrolysis reactor is preferably tower reactor among the present invention.Can or be multistage tower series connection for the one-level tower.
When adopting tower reactor as the reactor of glyphosate continuous hydrolysis, acidizing synthetic liquid is from cat head or go up, the middle part enters the reaction that is hydrolyzed in the tower continuously, the hydrolyzate that hydrolysis generates flows out at the bottom of tower continuously, and in going and crystallization, and solvent is deviate from continuously from cat head in the synthetic liquid.
In order to improve hydrolysis efficiency and to be beneficial to precipitation, acidizing synthetic liquid enters the mode of reaction tower continuously can be various, can one charging in cat head or tower, and also can divide multiple spot to add hydrochloric acid at tower body.Simultaneously in order to utilize steam thermal energy to greatest extent, can carry out the secondary steam utilization, that is: cat head is deviate from steam such as solvent and be can be used as thermal source, described synthetic liquid and hydrochloric acid are carried out preheating before entering in the tower continuously, form 70-90 ℃ gas-liquid mixture, carry out precipitation, enter the reaction that is hydrolyzed in the tower again.
Simultaneously, after reaction mass enters tower, along with the rising of temperature, have HCl gas to separate out, HCl gas contacts with the synthetic liquid anti-phase of top-down liquid in tower from bottom to top, mixes, and reaction mass transfer conducts heat, and finishes reaction, helps improving the utilization ratio of hydrochloric acid.
Because the utilization ratio of hydrochloric acid improves, obvious, the consumption of alkali significantly reduces after hydrolysis is finished, thereby makes that salts contg reduces greatly in the mother liquor.At present, normally, contain a large amount of Cl in the mother liquor by adding in 30% the NaOH aqueous solution and hydrochloric acid
-, aftertreatment is brought very big pressure.Use tower reactor then effectively raises the utilization ratio of hydrochloric acid, has reduced to contain Cl
-The discharging of waste water alleviates environmental protection pressure.
Certainly, method of the present invention also can be two kinds of dissimilar combinations in the plug flow hydrolysis reactor.For example, the combination of tower and thin-film evaporator, wherein tower and thin-film evaporator all can be that one-level is also multistage.
In a word, adopt the advantage of plug flow hydrolysis reactor to be: to utilize the anti-phase of material to contact this characteristics, be more convenient for carrying out the reasonable utilization of heat energy and making full use of of hydrochloric acid.
Hydrolysis reactor also can be a perfectly mixed reactor in the continuation method of the present invention, preferred many still series connection, more preferably three stills series connection.
Characteristics based on complete mixed reaction: in perfectly mixed reactor, the various parameter unanimities of the material of all locus, and also the discharge port material properties is interior identical with reactor, and the residence time of material in reactor is not necessarily identical.Adopt perfectly mixed reactor in first step reactor, to have a certain proportion of reactant and do not have enough time to participate in reaction because of the residence time is too short.In like manner, in secondary and three grades, also there is same problem, so generally need to adopt reaction of high order realize making reaction more thorough the factor of integrated equipment investment and other each side, preferred three stills series connection when adopting perfectly mixed reactor.
Selectable, the placed in-line embodiment of three stills can followingly be carried out: be continuously fed into the first order reaction still through the synthetic liquid of cycle acidification device acidifying, reactor temperature is controlled at about 70-90 ℃, mean residence time 20～30 minutes, material is in certain liquid level in the maintenance first order reaction still, discharging is to the second order reaction still continuously, the second order reaction temperature in the kettle is controlled at 100～110 ℃, mean residence time 20～40 minutes, material is in certain liquid level in the maintenance second order reaction still, discharging is to the third order reaction still continuously, the third order reaction temperature in the kettle is controlled at 115～140 ℃, mean residence time 30～40 minutes, and the material liquid level remains on certain level in the third order reaction still, during continuously discharging is gone and Crystallization Procedure, hydrolysis finishes.And synthetic liquid and hydrochloric acid can be used as phlegma before entering hydrolytic reaction pot continuously, collect steam as thermal source, and the heat energy that utilizes steam to take out of carries out preheating to phlegma.
When adopting the many stills series connection of fully mixing, continuous stir reactor or the series connection of two stills, hydrolysis efficiency is not high, and many stills series connection can effectively improve the glyphosate hydrolysis efficiency, but have increased facility investment and the reaction times prolongs, and uneconomical.So through repeatedly experimental results show that three stills series connection, and control the residence time of each order reaction, can be good at realizing serialization, and improve the glyphosate yield.
Its advantage of the many still series connection of fully mixing continuous hydrolyzing is: because this hydrolytic process is a distillation reaction process, carrying out along with reaction, a large amount of products and solvent steam, the reaction mass volume significantly reduces, and in the batch reactor of existing technology, significantly reduces with the heat exchange contact area, influenced heat exchanger effectiveness, prolonged the reaction times greatly, plant factor reduces, and the heat energy utilization rate reduces.And the many stills of fully mixing series connection serialization can remain that material makes the tank reactor heat exchange be able to the optimum utilization state at optimal liquid level in the reactor, produces stable methyl chloride and hot steam simultaneously, is convenient to the recovery of methyl chloride and carries out the secondary steam utilization.And many stills tandem energy effectively solves the crystallisation problems in the hydrolytic process, but hydrochloric acid fails to be fully used, and heat energy utilization is also inferior to tower reaction.Bigger advantage is: the strict control of many stills tandem energy temperature of reaction at different levels reacts reaction mass, to improve the transformation efficiency of reaction in a stable optimum environment.
In the method for the present invention, the combination of preferred piston flow reactor of hydrolysis reactor and perfectly mixed reactor in the hydrolysis reaction zone, the preferred combination of tower still, the i.e. combination of tower reactor and tank reactor, the combination of an especially preferred tower two stills, preferably combination are tower-still-still in proper order.
Selectable, the embodiment of one tower, two stills can followingly be carried out: the synthetic liquid that acidifying is good is from cat head or middle part continuously feeding, the interior temperature of tower is controlled at 80～105 ℃ and carries out one-step hydrolysis just, solvent methanol and by product methylal are deviate from from cat head simultaneously, hydrolysate that generates and unreacted synthetic liquid and intermediate reaction mixture enter first step still formula hydrolysis reactor continuously at the bottom of the tower and carry out continuous hydrolysis, 100～110 ℃ of controlled temperature, continuing to enter second stage tank reactor then is hydrolyzed, controlled temperature gets glyphosate former powder with crystallization at 115～140 ℃ during discharging is gone continuously.
Tower in one tower, two stills can be tray column, packing tower or void tower etc., and is mounted in above the tank reactor of the second stage.
Aforesaid method has utilized the heat energy of steam to carry out the precipitation depickling to greatest extent, avoids rhythmic reaction owing to solvent vapo(u)r effusion imbalance and concentrated heat-energy losses that causes and heat energy are difficult to utilize.
Equally, the by-product methylal of generation also can make full use of heat energy from cat head and deviates from.
After second stage still hydrolysis reaction is finished, generate gas in addition and can return the tower bottom, heat energy is replenished in the tower, make full use of heat energy and keep temperature in the tower, and deviate from, simultaneously, be used in preheating tower jacking material, carry out the precipitation depickling from cat head.
Tank reactor can be that the heating of conventional chuck also can be adopted external hydrocone type well heater also can adopt coil heater but need add stirring among the present invention.External hydrocone type well heater need not stir, and can use the acid proof graphite material, not only can solve the problem that coil heater needs expensive high strength acid resistant material, and also can solve has crystal to separate out the problem of discharging difficulty in hydrolysis reactor sometimes.
This technical scheme has a lot of significantly beneficial effects to the hydrolysis reaction of glyphosate: (1) has realized the hydrolysis process serialization of glyphosate; (2) help improving the utilization ratio of hydrochloric acid; (3), thereby make that salts contg reduces greatly in the mother liquor because the utilization ratio of hydrochloric acid improves, and clearly the consumption of alkali significantly reduces after hydrolysis is finished.At present, normally, contain a large amount of Cl in the mother liquor by adding in 30% the NaOH aqueous solution and hydrochloric acid
-, aftertreatment is brought very big pressure.Use tower reactor then effectively raises the utilization ratio of hydrochloric acid, has reduced to contain Cl
-The discharging of waste water alleviates environmental protection pressure.(4) improve reaction efficiency, make reaction more thorough.
The method of the invention can also obtain continuously methyl chloride by-product gas stably.
As you know, alkyl esterification method is produced the glyphosate byproduct chloromethane, methyl chloride has to stimulate and anesthetic action, the major injury central nervous system functions such as human liver of unifying, enter atmosphere and can cause severe contamination, methyl chloride is the raw materials for production of a lot of products simultaneously, such as carboxymethyl cellulose, chloroprene rubber etc., the especially raw material of synthesizing organosilicon monomer.What adopt usually at present is through washing, alkali cleaning, dry tertiary treatment, and the method for recompression condensation liquefaction storage reclaims.But owing to all be to adopt interrupter method during dimethyl ester method synthesizing glyphosate at present, the methyl chloride gas of generation is not steady, is wavy, and inevitably brings air into during the course, and these have all influenced the rate of recovery and the methyl chloride quality product of methyl chloride.
The method of the invention can obtain methyl chloride gas continuously stably, and the benefit that obtains continuous methyl chloride gas stably is obvious: at first avoided carrying secretly of non-condensable gases, effectively raised the rate of recovery of methyl chloride; Secondly because the methyl chloride gas flow is steady, reduce recovery difficult, simplify recovery system; The methyl chloride gas flow is steady once more, and whole production and recovery system stopping property are strong, and leak point and reduce with the point of contact in the external world helps reducing the moisture of methyl chloride, controls the quality that it reclaims methyl chloride.
In addition, synthetic liquid can carry out acidifying by continuously acidizing mixing tank and hydrochloric acid among the present invention, and the synthetic liquid that acidifying is good enters the hydrolysis reaction zone reaction.The continuously acidizing mixing tank can be still formula or tubular type, also can be for circulating.
In sum, glyphosate continuous production method among the present invention has beyond thought beneficial effect, is mainly reflected in:
(1), realized the hydrolysis serialization of glyphosate production;
(2), improved the hydrolysis efficiency of glyphosate production, reduced the consumption of follow-up alkali, the salt amount reduces in the mother liquor thereby make, and alleviates environmental protection pressure.
(3), continuously obtain methyl chloride gas stably, improve the rate of recovery.
(4), simultaneously realize the precipitation depickling, effectively utilize heat energy.
Description of drawings
Fig. 1 is the schematic flow sheet of " tower two stills " provided by the present invention embodiment.
Embodiment
The invention provides a kind of method of continuous synthesizing glyphosate, comprise: will be that the synthetic liquid of feedstock production mixes the laggard hydrolysis reaction zone of going into hcl acidifying with Paraformaldehyde 96, glycine, dimethyl ester, reaction mass is continuous hydrolysis in hydrolysis reactor, form glyphosate salt, obtain the former powder of glyphosate with crystallization in the discharging also continuously.
Embodiment 1
The mol ratio of synthetic liquid (in glycine) and hydrochloric acid is 1: 3.1 a acidizing synthetic liquid, input speed with 1.28 tons/h enters hydrolysis reaction zone, hydrolysis reactor adopts the combined reactor of a tower two stills, acidizing synthetic liquid is first from the cat head continuously feeding, the interior temperature of tower is controlled at 90～100 ℃ and carries out one-step hydrolysis just, solvent methanol is deviate from from cat head simultaneously, hydrolysate that generates and unreacted synthetic liquid and intermediate reaction mixture enter first step still formula hydrolysis reactor continuously at the bottom of the tower and carry out continuous hydrolysis, 100～110 ℃ of controlled temperature, continuing to enter second stage tank reactor then is hydrolyzed, controlled temperature is at 124～128 ℃, get the former powder of glyphosate with crystallization during discharging is gone continuously, the glyphosate total recovery is 84.1%.
Embodiment 2
The mol ratio of synthetic liquid (in glycine) and hydrochloric acid is 1: 3.4 a acidizing synthetic liquid, input speed with 1.28 tons/h enters hydrolysis reaction zone, hydrolysis reactor adopts the combined reactor of a tower two stills, acidizing synthetic liquid is first from tower middle part continuously feeding, the interior temperature of tower is controlled at 90～100 ℃ and carries out one-step hydrolysis just, solvent methanol is deviate from from cat head simultaneously, hydrolysate that generates and unreacted synthetic liquid and intermediate reaction mixture enter first step still formula hydrolysis reactor continuously at the bottom of the tower and carry out continuous hydrolysis, 100～110 ℃ of controlled temperature, continuing to enter second stage tank reactor then is hydrolyzed, controlled temperature is at 124～128 ℃, get the former powder of glyphosate with crystallization during discharging is gone continuously, the glyphosate total recovery is 84.0%.Having made full use of steam thermal energy among the present invention, is the condenser of overhead vapours in the first-stage condenser of cat head, and the preheater that also is initial material is to make full use of heat energy.
Embodiment 3
Synthetic liquid (in glycine) is squeezed into circulation blender with 1: 3.4 ratio with the constant current volume pump with the mol ratio of hydrochloric acid, its total flux is 1.28 tons/h, circular flow is 10 tons/h, attach together through the laggard entry system of solutions of first-stage condenser then and put (tower two stills) and be hydrolyzed, tower top temperature is controlled at 92 ℃, one-stage hydrolysis tower still temperature is 110 ℃, secondary hydrolysis tower still temperature is 120 ℃, in synthetic liquid still mean residence time all is 35min, hydrolyzed solution add alkali crystallization 8h filter the product glyphosate, the glyphosate total recovery is 84.5%.
Embodiment 4
Synthetic liquid (in glycine) is squeezed into circulation blender with 1: 3.1 ratio with the constant current volume pump with the mol ratio of hydrochloric acid, its total flux is 1.28 tons/h, circular flow is 10 tons/h, attach together to put through the laggard entry system of solutions of first-stage condenser then and be hydrolyzed, the hydrolysis associated plant is got the combination of two stills, two towers, the one-stage hydrolysis tower top temperature is controlled at 64.5 ℃, the still temperature is 110 ℃, secondary hydrolysis tower top temperature is controlled at 98 ℃, the still temperature is 128 ℃, in synthetic liquid still mean residence time all is 35min, hydrolyzed solution add alkali crystallization 8h filter the product glyphosate, the glyphosate total recovery is 85.0%.
Embodiment 5
Synthetic liquid (in glycine) is squeezed into circulation blender with 1: 3.1 ratio with the constant current volume pump with the mol ratio of hydrochloric acid, its total flux is 1.28 tons/h, circular flow is 10 tons/h, attach together to put through the laggard entry system of solutions of first-stage condenser then and be hydrolyzed, the hydrolysis associated plant is got the combination of two stills, one tower, the one-stage hydrolysis tower top temperature is controlled at 64.5 ℃, the still temperature is 110 ℃, secondary hydrolysis tower top temperature is controlled at 98 ℃, the still temperature is 128 ℃, in synthetic liquid still mean residence time all is 35min, hydrolyzed solution add alkali crystallization 8h filter the product glyphosate, the glyphosate total recovery is 85.2%.
Embodiment 6
Synthetic liquid (in glycine) is squeezed into circulation blender with 1: 3.4 ratio with the constant current volume pump with the mol ratio of hydrochloric acid, its total flux is 1.28 tons/h, circular flow is 10 tons/h, attach together to put through the laggard entry system of solutions of first-stage condenser then and be hydrolyzed, the hydrolysis associated plant is got the combination of two stills, one-stage hydrolysis still temperature is 110 ℃, secondary hydrolysis kettle temperature is 128 ℃, in synthetic liquid mean residence times at different levels is 30min, hydrolyzed solution add alkali crystallization 8h filter the product glyphosate, the glyphosate total recovery is 83.5%.
Embodiment 7
Synthetic liquid (in glycine) is squeezed into circulation blender with 1: 3.4 ratio with the constant current volume pump with the mol ratio of hydrochloric acid, its total flux is 1.28 tons/h, circular flow is 10 tons/h, attach together to put through the laggard entry system of solutions of first-stage condenser then and be hydrolyzed, the hydrolysis associated plant is got the combination of three stills, one-stage hydrolysis still temperature is 70 ℃, secondary hydrolysis kettle temperature is 100 ℃, three grades of hydrolysis kettle temperature are 115 ℃, in synthetic liquid mean residence times at different levels is 30min, hydrolyzed solution add alkali crystallization 8h filter the product glyphosate, the glyphosate total recovery is 84.6%.
Synthetic liquid (in glycine) is squeezed into circulation blender with 1: 3.3 ratio with the constant current volume pump with the mol ratio of hydrochloric acid, its total flux is 1.28 tons/h, circular flow is 10 tons/h, attach together to put through the laggard entry system of solutions of first-stage condenser then and be hydrolyzed, the hydrolysis associated plant is got the combination of three stills, one-stage hydrolysis still temperature is 90 ℃, secondary hydrolysis kettle temperature is 110 ℃, three grades of hydrolysis kettle temperature are 140 ℃, in synthetic liquid grade mean residence time is about 30min, hydrolyzed solution add alkali crystallization 8h filter the product glyphosate, the glyphosate total recovery is 85.0%.
Comparing embodiment 1
Rhythmic reaction, the mol ratio of synthetic liquid (in glycine) and hydrochloric acid slowly was warmed up to 130 ℃ in 1.5 hours then with 1: 3.4 ratio acidifying, hydrolyzed solution add alkali crystallization 8h filter the product glyphosate, the glyphosate total recovery is 80.3%.
Claims (15)
1, a kind of dimethyl ester legal system is equipped with the continuous production method of glyphosate, and this method comprises: will be that the synthetic liquid of feedstock production mixes the laggard hydrolysis reaction zone of going into hcl acidifying with Paraformaldehyde 96, glycine, dimethyl ester, and keep continuous regime in hydrolysis reaction zone; Acidizing synthetic liquid is continuous hydrolysis in hydrolysis reaction zone, form the glyphosate hydrochloride product, obtain glyphosphonic acid with crystallization in the continuous discharging of mixture of generation product or generation product and acidizing synthetic liquid also, it is characterized in that, comprise one or more hydrolysis reactors in the hydrolysis reaction zone, this hydrolysis reactor is the plug flow hydrolysis reactor, or is complete mixed hydrolysis reactor, or is plug flow hydrolysis reactor and full arbitrary combination of mixing hydrolysis reactor.
2, the method for claim 1 is characterized in that the plug flow hydrolysis reactor is tower reactor, tubular reactor or thin-film evaporator.
3, method as claimed in claim 2 is characterized in that the plug flow hydrolysis reactor is tower hydrolysis reactor.
4, the method for claim 1 is characterized in that mixing hydrolysis reactor entirely is tank reactor.
5, method as claimed in claim 4 is characterized in that described tank reactor adopts external hydrocone type well heater or coil heater.
6, the method for claim 1, it is characterized in that the hydrolysis reactor that hydrolysis reaction zone comprises is the combination of a tower reactor and placed in-line two tank reactors, the synthetic liquid that acidifying is good is introduced into tower reactor continuously, enters tank reactor then and obtains glyphosphonic acid with crystallization in the discharging more continuously.
7, method as claimed in claim 6 is characterized in that the interior temperature of tower of tower reactor is controlled to be 80-105 ℃, and first still still temperature control of material process is made as 90-115 ℃, and the temperature control of second still still is made as 115-140 ℃.
8, method as claimed in claim 6, it is characterized in that mode that acidizing synthetic liquid enters tower reactor continuously be acidizing synthetic liquid by one charging in cat head or the tower, or divide multiple spot to add hydrochloric acid at tower body.
9, as claim 6 or 7 described methods, it is characterized in that described synthetic liquid and hydrochloric acid before entering in the tower continuously, carry out preheating earlier, form 70-90 ℃ gas-liquid mixture, enter again and carry out elementary hydrolysis reaction in the tower.
10, method as claimed in claim 9 is characterized in that previous crops is a phlegma in the tower entering continuously for described synthetic liquid and hydrochloric acid, and cat head is deviate from steam as thermal source, and the heat energy that utilizes steam to take out of carries out preheating to phlegma.
11, method as claimed in claim 6, it is characterized in that hydrolysis reaction finish after gas enter the tower bottom, and deviate from from cat head.
12, the method for claim 1 is characterized in that hydrolysis reactor is three tank reactor series connection.
13, method as claimed in claim 12, when it is characterized in that the synthetic liquid of acidifying is continuously fed into first reactor, the first reactor temperature in the kettle is controlled to be 70-90 ℃, when discharging is in second reactor continuously, controlling second temperature of reaction kettle is 100-110 ℃, in the time of in continuous again discharging to the three reactors, controlling the 3rd temperature of reaction kettle is 115-140 ℃.
14, method as claimed in claim 13, it is characterized in that hydrolysis material mean residence time in first reactor is 20-30 minute, mean residence time is 20-40 minute in second reactor, and mean residence time is 30-40 minute in the 3rd reactor.
15, the method for claim 1 is characterized in that this method obtains methyl chloride continuously reposefully.
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| CN101085783B (en) * | 2007-07-04 | 2011-09-14 | 四川省乐山市福华通达农药科技有限公司 | Method for hydrolyzing glyphosate acid |
| CN101628878A (en) * | 2008-07-20 | 2010-01-20 | 李坚 | N-hydroxymethylglycine phosphite, preparation thereof and application thereof |
| CN101704840B (en) * | 2009-04-27 | 2012-06-13 | 南通泰禾化工有限公司 | Crystallization method for continuous desolvation production of glyphosate by using glycocoll method |
| CN101704843B (en) * | 2009-04-27 | 2013-09-18 | 南通泰禾化工有限公司 | Glyphosate continuous desolventizing production process |
| CN104744509B (en) * | 2013-12-31 | 2017-02-08 | 浙江金帆达生化股份有限公司 | Hydrolysis device for continuously synthesizing glyphosate and application of hydrolysis device |
| CN108285426A (en) * | 2017-10-30 | 2018-07-17 | 赵君 | A kind of continuously acidizing device and its technique |
| CN110922426B (en) * | 2019-11-22 | 2022-04-22 | 湖北泰盛化工有限公司 | Alkyl ester method glyphosate continuous production system and process |
| CN111214944A (en) * | 2020-03-16 | 2020-06-02 | 浙江新安化工集团股份有限公司 | Method and system for recovering hydrolysis tail gas of glyphosate synthetic liquid |
| CN111269089A (en) * | 2020-03-16 | 2020-06-12 | 浙江新安化工集团股份有限公司 | Method and system for recovering hydrolysis tail gas of glyphosate synthetic liquid |
| CN111205319B (en) * | 2020-03-16 | 2023-08-22 | 浙江新安化工集团股份有限公司 | Continuous synthesis method and system of glyphosate |
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