CN106699808B - A kind of acidolysis of producing glyphosate by using glycine and solvent recovery process and device - Google Patents
A kind of acidolysis of producing glyphosate by using glycine and solvent recovery process and device Download PDFInfo
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- CN106699808B CN106699808B CN201611097724.8A CN201611097724A CN106699808B CN 106699808 B CN106699808 B CN 106699808B CN 201611097724 A CN201611097724 A CN 201611097724A CN 106699808 B CN106699808 B CN 106699808B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/3804—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se) not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
- C07F9/3813—N-Phosphonomethylglycine; Salts or complexes thereof
Abstract
The present invention relates to a kind of glyphosate by using glycine production process acidolysis and solvent recovery process, belong to glyphosate production process technical field.It includes the processes such as the pretreatment of Synthesis liquid separating methanol, sour methanol acidolysis, hydrochloric acidolysis, solvent recovery, and hydrochloric acid is substituted for Synthesis liquid acidolysis using sour methanol, and the acidolysis later stage, which mends, throws a small amount of hydrochloric acid to stablize high temperature section acid hemolysis process.The dimethoxym ethane and methanol aqueous solution generated in acid hemolysis process separates dimethoxym ethane through rectifying, remaining methanol aqueous solution supplements a small amount of methanol allotment content after cooling, it is then directly used for absorbing hydrogen chloride gas, control hydrogen chloride, methanol reach output acid methanol after set content, return to hydrolysis procedure use.It is of the invention compared with existing glyphosate by using glycine acidolysis and solvent recovery technology, it can reduce more than Methanol Recovery waste water 2.5t/t, reduce more than mother liquor amount 0.3t/t, reduce more than steam steam consumption 1.5t/t, save electricity more than 80KWh/t, improve chloromethanes yield 0.3t/t, improve glyphosate yield more than 0.3%, glyphosate production cost reduction 15~20%.
Description
Technical field
The present invention relates to the new of a kind of glyphosate by using glycine production process acidolysis (hydrolysis) process and solvent recovery process
Type technique belongs to glyphosate production process technical field.
Background technology
Glyphosate is a kind of inner sucting conduction type, efficient, low toxicity, wide spectrum, steriland herbicide, at first by U.S.'s Monsanto public affairs
Department's exploitation has the production of more than 40 years, usage history, is at present the pesticide species of global volume of production and marketing maximum.China is glyphosate master
One of producing country is wanted, about 700,000 tons of 2015 annual capacity of glyphosate industry, about 460,000 tons of actual production, production capacity, yield are the whole world
First.The production line of glyphosate is divided into glycine-alkyl esterification method (abbreviation glycine method) and iminodiacetic acid (salt) acid system (referred to as
IDA methods) two kinds.China's glyphosate industry, glycine method occupy leading position again, and 2015, national glyphosate by using glycine produced
Can be about that 75%, actual production is about 80%.
Glycine method mainstream route is divided into dimethyl phosphate method and Trimethyl phosphite method.In China, due to using sub-
The enterprise of dimethyl phosphate method production glyphosate is more, and process units is larger, which is produced in recent years by optimizing, work
Skill condition, appliance arrangement, automation operating system etc. all achieve a series of technological progress, and product quality indicator reaches
International market requirement, thus " glycine-dimethylphosphite " route occupy leading position in China." glycine-phosphorous acid
Dimethyl ester " route, be by paraformaldehyde, glycine, dimethylphosphite in the presence of solvent methanol and catalyst of triethylamine into
Row synthetic reaction generation main component is the Synthesis liquid of organophosphor intermediate, and acidolysis (hydrolysis) is then carried out with hydrochloric acid and reacts obtained
Glyphosate.
" glycine-Trimethyl phosphite " route compared with dimethylphosphite route, makes of water instead of methanol molten
Agent makees catalyst with sodium hydroxide instead of triethylamine, reduces post processing, but since the price of trimethyl is higher than dimethyl ester,
Consequently only that its cost of the enterprise of the self-produced trimethyl of only a few just has certain market competitiveness, according to the open source information country
No enterprise uses the technique." glycine-dimethylphosphite " route key reaction formula is as follows：
★ glyphosate synthesis solution key reactions are as follows：
First：Depolymerization reaction
Second：Condensation reaction
Third：Esterification
Existing glyphosate by using glycine acidolysis (hydrolysis) process (it is water-soluble to refer in particular to hydrogen chloride using the hydrochloric acid of 30% or so content
Liquid, similarly hereinafter) carry out acidolysis (hydrolysis).
Hydrochloric acid is the aqueous solution also known as hydrochloric acid of hydrogen chloride, is chemical process to be colourless to light yellow transparent liquid
In a kind of customary acid, technical hydrochloric acid is generally configured to 30% or so content.Salt acid starting material is easy to get, cheap, and and water
Azeotropic mixture can be formed, so industrial use is extensive, this is also the main original of the acidolysis of glyphosate tradition (hydrolysis) process choice hydrochloric acid
Cause.
But this method shortcoming is also apparent.Acidolysis (hydrolysis) process, active ingredient are only the chlorination for 30% ratio that accounts for
Hydrogen, up to 70% water then passively introduce reaction system.The introducing of a large amount of water, causes the process waste liquors such as mother liquor and methanol waste water
A series of problems, such as amount is big, waste liquid entrainment and dissolved material loss are big, environmental protection pressure is big, process energy consumption is big.In addition, because of introducing
Water is big, and the specific heat capacity of water and enthalpy of phase change are higher, the high energy consumption during heating, evaporation, cooling condensation, rectifying separation etc..
According to measuring and calculating, in the technique that acidolysis (hydrolysis) is carried out using hydrochloric acid, only solvent recovery process energy consumption just accounts for glyphosate energy consumption
More than 40%, wherein because the energy consumption that this part water that hydrochloric acid is brought into triggers accounts for major part.
Furthermore " methoxyl group " in system is introduced into when Synthesis liquid synthesis procedure adds in dimethylphosphite raw material both can be with
Acidolysis generation chloromethanes occurs with hydrogen chloride, and hydrolysis generation methanol can occur with water.Its key reaction formula is：
Acidolysis (hydrolysis) is carried out in ★ traditional handicrafts with Synthesis liquid using hydrochloric acid (aqueous solution of hydrogen chloride) to react, it is main anti-
It should be as follows：
Fourth：Acidolysis (hydrolysis) is reacted
From more than reaction equation, in the technique that hydrochloric acid is used to carry out acidolysis (hydrolysis), " methoxyl group " while and chlorination
Hydrogen and
(1), (2) two reactions have occurred in water：
Wherein, only about 60% " methoxyl group " generates chloromethanes with hydrogen chloride generation acidolysis reaction, separately there is about 40%
" methoxyl group " occurs hydrolysis with water and generates methanol.
In the production process of glyphosate by using glycine, the technique of traditional glyphosate synthesis solution acidolysis (hydrolysis) uses
30% specification hydrochloric acid carries out acidolysis (hydrolysis).Synthesis liquid and hydrochloric acid bring the water in system into, and a part is through gas-guide tube with gas phase
Into solvent recovering system and finally entered in the form of methanol waste water at dirt and stood, another part enters Crystallization Procedure and most with liquid phase
Enter eventually in glyphosate mother solution.In the technical process, the water that hydrochloric acid is brought into converts into 2.1t/t or so (i.e.：Glyphosate production per ton
The water system hydrochloric acid for having about 2.1 tons in raw waste water brings system into), account for waste liquid (Methanol Recovery waste water and mother liquor) total amount 20% is left
The right side accounts for 40% or so of total Water in waste liquid.
Whether glyphosate mother solution or Methanol Recovery waste liquid, in view of its attribute,《National Hazard waste register》Its is bright
Hazardous waste really is defined as, must be managed, dispose according to hazardous waste, to prevent environmental pollution, environmental protection and human body are good for
Health.And it is always an industry problems and Chinese pesticide industry association, China Environmental Science research that glyphosate mother solution processing is difficult
The problem that the government departments such as Yuan Deng mechanisms and Environmental Protection Department pay high attention to.For enterprise, then concerning survival, how effectively to locate
The problem of managing mother liquor, decontrol waste water almost becomes the life and death board of each glyphosate by using glycine manufacturer.Therefore, innovation production
Technique from glyphosate mother solution is reduced in glyphosate synthesis production technology source, Methanol Recovery waste liquid generates, is set about from post processing link
The degradation efficiency of the waste liquids such as mother liquor is improved, is the important research direction of glyphosate industry pollution control problem, this process program
It is the optimization innovation carried out on this direction.
The content of the invention
Present invention aims at by new process, the water in addition system is reduced, the waste liquids such as mother liquor is reduced and generates
Amount improves glyphosate yield；Novel solvent recovery method is taken, reduces electricity, steam energy in glyphosate by using glycine production process
Source consumes；The reaction selectivity for the methoxyl group that dimethylphosphite is brought into is improved, orientation is converted into the higher chloromethanes of added value,
Increase chloromethanes yield.Generally achieve the purpose that energy-saving and environmental protection, reduce production cost, improve comprehensive benefit.
The utility model technique carries out acidolysis (hydrolysis) using the methanol solution (referred to as sour methanol, similarly hereinafter) of hydrogen chloride, only in height
Thermophase supplements a small amount of hydrochloric acid.
Sour methanol is the methanol solution of hydrogen chloride, to be colourless to light yellow transparent liquid, is mainly used in medicine, pesticide
Organic syntheses aspect is waited to play the role of blocking group to anhydrous response acid adding.Industrial acids methanol is generally its saturated solution,
Wherein hydrogen chloride content is generally in 20-35%.Since hydrogen chloride and methanol cannot form azeotropic mixture, with respect to hydrochloride aqueous solution
For (i.e. hydrochloric acid), 70 DEG C of temperatures above stability inferiors are poor, so specific group technology measure is taken in the present invention, with
Ensure that stable reaction carries out and reaches technological requirement.Carrying out industrial analysis to glyphosate by using glycine acidolysis (hydrolysis) process can
Know, the hydrogen chloride in addition system is with glycine molar ratio in (2.8~3.3):1, wherein 32% hydrogen chloride is sent out with triethylamine
Acidolysis reaction occurs for raw reaction, 46% hydrogen chloride, and only 22% hydrogen chloride is to provide acidity.In this process program, using acid
Methanol substitutes hydrochloric acid, and controls the hydrogen chloride in addition system with glycine molar ratio in (3.3~3.9):1, in addition take group
Closing technological measure ensures process stabilizing.
It should be strongly noted that because glyphosate acidolysis (hydrolysis) process is not to avoid water reaction, so being prepared in sour methanol
In the process, it is not necessary to it is required that being absolute, dilute methanol, dilute hydrochloric acid etc. are all kinds of can be used to be carried out containing the solution of methanol and hydrogen chloride
Allotment, it is ensured that hydrogen chloride, methanol content are in control range.
Its main acidolysis (hydrolysis) reaction equation is as follows：
In ★ novel process of the present invention acidolysis (hydrolysis) is carried out with Synthesis liquid using sour methanol (methanol solution of hydrogen chloride)
Reaction, key reaction are as follows：
Penta：Acidolysis (hydrolysis) is reacted
Comparison understands that this method is substantially to substitute carrier of the water as hydrogen chloride gas using methanol, is meeting grass
On the premise of sweet phosphonic acids solution (hydrolysis) technological requirement, the water in the system of bringing into is greatly reduced.Meanwhile linkage uses solvent
New recovering technology, during being somebody's turn to do, it is only necessary to separate the dimethoxym ethane in methanol, dimethoxym ethane aqueous solution, remaining methanol-water
Solution adds in a small amount of methanol allotment content after cooling, is then directly used for absorbing hydrogen chloride gas, and production contains a small amount of water
Sour methanol.Realize the linkage benefit such as energy saving, consumption reduction, emission reduction, synergy.
In former technique, after Synthesis liquid and mixed in hydrochloric acid, because the objective reality of water, about 40% " methoxyl group " hydrolyzes
Reaction generates methanol.And in the present invention, due to addition be methanol hydrogen chloride solution, introduce water it is few, methoxyl group master
It reacts (1)：CH3O-+HCl→CH3Cl reduces reaction (2)：
CH3O-+H2O→CH3OH, " methoxyl group " that dimethylphosphite is brought into overwhelming majority orientation be converted into added value compared with
High chloromethanes, improves reaction selectivity.
Process before the synthesis, the raw materials such as methanol, paraformaldehyde, glycine, dimethylphosphite are through depolymerization, condensation, esterification
The mixed liquor (mixed liquor being referred to as Synthesis liquid, similarly hereinafter) that main component is organophosphor intermediate is generated, which is specially
The novel process of Synthesis liquid acidolysis (hydrolysis) and the novel process of follow-up solvent recovery.Present invention aims at pass through glyphosate
New acidolysis (hydrolysis) process of Synthesis liquid reduces the water in addition system, reduces the waste liquids yields such as mother liquor, improves
Glyphosate yield；Novel solvent recovery method is taken, reduces the electricity in glyphosate by using glycine production process, steam energy consumes；
The reaction selectivity for the methoxyl group that dimethylphosphite is brought into is improved, orientation is converted into the higher chloromethanes of added value, increases chlorine
Methane production.Generally achieve the purpose that energy-saving and environmental protection, reduce production cost, improve comprehensive benefit.
Specific process step includes
(1) Synthesis liquid pre-processes：The methods of first being pre-processed to glyphosate synthesis solution, that is, taking vacuum distillation will synthesize
Solvent methanol removing in liquid, to reduce free methanol amount in Synthesis liquid, reduces follow-up acidolysis reaction kettle material total amount, increases simultaneously
Big main reaction material molar concentration promotes positive reaction to carry out.Optimal Control index：50-65 DEG C of vacuum degree >=75KPa, temperature.First
Whether alcohol removing amount (removing ratio) selects to remove, with specific reference to follow-up acidolysis reaction kettle and its corollary apparatus technological design
Situation determines, if the volume and treating capacity of acidolysis reaction kettle and its corollary apparatus are enough, also methanol in Synthesis liquid can not be carried out
Removing.
(2) the acidolysis early period stage：By since being added in sour methanol acidolysis be known as acidolysis early period to the stage for being warming up to 78 DEG C
Stage.Concrete scheme is that pretreated Synthesis liquid is put into acidolysis kettle, in the sour methanol that 20-45 DEG C adds in described in sour methanol
Middle hydrogen chloride content is 20-35%, methanol content is 50-80% and aqueous 0-30%, and inventory is according to wherein hydrogen chloride
Content and process unit concrete condition make choice and calculate：The molar ratio of hydrogen chloride and glycine control 1.5~2.8：1,
It is denoted as a:1.Slowly heated up to material in acidolysis kettle by chuck using steam, by the mixeding liquid temperature of Synthesis liquid and sour methanol by
45 DEG C or so are raised slowly to 78 DEG C or so, and for stage control Wen Sheng per 4.5 DEG C or so of half an hour, control reaction time 3-4 is small
When.It should be strongly noted that because glyphosate hydrolysis procedure is not to avoid water reaction, so in sour methanol preparation process, it is not necessary to
It is required that being absolute, all kinds of solution containing methanol and hydrogen chloride such as dilute methanol, dilute hydrochloric acid can be used to be allocated, it is ensured that
Hydrogen chloride, methanol content are in control range.
(3) the later stage acidolysis stage：78 DEG C to 108 DEG C of stage is known as the acidolysis stage in later stage.In the acidolysis later stage, add in few
Hydrochloric acid is measured, to make up the problem of sour methanol high-temperature stability is bad, continues acidolysis reaction.Specially：Treat object in acidolysis kettle
When material temperature degree rises to 78 DEG C, the hot hydrochloric acid that content is 30%, temperature is 78 DEG C is quantitatively adding, specific inventory is according to wherein chlorine
Change the sour quantity of methyl alcohol added in the content of hydrogen and early period acid hemolysis process (to be converted see step 2)：Hydrogen chloride and glycine
Molar ratio controls [(3.3~3.9)-a]：1.Hydrochloric acid is added, continues slowly to heat up to material in acidolysis kettle, by temperature by 78 DEG C of left sides
The right side is raised slowly to 108 DEG C or so, and stage control Wen Sheng is per 5 DEG C or so of half an hour, when control reaction time 3-4 is small.
(4) high temperature deacidification stage：By 108 DEG C to reaction finishes, the stage of blowing is known as high temperature deacidification stage.In acidolysis kettle
When temperature of charge rises to 108 DEG C, remaining hydrogen chloride and water form azeotropic in kettle, at this time switch tail gas, the azeotrope warp steamed
The dilute hydrochloric acid that content is 20% is obtained after condenser cooling, goes to the sour methanol of allotment production；Incoagulable gas is gone to chloromethanes and is returned
Sequence of knocking off recycles chloromethanes.When being warming up to 115 DEG C or so, reach reaction end, material starts to crystallize, and turns down steam, heat preservation about
A small amount of water is added in after half an hour to cool down material, is then discharged to crystallization kettle, is transferred to and is washed after glyphosate sufficient crystallising
Material machine carries out washing material, obtains glyphosate.
(5) solvent recovery process：108 DEG C of pervious condensed device condensations of tail gas, obtain the aqueous solution of dimethoxym ethane, methanol,
Incoagulable gas goes to chloromethanes recovery process recycling chloromethanes.Dimethoxym ethane, the aqueous solution of methanol enter dimethoxym ethane rectifying column, control
39~46 DEG C of tower top temperature processed, 77~82 DEG C of column bottom temperature, tower top pressure -10~10KPa, the isolated dimethoxym ethane production of tower top
Product；Bottom of towe obtains the methanol aqueous solution that methanol content is 80% or so, goes to absorption plant absorbing hydrogen chloride gas after cooling,
The sour methanol of allotment production.Sour methanol goes to hydrolysis procedure reuse.Technical scheme has the following effects that：
1st, electricity, steam energy consumption are reduced.This method brings the water in system into during reducing acidolysis (hydrolysis), while to wash
The processing of methanol aqueous solution provides a kind of new way, thus the energy saving amplitude in acidolysis (hydrolysis) process and solvent recovery process
Greatly.
2nd, reduce glyphosate by using glycine production process waste liquid to generate, reduce the discharge of pollutant, reduce liquid waste processing into
Sheet and environmental protection pressure.At the same time, the discharge reduction in the technique addition system is returned with the glyphosate of mother liquor loss and with methanol
It receives the methanol that waste water is lost in reduce, realizes and improve glyphosate yield, reduce methanol unit consumption.
3rd, increase the yield of the higher chloromethanes byproduct of added value, promote glyphosate production process comprehensive benefit.Relatively
Traditional hydrochloric acidolysis (hydrolysis) technique during the invented technology, selectively brings raw material dimethylphosphite into
Methoxyl group is converted into the higher chloromethanes of added value in acidolysis (hydrolysis) process orientation reaction, can increase chloromethanes by-product total amount,
Increase glyphosate production process overall economic efficiency.
4th, glyphosate mother solution oxidative degradation efficiency is improved.Due to discharge reduction, glyphosate mother solution concentration increases, after mother liquor
Oxidative degradation efficiency improves during reason, achievees the purpose that reduce glyphosate mother solution processing environmental protection pressure and processing cost.
(i.e. hydrogen chloride is water-soluble using hydrochloric acid in sour methanol (i.e. the methanol solution of hydrogen chloride) replacement traditional handicraft by the present invention
Liquid) and Synthesis liquid progress acidolysis reaction.In traditional handicraft, the main content of hydrochloric acid that glyphosate acidolysis uses is remaining 30% or so
70% ingredient is water.This programme carries out acidolysis reaction using sour methanol with Synthesis liquid, in the case where not influencing main reaction, reduces
It brings the water in system into, reduces mother liquor and Methanol Recovery waste water total amount.
Meanwhile solvent recovery process is also improved, in the present invention, methanol, the dimethoxym ethane of hydrolysis procedure output are water-soluble
Liquid separates dimethoxym ethane through rectifying, and remaining methanol aqueous solution adds in a small amount of methanol allotment content, is then directly used for after cooling
Absorbing hydrogen chloride gas produces sour methanol, is back to use hydrolysis procedure；Only a small amount of methanol aqueous solution is refined through methanol column rectifying output
Methanol, with the material total amount in balance system.Energy consumption and wastewater flow rate in production process are greatly reduced.
This method compares traditional handicraft, and emission reduction, energy-saving benefit are big.First, hydrolysis procedure reduction brings in system water into about
Water about 1.2t/t in system is brought in 1.6t/t, the reduction of solvent recovery process into, and overall process consumes steam about 1.5t/t less, few to generate
More than mother liquor 0.3t/t generates more than Methanol Recovery waste water 2.5t/t less.Second is that solvent recovery process, rectifying separate dimethoxym ethane with
Methanol aqueous solution afterwards directly to absorbing hydrogen chloride gas, produces sour methanol, is back to use hydrolysis procedure after cooling, only few
Amount methanol aqueous solution goes to methanol rectifying tower and purifies to obtain refined methanol with the total material of balance system.Because no longer high-volume carries out first
Alcohol rectifying is recycled, so save point and steam, and is realized when no longer largely discharging the methanol waste water of high COD and to be reduced methanol and disappear
Consumption.Only the process can save a large amount of steam, and reduce more than waste water 1.2t/t that (the tower steam condensate (SC) enters useless in former technique
In water).
Hydrochloric acid (aqueous solution for refering in particular to hydrogen chloride) in traditional handicraft, which is replaced, using sour methanol carries out acidolysis reaction with Synthesis liquid.
The methoxyl group that raw material dimethylphosphite is brought into largely turns to be selectively converted to the higher chlorine of added value in acid hemolysis process
Methane, the yield of byproduct chloromethanes rise 0.3t/t or so (rising to 0.85t/t or so by 0.55t/t or so), increase grass
Sweet phosphine production process overall economic efficiency.
Because glyphosate hydrolysis procedure is not to avoid water reaction, so in sour methanol preparation process, it is not necessary to it is required that being absolute nothing
Water can use all kinds of solution containing methanol and hydrogen chloride such as dilute methanol, dilute hydrochloric acid to be allocated, it is ensured that hydrogen chloride, methanol
Content is in control range.Therefore, the link of hydrogen chloride and methanol-fueled exhaust, tail gas washing are related in production process
Tower, which absorbs water, to realize emission reduction with reuse for allocating the sour methanol of production.
Hydrogen chloride gas source in above-mentioned may be from the chlorination of glyphosate material process dimethylphosphite device by-product
Hydrogen or from chlor-alkali, the synthesising hydrogen of glyphosate cogeneration enterprise chlor-alkali devices or from organosilicon, glyphosate cogeneration enterprise
The hydrogen chloride tail gas of chloromethanes synthesizer or other source hydrogen chloride tail gas for enterprise is produced in above-mentioned association, have production
The mating comprehensive benefit of industry chain.
Because hydrolysis procedure introduce water it is few, under the premise of depickling link, same soaking time and energy consumption, hydrogen chloride and
Water removal effect is more preferable, and crystal solution glyphosate mother liquor is contributed to be reduced.
(6) multistage cyclone demister is set in acidolysis kettle top portion, the Synthesis liquid drop that chloromethanes tail gas is carried secretly is divided
Reaction kettle is passed back into from after, Vapor Entrainment phenomenon is avoided on the basis of system pressure drop is controllable.
The present invention can reduce the energy and the consumption of raw materialss such as electricity, steam, the methanol in glyphosate by using glycine production process, carry
High glyphosate yield, selectivity increase the yield of high added value byproduct chloromethane, reduce production cost；It reduces in addition system
Water, reduce waste liquid yield, reduce environmental protection pressure.
1st, environmental benefit.It can reduce more than glyphosate by using glycine production process mother liquor amount 0.3t/t, methanol waste water amount
More than 2.5t/t adds up to and generates waste liquid 2.8t/t less, reduces treatment cost of waste liquor and environmental protection pressure.
2nd, economic benefit
(1) more than the water 1.6t/t brought into acid hemolysis process in system is the method reduce, this part water is avoided and exists
The process of solvent and solvent rectifying recycling experience " distillation removing, cooling, redistillation separation " is removed, steam 0.3t/t can be saved；
Solvent recovery process reduces air consumption about 1.2t/t because of no longer a large amount of distillating carbinol aqueous solutions.Above total reduction steam consumption
1.5t/t, electricity 80KWh/t is saved.
(2) because reducing into the water in system, glyphosate mother solution dissolving, the glyphosate amount of entrainment are reduced, and can improve grass
Sweet phosphine yield 0.3%.The methanol being lost in Methanol Recovery waste water is also reduced, and methanol consumption declines more than 3kg/t.
(3) methoxyl group that raw material dimethylphosphite is brought into largely turns to be selectively converted to add in acid hemolysis process
The higher chloromethanes of value, conversion ratio improve about 50%, and the yield of byproduct chloromethanes rises 0.3t/t or so (by a 0.55t/t left sides
Upper right is raised to 0.85t/t or so), increase glyphosate production process overall economic efficiency.
(4) glyphosate mother solution oxidative degradation efficiency is improved.Due to discharge reduction, glyphosate mother solution concentration increases, after mother liquor
Oxidative degradation efficiency can improve more than 8% in processing procedure, reach and reduce glyphosate mother solution processing environmental protection pressure and processing cost
Dual purpose.
3rd, the mating benefit of industrial chain
Organosilicon factory synthesizes the chloromethanes hydrochloride aqueous solution that meeting by-product contains methanol in the process, and (hereinafter referred to as " containing alcohol is dilute
Hydrochloric acid ").It is defined according to " hazardous waste ",《National Hazard waste register》Clearly above-mentioned containing alcohol dilute hydrochloric acid is defined as dangerous useless
Object, wherein methanol are its characteristic contamination.After can this kind of further absorbing hydrogen chloride of containing alcohol dilute hydrochloric acid being reached a certain concentration, fit
For this technique, comprehensively utilize in glyphosate acidolysis (hydrolysis) process, provided one " turning waste into wealth " to organosilicon enterprise
Path, the comprehensive benefit for having industrial chain mating.
Description of the drawings
Fig. 1 is acidolysis process equipment drawing.
Fig. 2 is solvent recovery process equipment drawing.
Wherein, 1. synthesis reactor, 2. separating methanol kettles, 3. acidolysis kettles, 4. demisters, 5-1 condensers one, 5-2 condensers two, 5-
3 condensers four, 5-5 condensers five, 5-6 condensers six, 5-7 condensers seven, 5-8 condensers eight, 5-9 condensers nine, 5-10 is cold
Condenser ten, 6. dilute hydrochloric acid grooves, 7. methanol, dimethoxym ethane aqueous solution groove, 8. crystallization kettles, 9. glyphosate material washing machines, 10. heating
Device, 11. hydrochloric acid measuring tanks, 12. sour methanol measuring tanks, 13. methanol grooves, 14. preheaters, 15. dimethoxym ethane rectifying columns, 16. again
Boil device, 17. methanol aqueous solution groove, 1,18. dimethoxym ethane return tank, 19. methanol aqueous solution groove, 2,20. level-one hydrogen chloride absorption
Tower circulating slot, 21. secondary chlorination hydrogen absorption tower circulating slots, 22. concentrated acid methanol tanks, 23. level-one hydrogen chloride absorption towers follow, and 24.
Secondary chlorination hydrogen absorption tower, 25. sour methanol extraction tanks, 26. hydrogen chloride gas storage tanks, 27. refined methanol storage tanks, 28. dimethoxym ethanes are adopted
Go out tank, 29. tail gas absorbers, 30. hydrochloric acid tanks, 31. sour methanol tanks.
Specific embodiment
Acidolysis (hydrolysis) process flow chart, solvent recovery process flow chart are shown in attached sheet.
(i.e. hydrogen chloride is water-soluble using hydrochloric acid in sour methanol (i.e. the methanol solution of hydrogen chloride) replacement traditional handicraft by the present invention
Liquid) it is reacted with Synthesis liquid progress acidolysis (hydrolysis).Meanwhile solvent recovery process is also improved, acidolysis (hydrolysis) process output
Methanol, dimethoxym ethane aqueous solution separate dimethoxym ethane through rectifying, remaining methanol aqueous solution adds in the allotment of a small amount of methanol after cooling
Content, is then directly used for absorbing hydrogen chloride gas, and control hydrogen chloride, methanol reach set content, obtains sour methanol, be back to use
Acidolysis (hydrolysis) process；Only a small amount of methanol aqueous solution refines methanol through methanol column rectifying output, total with the material in balance system
Amount.
Acidolysis (hydrolysis) is fed and gaseous pressure control, the control of each temperature of reaction kettle pressure, the allotment of methanol aqueous solution content
And the critical process such as hydrogen chloride absorption are carried out automatically controlling using central control system, and it is specifically chain to see process flow chart, it is steady to improve
Qualitative and proportioning accuracy.
Specific implementation process and method：
1st, Synthesis liquid separating methanol pre-processes：The methods of first being pre-processed to glyphosate synthesis solution, that is, taking vacuum distillation
Solvent methanol in Synthesis liquid is removed, to reduce free methanol amount in Synthesis liquid, reduces follow-up acidolysis (hydrolysis) reaction kettle object
Expect total amount, while increase main reaction material molar concentration and positive reaction is promoted to carry out.Optimal Control index：Vacuum degree 80KPa, temperature
60℃.Whether methanol stripper amount (removing ratio) selects to remove, with specific reference to follow-up acidolysis reaction kettle and its corollary apparatus
Technological design situation determines, also can not be in Synthesis liquid if the volume and treating capacity of acidolysis reaction kettle and its corollary apparatus are enough
Methanol is removed.
2nd, the acidolysis early period stage：By since being added in sour methanol acidolysis be known as acidolysis early period rank to the stage for being warming up to 78 DEG C
Section.Concrete scheme is that pretreated Synthesis liquid is put into acidolysis kettle, and add in hydrogen chloride content at 35 DEG C contains for 32%, methanol
Measure for 60% and water content be 6% sour methanol carry out acidolysis, inventory according to wherein hydrogen chloride content and technique dress
Concrete condition is put to make choice and calculate：The molar ratio of hydrogen chloride and glycine control 2.5：1, it is denoted as a:1.Passed through using steam
Chuck slowly heats up to material in acidolysis kettle, and Synthesis liquid and the mixeding liquid temperature of sour methanol are raised slowly to 78 DEG C by 45 DEG C,
Stage control Wen Sheng is per 4.5 DEG C of half an hour, when control reaction time 3-4 is small.
It should be strongly noted that because glyphosate hydrolysis procedure is not to avoid water reaction, so in sour methanol preparation process,
Without requiring for absolute, all kinds of solution containing methanol and hydrogen chloride such as dilute methanol, dilute hydrochloric acid can be used to be allocated,
Ensure hydrogen chloride, methanol content in control range.
3rd, the later stage acidolysis stage：78 DEG C to 108 DEG C of stage is known as the acidolysis stage in later stage.In the acidolysis later stage, add in few
Hydrochloric acid is measured, to make up the problem of sour methanol high-temperature stability is bad, continues acidolysis reaction.Specially：Treat object in acidolysis kettle
When material temperature degree rises to 78 DEG C, the hot hydrochloric acid that content is 30%, temperature is 78 DEG C is quantitatively adding, specific inventory is according to wherein chlorine
Change the sour quantity of methyl alcohol added in the content of hydrogen and early period acid hemolysis process (to be converted see step 2)：Hydrogen chloride and glycine
Molar ratio controls [3.6-a]：1.Hydrochloric acid is added, continues slowly to heat up to material in acidolysis kettle, by temperature by 78 DEG C or so slowly
108 DEG C or so are risen to, stage control Wen Sheng is per 5 DEG C or so of half an hour, when control reaction time 3-4 is small.
4th, high temperature deacidification stage：By 108 DEG C to reaction finishes, the stage of blowing is known as high temperature deacidification stage.In acidolysis kettle
When temperature of charge rises to 108 DEG C, remaining hydrogen chloride and water form azeotropic in kettle, at this time switch tail gas, the azeotrope warp steamed
The dilute hydrochloric acid that content is 20% is obtained after condenser cooling, goes to the sour methanol of allotment production；Incoagulable gas is gone to chloromethanes and is returned
Sequence of knocking off recycles chloromethanes.When being warming up to 115 DEG C, reach reaction end, material starts to crystallize, and it is about half small to turn down steam, heat preservation
When after add in a small amount of water material cooled down, be then discharged to crystallization kettle, material washing machine be transferred to after glyphosate sufficient crystallising
It carries out washing material, obtains glyphosate.
5th, solvent recovery process：108 DEG C of pervious condensed device condensations of tail gas, obtain the aqueous solution of dimethoxym ethane, methanol, no
Solidifying property gas goes to chloromethanes recovery process recycling chloromethanes.Dimethoxym ethane, the aqueous solution of methanol enter dimethoxym ethane rectifying column, control
44 DEG C of tower top temperature, 80 DEG C of column bottom temperature, tower top pressure -5KPa, the isolated dimethoxym ethane product of tower top；Bottom of towe obtains methanol and contains
The methanol aqueous solution for 80% or so is measured, goes to absorption plant absorbing hydrogen chloride gas, the sour methanol of allotment production after cooling.Acid
Methanol goes to hydrolysis procedure reuse.
Acidolysis and solvent recovery unit the present invention also provides a kind of producing glyphosate by using glycine, synthesis reactor bottom is through pipe
Line is connected with separating methanol kettle top portion, and separating methanol bottom portion converges after pipeline is connected with U-tube with the pipeline of sour methanol measuring tank again
It is connected again with acidolysis kettle top portion after conjunction, hydrochloric acid measuring tank is connected through pipeline with acidolysis kettle top portion；
Acidolysis kettle top portion divides two-way through pipeline, is connected all the way with condenser one, and one bottom of condenser connects with dilute hydrochloric acid groove
It connects, dilute hydrochloric acid groove is provided with tail gas absorber and removes methanol aqueous solution groove two, and tail gas absorber is removed at one top of condenser；
Another way is connected with demister, and demister is connected through pipeline with condenser two, and two top of condenser goes chloromethanes to return
Post is received, two bottom of condenser is connected with methanol, dimethoxym ethane aqueous solution groove, and methanol, dimethoxym ethane aqueous solution groove connect respectively
To solvent recovery post and tail gas absorber；Acidolysis bottom portion is connected through pipeline with crystallization kettle, and crystallization kettle is connected to glyphosate and washes
Material machine, obtains glyphosate.Demister lower part is connected through pipeline with acidolysis kettle top portion, and demister lower part is connected with acidolysis kettle so as to liquid
Mutually flow back.
Separating methanol kettle top portion is connected after pipeline is connected with condenser ten with methanol groove again, and methanol is by trench bottom and synthesis
Kettle connects；It is connected at the top of methanol groove through pipeline with tail gas absorber, condenser ten is connected through pipeline with tail gas absorber, sour first
Alcohol measuring tank is connected hydrochloric acid measuring tank with tail gas absorber through pipeline and is connected through pipeline with tail gas absorber.The tail gas absorption
Tower is connected with methanol aqueous solution groove two.
Methanol, dimethoxym ethane aqueous solution groove are connected through pipeline with preheater, and preheater connects through pipeline and dimethoxym ethane rectifying column
It connecing, dimethoxym ethane rectifier bottoms are connected through pipeline with methanol aqueous solution groove one, and methanol aqueous solution groove one is connected with preheater,
Preheater is connected with condenser three, and condenser three is connected through pipeline with methanol aqueous solution groove two；Methanol aqueous solution groove two divides
Two-way removes level-one hydrogen chloride absorption tower circulating slot, removes methanol aqueous solution rectifying column all the way all the way；Level-one hydrogen chloride absorption tower cycles
Trench bottom is connected through pipeline with condenser five, and condenser Five Classics pipeline divides two-way, is connected all the way with level-one hydrogen chloride absorption tower, one
Grade hydrogen chloride absorption tower is connected to form Xun Huan with level-one hydrogen chloride absorption tower circulating slot again, another way and secondary chlorination hydrogen absorption tower
Circulating slot connects；Secondary chlorination hydrogen absorption tower Xun Huan trench bottom is connected through pipeline with condenser six, and condenser the six channels pipeline is divided to two
Road is connected all the way with secondary chlorination hydrogen absorption tower, and secondary chlorination hydrogen absorption tower is connected again with secondary chlorination hydrogen absorption tower circulating slot,
Another way is connected with concentrated acid methanol storage tank, and concentrated acid methanol storage tank is connected after being connected with condenser nine with sour methanol extraction tank again.
It is connected at the top of the dimethoxym ethane rectifying column through pipeline with condenser four, condenser four connects with dimethoxym ethane return tank
It connects, condenser is provided at the top of dimethoxym ethane return tank；Two-way is divided in dimethoxym ethane return tank lower part through pipeline, connects all the way with condenser eight
Dimethoxym ethane extraction tank is connected to after connecing, is connected to dimethoxym ethane rectifier all the way.Secondary chlorination hydrogen absorption tower is additionally provided with chlorine
Change hydrogen intake pipeline.
Level-one hydrogen chloride absorption tower circulating slot, secondary chlorination hydrogen absorption tower circulating slot, concentrated acid methanol storage tank top are all connected with
To tail gas absorber.
Explanation：Synthesis liquid from synthesis reactor is squeezed into separating methanol kettle with dnockout pumps, is heated up under the conditions of vacuum decompression de-
Except methanol therein, enter methanol groove after methanol condensed, be back to use synthesis post.The Synthesis liquid of methanol removal is beaten with dnockout pumps
Enter acidolysis kettle, add in the sour methanol measured through sour methanol measuring tank, carry out acidolysis early period in 45 DEG C of scopes, add a small amount of warp
The hot hydrochloric acid that hydrochloric acid measuring tank measures carries out later stage hydrolysis.Acidolysis kettle inner exhaust gas carries out foam removal separation through multistage cyclone demister
It is condensed after drop into multi-stage condensing device, incoagulable gas main component is chloromethanes, goes to chloromethanes recycling post and is returned
It receives；Liquid phase main component is dimethoxym ethane, methanol, water, goes to methanol, dimethoxym ethane aqueous solution groove, then with from dimethoxym ethane rectifying
The hot material of tower goes to dimethoxym ethane rectifying column after preheater is exchanged heat and carries out rectifying separation, and tower top obtains dimethoxym ethane product,
Dimethoxym ethane return tank is gone to, is produced after condensed device cooling to tank field；Bottom of towe obtains the methanol-water that methanol content is 80% or so
Solution into methanol aqueous solution groove 1 (before cooling), after preheated device, condenser cooling, is beaten with pump toward methanol aqueous solution groove
2 (after coolings) are then beaten with pump toward hydrogen chloride absorption tower circulating slot, the sour first of hydrogen chloride absorption tower absorbing hydrogen chloride allotment production
Alcohol, control hydrogen chloride, methanol are beaten with pump toward concentrated acid methanol storage tank after reaching set content, return hydrolysis procedure use.
When material is warming up to 108 DEG C in acidolysis kettle, remaining hydrogen chloride and water form azeotropic in kettle, at this time switch tail gas,
It is collected after condensed device cooling, obtains 20% dilute hydrochloric acid, go to dilute hydrochloric acid groove, then beaten toward (the cooling of methanol aqueous solution groove 2
It mixes, then beats toward the sour methanol of level-one hydrogen chloride absorption tower circulating slot allotment production with methanol aqueous solution afterwards).
Hydrogen chloride involved in production process and methanol-fueled exhaust introduce hydrogen chloride, methanol-fueled exhaust absorption tower carries out multistage and washes
It washs, incoagulable gas emptying, water lotion is beaten toward methanol aqueous solution groove 2 (after cooling) with pump and mixed with methanol aqueous solution, then
It beats toward hydrogen chloride absorption tower circulating slot, the sour methanol of hydrogen chloride absorption tower allotment production.
A small amount of methanol aqueous solution refines methanol through methanol column rectifying output, with the material total amount in balance system.It obtains
Refined methanol fills into the sour methanol of level-one hydrogen chloride absorption tower circulating slot allotment production.
It is of the invention compared with existing glyphosate by using glycine acidolysis and solvent recovery technology, Methanol Recovery waste water can be reduced
More than 2.5t/t, reduce more than mother liquor amount 0.3t/t, reduce more than steam steam consumption 1.5t/t, save electricity more than 80KWh/t,
It improves chloromethanes yield 0.3t/t, improve glyphosate yield more than 0.3%, glyphosate production cost reduction 15~20%.
Claims (9)
1. acidolysis and the solvent recovery process of a kind of producing glyphosate by using glycine, which is characterized in that include the following steps：
（1）Synthesis liquid separating methanol pre-processes：First glyphosate synthesis solution is pre-processed, that is, takes distillation under vacuum by Synthesis liquid
In solvent methanol removing, to reduce free methanol amount in Synthesis liquid, vacuum distillation Con trolling index is vacuum degree >=75KPa, temperature
50-65 DEG C of degree；
（2）Acidolysis stage early period：Pretreated Synthesis liquid is put into acidolysis kettle, the methanol of hydrogen chloride is added at 20-45 DEG C
Solution carries out acidolysis, controls the molar ratio of hydrogen chloride and glycine control 1.5~2.8：1, count a：1, pass through chuck using steam
It slowly heats up to material in acidolysis kettle, the mixeding liquid temperature of Synthesis liquid and the methanol solution of hydrogen chloride is raised slowly to by 45 DEG C
78 DEG C, when which is that per 4.5 DEG C of half an hour, control reaction time 3-4 are small；
（3）The acidolysis stage in later stage：When acidolysis material temperature in kettle rises to 78 DEG C, addition content is 30%, the heat that temperature is 78 DEG C
Hydrochloric acid controls the molar ratio of hydrogen chloride and glycine control [(3.3~3.9)-a] in system：1, hydrochloric acid is added, is continued to acid
Material slowly heats up in solution kettle, and temperature is raised slowly to 108 DEG C by 78 DEG C, and stage control Wen Sheng is per 5 DEG C of half an hour, control
When reaction time 3-4 is small；
（4）High temperature deacidification stage：When acidolysis material temperature in kettle rises to 108 DEG C, remaining hydrogen chloride and water form azeotropic in kettle, this
When tail gas is switched, the dilute hydrochloric acid that content is 10-25% is obtained after the cooling of the azeotrope steamed condensed device, goes to allotment production
The methanol solution of hydrogen chloride；Incoagulable gas goes to chloromethanes recovery process recycling chloromethanes；It is continuously heating to 100-120 DEG C
When, reach reaction end, material starts to crystallize, and turns down steam, adds in a small amount of water after heat preservation half an hour material is cooled down, so
After be discharged to crystallization kettle, being transferred to material washing machine after the glyphosate sufficient crystallising carries out washing material, obtains glyphosate；
（5）Solvent recovery process：108 DEG C of pervious tail gas are after demister separates drop into condenser, condensed device condensation
Obtain the aqueous solution of dimethoxym ethane, methanol, incoagulable gas goes to chloromethanes recovery process recycling chloromethanes, dimethoxym ethane, methanol
Aqueous solution enters dimethoxym ethane rectifying column, and 39~46 DEG C of tower top temperature of control, 77~82 DEG C of column bottom temperature, tower top pressure -10~
10KPa, the isolated dimethoxym ethane product of tower top；Bottom of towe obtains the methanol aqueous solution that methanol content is 75-85%, goes after cooling
Toward absorption plant absorbing hydrogen chloride gas, the methanol solution of allotment production hydrogen chloride, the methanol solution of hydrogen chloride goes to acidolysis work
Sequence reuse.
2. acidolysis and the solvent recovery process of producing glyphosate by using glycine described in claim 1, which is characterized in that described
Hydrogen chloride content is 20-35% in the methanol solution of hydrogen chloride, methanol content is 50-80% and aqueous 0-30%.
3. acidolysis and the solvent recovery unit of a kind of producing glyphosate by using glycine, which is characterized in that synthesis reactor bottom is through pipeline
It is connected with separating methanol kettle top portion, separating methanol bottom portion methanol solution measuring tank with hydrogen chloride again after pipeline is connected with U-tube
Pipeline converge in mixer, be connected again with acidolysis kettle top portion after mixing, hydrochloric acid measuring tank connects through pipeline and acidolysis kettle top portion
It connects；
Acidolysis kettle top portion divides two-way through pipeline, is connected all the way with condenser one, and one bottom of condenser is connected with dilute hydrochloric acid groove, dilute
Hydrochloric acid groove is provided with tail gas absorber and removes methanol aqueous solution groove two, and tail gas absorber is removed at one top of condenser；
Another way is connected with demister, and demister is connected through pipeline with condenser two, two top dechlorination methane recovery hilllock of condenser
Position, two bottom of condenser are connected with methanol, dimethoxym ethane aqueous solution groove, and methanol, dimethoxym ethane aqueous solution groove are respectively connected to molten
Post and tail gas absorber are recycled in agent；Demister lower part is connected through pipeline with acidolysis kettle top portion, and demister bottom connects with acidolysis kettle
It connects so that wherein separated liquid phase substance reflux, acidolysis bottom portion are connected through pipeline with crystallization kettle, crystallization kettle is connected to glyphosate
Material washing machine obtains glyphosate.
4. acidolysis and the solvent recovery unit of the producing glyphosate by using glycine described in claim 3, which is characterized in that separating methanol
Kettle top portion is connected after pipeline is connected with condenser ten with methanol groove again, and methanol is connected by trench bottom with synthesis reactor；Methanol by
Groove top portion is connected through pipeline with tail gas absorber, and condenser ten is connected through pipeline with tail gas absorber, the methanol solution of hydrogen chloride
Measuring tank is connected through pipeline with tail gas absorber, and hydrochloric acid measuring tank is connected through pipeline with tail gas absorber.
5. acidolysis and the solvent recovery unit of the producing glyphosate by using glycine described in claim 3 or 4, which is characterized in that institute
The tail gas absorber stated is connected with methanol aqueous solution groove two.
6. acidolysis and the solvent recovery unit of the producing glyphosate by using glycine described in claim 3, which is characterized in that methanol,
Dimethoxym ethane aqueous solution groove is connected through pipeline with preheater, and preheater is connected through pipeline with dimethoxym ethane rectifying column, dimethoxym ethane rectifying
Tower bottom is connected through pipeline with methanol aqueous solution groove one, and methanol aqueous solution groove one is connected with preheater, preheater and condensation
Device three connects, and condenser three is connected through pipeline with methanol aqueous solution groove two；Methanol aqueous solution groove two divides two-way, goes one all the way
Grade hydrogen chloride absorption tower circulating slot, removes methanol aqueous solution rectifying column all the way；Level-one hydrogen chloride absorption tower cycles trench bottom through pipeline
It is connected with condenser five, condenser Five Classics pipeline divides two-way, is connected all the way with level-one hydrogen chloride absorption tower, level-one hydrogen chloride absorption
Tower is connected to form Xun Huan with level-one hydrogen chloride absorption tower circulating slot again, and another way is connected with secondary chlorination hydrogen absorption tower circulating slot；
Secondary chlorination hydrogen absorption tower Xun Huan trench bottom is connected through pipeline with condenser six, and condenser the six channels pipeline divides two-way, all the way
It is connected with secondary chlorination hydrogen absorption tower, secondary chlorination hydrogen absorption tower is connected again with secondary chlorination hydrogen absorption tower circulating slot, another way
It is connected with concentrated acid methanol storage tank, concentrated acid methanol storage tank connects after being connected with condenser nine with the methanol solution of hydrogen chloride extraction tank again
It connects.
7. acidolysis and the solvent recovery unit of the producing glyphosate by using glycine described in claim 6, which is characterized in that dimethoxym ethane
It is connected at the top of rectifying column through pipeline with condenser four, condenser four is connected with dimethoxym ethane return tank, is set at the top of dimethoxym ethane return tank
It is equipped with condenser；Two-way is divided in dimethoxym ethane return tank lower part through pipeline, and dimethoxym ethane extraction is connected to after being connected all the way with condenser eight
Tank is connected to dimethoxym ethane rectifier all the way.
8. acidolysis and the solvent recovery unit of the producing glyphosate by using glycine described in claim 6, which is characterized in that two level chlorine
Change hydrogen absorption tower and be additionally provided with hydrogen chloride gas intake pipeline.
9. acidolysis and the solvent recovery unit of the producing glyphosate by using glycine described in claim 6, which is characterized in that level-one chlorine
Change hydrogen absorption tower circulating slot, secondary chlorination hydrogen absorption tower circulating slot, concentrated acid methanol storage tank top are connected to tail gas absorber.
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| CN108329349A (en) * | 2018-04-20 | 2018-07-27 | 湖北泰盛化工有限公司 | A kind of glyphosate synthesis hydrolyzes and recycles in the process the device and method of triethylamine |
| CN108409532B (en) * | 2018-04-20 | 2023-07-11 | 湖北泰盛化工有限公司 | System and process for recycling solvent for producing glyphosate by alkyl ester method based on secondary condensation |
| CN110862308A (en) * | 2018-08-27 | 2020-03-06 | 湖北泰盛化工有限公司 | Preparation method and application of formaldehyde alcohol solution |
| CN110759944B (en) * | 2019-10-29 | 2022-03-08 | 湖北泰盛化工有限公司 | Heterogeneous continuous acidolysis device and process for producing glyphosate by using glycine method |
| CN111214943A (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 |
| 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 |
| CN112250235B (en) * | 2020-10-10 | 2023-02-17 | 镇江江南化工有限公司 | Method for resource utilization of white carbon black production waste gas and alcohol-containing wastewater in glyphosate production by gas phase method |
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