CN103641854B - A kind of method comprehensively utilizing glycine crystallization mother liquid production glyphosate - Google Patents
A kind of method comprehensively utilizing glycine crystallization mother liquid production glyphosate Download PDFInfo
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- CN103641854B CN103641854B CN201310585021.XA CN201310585021A CN103641854B CN 103641854 B CN103641854 B CN 103641854B CN 201310585021 A CN201310585021 A CN 201310585021A CN 103641854 B CN103641854 B CN 103641854B
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- iminodiacetic acid
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Abstract
The invention belongs to technical field of pesticide; relate to a kind of method utilizing glycine crystallization mother liquid to produce glyphosate; the method is that glycine remaining in glycin mother liquid is converted into the mother solution of imido-diacetin by chemical reaction; then by Iminodiacetate mother solution and Phosphorous chloride. effect; it is converted into iminodiacetic acid hydrochlorid, then adds formaldehyde, regulate pH value; obtain N phosphonomethyliminoacidetic acidetic mixture, after it is oxidized, obtain N (phosphonomethyl) glycine.Glycine and the iminodiacetic acid of residual in discarded mother solution are effectively utilized production glyphosate by the method, glycine crystallization mother liquid has obtained effective comprehensive utilization, decrease glycine and produce " three wastes " discharge and the waste of resource thereof, create Social benefit and economic benefit, well solve the difficult problem that glycine crystallization mother liquid processes.
Description
Technical field
The invention belongs to technical field of pesticide, relate to a kind of side utilizing glycine crystallization mother liquid to produce glyphosate
Method.
Background technology
Glycine is the industrial important source material such as chemical industry, medicine, pesticide, and tool has been widely used.Closely
Nian Lai, the production method of glycine mostly uses hydroxyacetonitrile route to produce glycine method, such as Application No.
The method announced in the patent of invention of 201110351893.0, its method is: hydroxyacetonitrile reacts with ammonia,
To aminoacetonitriles, aminoacetonitriles hydrolyzes again, obtains Glycine sodium aqueous solution, and Glycine sodium aqueous solution is in acid
Obtain glycine after with, obtain glycine.In preparation process, the hydrolysis of aminoacetonitriles is divided into acidolysis and alkali
Solve two kinds, such as JP-A-2-286651, JP-A-04-066559, JP-A-02-306946, JP-A-53-028116,
In the patent of US2384816A, report is the method using acid solution to carry out post processing, uses mineral acid to carry out water
Xie Shi, glycine crystallization mother liquid through time with, take salt after, by-product iminodiacetic acid can the most long-pending more
Many, finally can affect the recycled of glycine crystallization mother liquid.Therefore must determine in glycine production process
A certain amount of mother solution of phase extraction processes as waste liquid, but through repeatedly recycled and sweet after taking salt
Propylhomoserin crystalline mother solution mainly contains glycine, iminodiacetic acid and a small amount of inorganic salt.And for example
JP-A-06-065168、JP-A-05-320106、JP-A-53-031616、US5225592A、
In JP-A-02-250854, WO92/06069, JP-A-53-028115, CN1107139A patent, report is
Use the alkali liquor method that carries out post processing, its exist with acidolysis as problem.
For the glycine remained in mother solution during above-mentioned production glycine crystallization and by-product iminodiacetic acid (salt) thereof
Acid, reports several processing method: the method mostly used is by after inorganic salt taking-up, containing sweet ammonia at present
Acid and the mother solution of iminodiacetic acid just carry out burning disposal, but so burning disposal often lead to energy consumption high,
The shortcomings such as the wasting of resources, and for example the patent of invention of Application No. 200510135493.0 reports glycine crystallization
The integrated conduct method of mother solution, and for example the patent of invention of Application No. 200910251042.1 reports a kind of returning
The method receiving useful ingredients in waste glycin mother liquor, but it is effective to there is presently no real appearance one
Solution, it is possible to make full use of in mother solution glycine and the by-product iminodiacetic acid of residual.
Still further aspect, in the production method of glyphosate, has had numerous research around IDA route exhibition
Open, as US5312973, US5023369 individually disclose with iminodiacetic acid (IDA) as initiation material
Prepare PMIDA and the method being prepared glyphosate by PMIDA oxidation；And ZL93120707, ZL96195765
Also individually disclose and prepared PMIDA by iminodiacetic acid (salt) acid alkali metal salt and prepared by PMIDA hydrogen peroxide oxidation
The method of glyphosate.Also there are many manufacturers with Iminodiacetonitrile 1,1'-Imidodiacetonitrile as initiation material, through hydrolysis,
To iminodiacetic acid, then reacting with formaldehyde, phosphorous acid, prepare PMIDA, PMIDA reoxidizes, and obtains
Glyphosate.All there is inevitable shortcoming in these methods, first, uses Iminodiacetonitrile 1,1'-Imidodiacetonitrile for initial former
Material, the production cost of glyphosate is relatively low, but often produces one ton of glyphosate and will produce the waste liquid of nearly 10 tons,
And these waste liquid biochemical treatments are relatively difficult；Furthermore, PMIDA aoxidizes glyphosate processed, selects two more
Chlorine monoxid, hydrogen peroxide, but relatively costly；Use air oxidation process, although efficiently, but to equipment with urge
The requirement of agent is high, and the especially recovery of the metal ion of catalyst is more difficult.Although, use iminodiacetic acid (salt)
Acid is initiation material, can be substantially reduced the discharge of waste water, but face oxidation PMIDA glyphosate equally
Problem.Either with Iminodiacetonitrile 1,1'-Imidodiacetonitrile as initiation material or iminodiacetic acid is as initiation material, all
It is faced with in oxidation PMIDA process, the recovery problem of by-product formaldehyde.
Summary of the invention
For above-mentioned the deficiencies in the prior art, present inventor, through research repeatedly and substantial amounts of experiment thereof, carries
Supply a kind of method utilizing glycine crystallization mother liquid to produce glyphosate, not only efficiently solve glycine crystallization
The process of mother solution, reduces material consumption energy consumption, makes three wastes resource, and utilizes the method to produce glyphosate and avoid
It was that initiation material prepares the problems referred to above present in glyphosate process with iminodiacetic acid (IDA) in the past.
To sum up, it is an object of the invention to provide the side of a kind of effective comprehensive utilization glycine crystallization mother liquid
Method, recycles, and reduces material consumption energy consumption, by the glycine in glycine crystallization mother liquid and by-product imido thereof
Base oxalic acid is converted into glyphosate, three wastes resource, and mother solution has obtained effective comprehensive utilization, created society
Can benefit and economic benefit.
For achieving the above object, the technical scheme is that
Utilize the method that glycine crystallization mother liquid produces glyphosate, the step including being carried out as follows:
(1) in glycine crystallization mother liquid, add inorganic base, be neutralized reaction, make the glycine in mother solution
It is fully converted to glycinate and Iminodiacetate with iminodiacetic acid, then adds chloracetate,
Described glycinate reacts with chloracetate, and described glycinate is fully converted to Iminodiacetate,
Obtain Iminodiacetate mother solution；Described glycine crystallization mother liquid is that hydroxyacetonitrile method produces glycine
The mother solution of residual eventually；
(2) the Iminodiacetate mother solution that step (1) obtains is reacted with Phosphorous chloride., by imino group
Diacetin is converted into iminodiacetic acid hydrochlorid, then adds formaldehyde, regulation pH value to 0.3-1,
Obtain N-phosphonomethyliminoacidetic acidetic；
(3) the N-phosphonomethyliminoacidetic acidetic that step (2) obtains is carried out oxidation reaction, obtain
Glyphosate.
In the present invention, described glycine crystallization mother liquid is that hydroxyacetonitrile method produces glycine final residue
Solution through repeatedly circulation take salt after mother solution, described mother solution mainly contains 10%～20% glycine,
The iminodiacetic acid of 10%～18% and the water of surplus, wherein possibly together with a small amount of inorganic salt.
Glyphosate is the chemical name of glyphosate, and glyphosate has another name called the sweet acid of phosphine, and chemical structural formula is as follows:
Glyphosate is a kind of herbicide being widely used at present.From eighties of last century the mid-1970s commercialization
Since, due to the herbicidal performance of its brilliance, range of application constantly expands.
Method of the present invention, in described step (1), adds inorganic base, enters in glycine crystallization mother liquid
Row neutralizes reaction；Described inorganic base can select any one, selects sodium hydroxide, hydrogen under normal circumstances
One or more in potassium oxide, calcium hydroxide, barium hydroxide, calcium oxide, sodium carbonate and potassium carbonate, special
Not preferably sodium hydroxide.In the present invention, neutralizing the consumption of reaction inorganic base is just make in its mother solution sweet
Propylhomoserin and iminodiacetic acid are glycinate and Iminodiacetate.
In the present invention, described chloracetate can select commercially available, it is also possible to by monoxone and inorganic base
The mode of synthesis is prepared voluntarily, and in preparation process, the amount of the inorganic base of addition wants that monoxone is the most complete
It is converted into chloracetate.Inorganic base is sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, oxidation
Calcium, sodium carbonate or potassium carbonate, particularly preferred sodium carbonate, when selecting sodium carbonate, monoxone and sodium carbonate
Mol ratio be 2:1.
Method of the present invention, in described step (1), described glycinate and chloracetate reaction temperature
Controlling at 50 DEG C～100 DEG C, described glycinate is 1:1～1.5 with the mol ratio of chloracetate, addition
The amount of chloracetate is wanted to make glycinate be fully converted to Iminodiacetate and is advisable.
In the present invention, the Iminodiacetate mother solution obtained by step (1) without separating-purifying, also without
The inorganic salt in mother solution need to be isolated, i.e. can be directly used for next step reaction, make response procedures simplification, more
It is to have saved cost.
Method of the present invention, in described step (2), described chloromethyl phosphonic acid one sodium salt and imino-diacetic
The reaction temperature of acetate mother solution is 50 DEG C～100 DEG C, described chloromethyl phosphonic acid one sodium salt and iminodiacetic acid (salt)
The mol ratio of hydrochlorate is 1～1.5:1, and the amount of chloromethyl phosphonic acid one sodium salt i.e. added is wanted to make imino-diacetic
Acetate can react completely is advisable.
In the present invention, in described step (2), described Phosphorous chloride. and Iminodiacetate react very
Carrying out under empty condition, reaction temperature is 50 DEG C～100 DEG C, described Phosphorous chloride. and Iminodiacetate
Mol ratio is 1～1.5:1, particularly preferred 1.2～1.5:1, and the hydrogen chloride that Phosphorous chloride. is discharged can be by Asia
Aminoacetaldehyde diethyl hydrochlorate is converted into iminodiacetic acid hydrochlorid.
Further, in the method for the invention, in described step (2), described formaldehyde and iminodiacetic acid (salt)
The temperature of acid hydrochloride reaction controls at 100-120 DEG C, described formaldehyde and iminodiacetic acid hydrochlorid
Mol ratio is 1～2:1, particularly preferably 1.2～1.5:1.
Further, in the present invention, in described step (2), described formaldehyde and Iminodiacetate acid
It is 0.3～1.6 that reactant salt terminates the pH of rear regulation system, obtains containing N-phosphonyl methyl imino diethyl
The mixture of acid.The general pH adding mineral acid regulation system, described mineral acid is sulphuric acid, hydrochloric acid and phosphorus
One or more in acid, preferably hydrochloric acid or sulphuric acid.
In the present invention, in step (2), obtained containing N-phosphonomethyliminoacidetic acidetic
Mixture is without the N-phosphonomethyliminoacidetic acidetic of independent purification step making pure, under can directly carrying out
Oxidation step processes, and makes response procedures simplification, has saved cost especially.
Method of the present invention, in described step (3), described oxidation reaction is with oxygen as oxygen source, described
The speed that is passed through of oxygen is 200～1000ml/min, and the pressure of described oxidation reaction is 0.3～1.5MPa, institute
The temperature stating oxidation reaction is 70 DEG C～110 DEG C, and the response time is 30～60min.
The oxygen source of oxidation reaction can be in air, oxygen, hydrogen peroxide etc. any one, here, especially
Preferably oxygen.
Method of the present invention, in described step (3), the catalyst used by described oxidation reaction is activity
Charcoal, the specific surface area of described activated carbon is 700～1300m2/ g, described activated carbon and N-phosphono first
The weight proportion of base iminodiacetic acid is 0.005～0.01:1.
Method of the present invention, activated carbon is catalyst, the heating-up temperature of described oxidation reaction be 70 DEG C～
110 DEG C, the temperature of filter activity charcoal is 80 DEG C～85 DEG C, and the activated carbon of filtration is capable of circulation to be used again.
Method of the present invention, in described step (3), after oxidation reaction terminates, through purification and crystallization
Processing to obtain glyphosate, described purification and crystallization treatment are first to concentrate, and thickening temperature is less than 70 DEG C, special
Other preferable temperature is 60 DEG C, and the weight ratio being concentrated into system glyphosate and water is 1:3～7, then cools down
Crystallization, temperature is 0 DEG C～20 DEG C, and crystallization time is 1～3 hour, and gained glyphosate crystals is dried,
Described drying temperature is 60 DEG C～80 DEG C.And in the present invention, after crystallisation by cooling, after glyphosate crystals filters
Obtained by glyphosate crystal mother solution can carry out, with recycled, the step that concentrates to lower batch glyphosate filtrate.
In the present invention, in described step (3), formaldehydeless generation in described oxidation reaction process, and with
Past production method all can produce a large amount of formaldehyde and waste liquid, and therefore, the method for the present invention has environmentally friendly
Advantage.
The following is the method utilizing glycine crystallization mother liquid joint production to produce glyphosate, described production
Device, including the glycine crystallization mother liquid collecting tank set gradually, neutralizes retort, synthetic reaction tank, oxygen
Change autoclave, segregation apparatus, vacuum concentration equipment and crystallization apparatus, described crystallization apparatus and described point
Being connected from device, also include drying device and chloracetate preparation tank, described drying device separates with described
Device is connected, and described chloracetate preparation tank is connected with described neutralization retort；Described synthetic reaction tank
It is additionally provided with vacuum extractor；
The glycine crystallization mother liquid collected in glycine crystallization mother liquid collecting tank is sent into and is neutralized in retort by a,
To neutralizing, retort adds inorganic base, be neutralized reaction, make the glycine in mother solution and iminodiacetic acid (salt)
Acid is fully converted to glycinate and Iminodiacetate, then by the chlorine of preparation in chloracetate preparation tank
Acetate joins in neutralization retort, and described glycinate reacts with chloracetate, by described glycinate
It is fully converted to Iminodiacetate, obtains Iminodiacetate mother solution；
The Iminodiacetate mother solution that step a is obtained by b is sent in synthetic reaction tank, is evacuated to
After 400mmHg, add Phosphorous chloride., carry out synthetic reaction and obtain iminodiacetic acid hydrochlorid, then will
Synthetic reaction tank recovers to normal pressure, adds formalin, obtained imino-diacetic in synthetic reaction tank
Acetic acid hydrochloride and formaldehyde carry out synthetic reaction, obtain N-phosphonomethyliminoacidetic acidetic；
The N-phosphonomethyliminoacidetic acidetic that step b is obtained by c is sent in oxidation autoclave, and
Adding catalyst activity charcoal, and be passed through oxygen and carry out oxidation reaction in oxidation autoclave, reaction terminates
After, the reactant liquor of gained to be sent in segregation apparatus and be separated off activated carbon, gained filtrate sends into enrichment facility
Middle concentration, stops when the weight ratio to filtrate glyphosate Yu water is 1:3～7 concentrating, is re-fed into crystallization apparatus
In carry out crystallisation by cooling, send in segregation apparatus after terminating and isolate glyphosate crystals, by sweet for gained grass
Phosphine crystal is sent in drying device and is dried.
Utilize the method that glycine crystallization mother liquid joint production produces glyphosate, in process of production, first
First, glycine crystallization mother liquid need not separate desalting purifying and i.e. can be directly used for reaction；Secondly, step a gained
The Iminodiacetate mother solution arrived is without separating-purifying, without the inorganic salt isolated in mother solution,
It is directly used in next step reaction；Furthermore, obtained N-phosphonomethyliminoacidetic acidetic hydrochlorate and first
After aldehyde reaction, the pH of regulation system is 0.3～1.6, and the N-phosphonomethyliminoacidetic acidetic obtained mixes
Compound, without being purified process, can directly carry out next step oxidation processes, utilize process units to give birth to
Produce, more can embody saving program, cost-effective advantage.
Beneficial effects of the present invention: 1) side of a kind of effective comprehensive utilization glycine crystallization mother liquid is provided
Method, recycles, and reduces material consumption energy consumption, by the glycine in glycine crystallization mother liquid and by-product imido thereof
Base oxalic acid is converted into glyphosate, three wastes resource, and mother solution has obtained effective comprehensive utilization, created society
Can benefit and economic benefit；2) utilizing the method to produce, intermediate product is without isolated and purified, it is not necessary to go
Except inorganic salt, i.e. can be directly used for next step reaction, make response procedures simplification, saved cost especially；3)
The method of the present invention, does not has a large amount of waste liquid to produce in whole course of reaction, environmentally friendly.
Accompanying drawing explanation
Fig. 1 is glyphosate production apparatus structure schematic diagram.
Detailed description of the invention
Hereinafter with reference to accompanying drawing, the preferred embodiments of the present invention are described in detail.In preferred embodiment not
Indicate the experimental technique of actual conditions, generally according to normal condition.With represented by percent in following example
Content of material if no special instructions be accordingly to be regarded as mass percent.
The technique produced for glycine has had patent of invention to be described in detail, and the most no longer introduces.
Embodiment 1
In glycine crystallization mother liquid and reaction, its concrete operations are as follows:
(wherein Glycine Levels is 14%, iminodiacetic acid content to weigh glycine crystallization mother liquid 507 grams
It is 16%) it is placed in 2000mL with agitator, thermometer, constant pressure funnel, the four-hole boiling flask of condensing tube
In, it being subsequently adding the sodium hydrate aqueous solution 155 grams of 40%, the ammonia in system is arranged by heating decompression completely
Except clean.
Monoxone is converted into sodium chloroacetate aqueous solution, and its concrete operations are as follows:
The monoxone weighing 100 grams is placed in the beaker of 500mL, adds the water of 300 grams, the most slowly drips
The sodium hydrate aqueous solution adding 40% 104 grams, controls neutral temperature and is less than 60 DEG C, after dropping,
To sodium chloroacetate aqueous solution.
The sodium chloroacetate aqueous solution obtained slowly is dropped to the glycine crystallization mother liquid after neutralization obtained above
In, keeping reaction temperature is 25 DEG C～30 DEG C, stirs 6 hours, by the glycine in glycine crystallization mother liquid
Sodium is fully converted to iminodiacetic acid sodium, be subsequently adding 3 grams of activated carbon carry out decolouring under the conditions of 50 DEG C,
Filtering, obtain iminodiacetic acid sodium aqueous solution 1060 grams, by analysis, the conversion ratio of glycine is 98%,
In iminodiacetic acid sodium mother solution, the content of iminodiacetic acid disodium salt is 25.67%.
The synthesis of PMIDA, its concrete operations are as follows:
1060 grams of iminodiacetic acid disodium salts obtained above are added reactor, are evacuated to 400mmHg,
313.6 grams of Phosphorous chloride .s of dropping afterwards, and control reflux temperature, temperature control when starting to drip Phosphorous chloride.
System is at 65 DEG C, and half an hour is warming up to 80 DEG C after dropping, and now the concentration of iminodiacetic acid is 14.9%.
At ambient pressure, it is warming up to 120 DEG C, in 60 minutes, drips the formalin 174.5 grams of 37%, and
Temperature of controlling well is 115 DEG C～120 DEG C, then insulation 2 hours, with salt acid for adjusting pH to 0.3～1, obtains
To PMIDA aqueous solution 1536 grams, wherein the content of PMIDA is 22.04%, and yield is 97%.Obtain double sweet
Phosphine mixture, it is not necessary to purification.
PMIDA is oxidized to glyphosate, and its concrete operations are as follows:
Being added in autoclave by PMIDA mixture obtained above, being subsequently adding specific surface area is
1100m2The activated carbon of/g 2.7 grams, stirring, it is warming up to 100 DEG C, then leads to the speed of 450mL/min
Entering oxygen, reaction pressure controls at 0.65MPa, and the response time is 1 hour, by turning of detection PMIDA
Rate is more than 99%.Stop being passed through oxygen, be depressurized to normal pressure, filter activity charcoal under the conditions of keeping 85 DEG C,
Activated carbon washs with 90 DEG C of water, and cleaning mixture merges with filtrate, and the activated carbon recycled obtained is to next batch
Reaction.It is evaporated to glyphosate: water is 1:3, is cooled to 15 DEG C by under the conditions of the filtrate obtained again 60 DEG C,
Stir crystallization in 3 hours, filter the Recycling Mother Solution after glyphosate to next group filter activity charcoal rear oxidation liquid together
Concentrate.Glyphosate, through 60 DEG C of vacuum drying, is product glyphosate 196.4 grams (with iminodiacetic acid
Meter), solids content is 97.6%, and yield is 93%.
Embodiment 2
In glycine crystallization mother liquid and reaction, its concrete operations are as follows:
Weigh glycine crystallization mother liquid 507 grams (Glycine Levels is 14%, and iminodiacetic acid content is 16%)
Be placed in 2000mL with agitator, thermometer, constant pressure funnel, condensing tube four-hole boiling flask in, then
Adding the sodium hydrate aqueous solution 155 grams of 40%, the ammonia in system is got rid of totally by heating decompression completely.
Monoxone is converted into sodium chloroacetate aqueous solution, and its concrete operations are as follows:
The monoxone weighing 100 grams is placed in the beaker of 500mL, adds the water of 300 grams, the most slowly drips
The sodium hydrate aqueous solution adding 40% 104 grams, controls neutral temperature and is less than 60 DEG C, after dropping,
To sodium chloroacetate aqueous solution.
The sodium chloroacetate aqueous solution obtained slowly is dropped to the glycine crystallization mother liquid after neutralization obtained above
In, keeping reaction temperature is 25 DEG C～30 DEG C, stirs 6 hours, by the glycine in glycine crystallization mother liquid
Sodium is fully converted to iminodiacetic acid sodium, adds 3 grams of activated carbon and carries out decolouring, filtering under the conditions of 50 DEG C,
Obtaining iminodiacetic acid sodium aqueous solution 1060 grams, by analysis, the conversion ratio of glycine is 98%, imido
In base sodium diacelate mother solution, the content of iminodiacetic acid disodium salt is 25.67%.
The synthesis of PMIDA, its concrete operations are as follows:
1060 grams of iminodiacetic acid disodium salts obtained above are added reactor, are evacuated to 400mmHg,
313.6 grams of Phosphorous chloride .s of dropping afterwards, and control reflux temperature, temperature control when starting to drip Phosphorous chloride.
System is at 65 DEG C, and half an hour is warming up to 80 DEG C after dropping, and now the concentration of iminodiacetic acid is 14.9%.
At ambient pressure, it is warming up to 120 DEG C, in 60 minutes, drips the formalin 174.5 grams of 37%, and
Temperature of controlling well is 115 DEG C～120 DEG C, then insulation 2 hours, with salt acid for adjusting pH to 0.3～1, obtains
To PMIDA aqueous solution 1536 grams, wherein the content of PMIDA is 22.04%, and yield is 97%.Obtain double sweet
Phosphine mixture, it is not necessary to purification.
PMIDA is oxidized to glyphosate, and its concrete operations are as follows:
Being added in autoclave by PMIDA mixture obtained above, being subsequently adding specific surface area is
1000m2The activated carbon of/g 3.1 grams, stirring, it is warming up to 100 DEG C, then leads to the speed of 500mL/min
Entering oxygen, reaction pressure controls at 0.75MPa, and the response time is 1 hour, by turning of detection PMIDA
Rate is more than 99%.Stop being passed through oxygen, be depressurized to normal pressure, filter activity charcoal under the conditions of keeping 85 DEG C,
Activated carbon washs with 90 DEG C of water, and cleaning mixture merges with filtrate, and the activated carbon recycled obtained is to next batch
Reaction.The filtrate obtained and embodiment 1 take the residue mother solution after glyphosate merge, then 60 DEG C of conditions
Under be evaporated to glyphosate: water is 1:4, is cooled to 15 DEG C, stirs crystallization in 3 hours, filters glyphosate
After Recycling Mother Solution concentrate together to the oxidation solution after next group filter activity charcoal.Glyphosate is through 60 DEG C of vacuum
Being dried, be product glyphosate 250.3 grams (in terms of iminodiacetic acid), solids content is 97.6%, receives
Rate is 94%.
Embodiment 3
The neutralization reaction of glycine crystallization mother liquid, its concrete operations are as follows:
Weigh glycine crystallization mother liquid 507 grams (Glycine Levels is 14%, and iminodiacetic acid content is 16%)
Be placed in 2000mL with agitator, thermometer, constant pressure funnel, condensing tube four-hole boiling flask in, then
Adding the sodium hydrate aqueous solution 155 grams of 40%, the ammonia in system is got rid of totally by heating decompression completely.
Monoxone is converted into sodium chloroacetate aqueous solution, and its concrete operations are as follows:
The monoxone weighing 100 grams is placed in the beaker of 500mL, adds the water of 300 grams, the most slowly drips
The sodium hydrate aqueous solution adding 40% 104 grams, controls neutral temperature and is less than 60 DEG C, after dropping,
To sodium chloroacetate aqueous solution.
The sodium chloroacetate aqueous solution obtained slowly is dropped to the glycine crystallization mother liquid after neutralization obtained above
In, keeping reaction temperature is 25 DEG C～30 DEG C, stirs 6 hours, by the glycine in glycine crystallization mother liquid
Sodium is fully converted to iminodiacetic acid sodium, add 3 grams of activated carbon carry out decolouring under the conditions of 50 DEG C, filter,
Obtaining iminodiacetic acid sodium aqueous solution 1060 grams, by analysis, the conversion ratio of glycine is 98%, imido
In base sodium diacelate mother solution, the content of iminodiacetic acid disodium salt is 25.67%.
The synthesis of PMIDA, its concrete operations are as follows:
1060 grams of iminodiacetic acid disodium salts obtained above are added reactor, are evacuated to 400mmHg,
313.6 grams of Phosphorous chloride .s of dropping afterwards, and control reflux temperature, temperature control when starting to drip Phosphorous chloride.
System is at 65 DEG C, and half an hour is warming up to 80 DEG C after dropping, and now the concentration of iminodiacetic acid is 14.8%.
At ambient pressure, it is warming up to 120 DEG C, in 60 minutes, drips the formalin 174.5 grams of 37%, and
Temperature of controlling well is 115 DEG C～120 DEG C, then insulation 2 hours, with salt acid for adjusting pH to 0.3～1, obtains
To PMIDA aqueous solution 1536 grams, wherein the content of PMIDA is 22.04%, and yield is 97%.Obtain double sweet
Phosphine mixture, it is not necessary to purification.
PMIDA is oxidized to glyphosate, and its concrete operations are as follows:
Being added in autoclave by PMIDA mixture obtained above, being subsequently adding specific surface area is
1100m2The activated carbon of/g (with the activated carbon reclaimed in above-described embodiment 2, inadequate 3.4 grams separately add work
Property charcoal to the most enough) totally 3.4 grams, be warming up to 100 DEG C, be then passed through oxygen with the speed of 500mL/min,
Reaction pressure controls at 0.85MPa, and the response time is 1 hour, is more than by the conversion ratio of detection PMIDA
99%.Stopping being passed through oxygen, be depressurized to normal pressure, filter activity charcoal under the conditions of keeping 80 DEG C, activated carbon is used
90 DEG C of water washings, cleaning mixture merges with filtrate, and the activated carbon recycled obtained to next batch reacts.Will
The filtrate obtained and embodiment 2 take the mother solution after glyphosate and merge, and are then evaporated under the conditions of 60 DEG C
Glyphosate: water is 1:4, is cooled to 15 DEG C, stirs crystallization in 3 hours, filters the Recycling Mother Solution after glyphosate
Oxidation solution to next group filter activity charcoal concentrates together.Glyphosate, through 70 DEG C of vacuum drying, is product
Product glyphosate 252.9 grams (in terms of iminodiacetic acid), solids content is 97.5%, and yield is 95%.
Embodiment 4
The neutralization reaction of glycine crystallization mother liquid, its concrete operations are as follows:
Weigh glycine crystallization mother liquid 507 grams (Glycine Levels is 14%, and iminodiacetic acid content is 16%)
Be placed in 2000mL with agitator, thermometer, constant pressure funnel, condensing tube four-hole boiling flask in, then
Adding the sodium hydrate aqueous solution 155 grams of 40%, the ammonia in system is got rid of totally by heating decompression completely.
Monoxone is converted into sodium chloroacetate aqueous solution, and its concrete operations are as follows:
The monoxone weighing 100 grams is placed in the beaker of 500mL, adds the water of 300 grams, the most slowly drips
The sodium hydrate aqueous solution adding 40% 104 grams, controls neutral temperature and is less than 60 DEG C, after dropping,
To sodium chloroacetate aqueous solution.
The sodium chloroacetate aqueous solution obtained slowly is dropped to the glycine crystallization mother liquid after neutralization obtained above
In, keeping reaction temperature is 25 DEG C～30 DEG C, stirs 6 hours, by the glycine in glycine crystallization mother liquid
Sodium is fully converted to iminodiacetic acid sodium, add 3 grams of activated carbon carry out decolouring under the conditions of 50 DEG C, filter,
Obtaining iminodiacetic acid sodium aqueous solution 1060 grams, by analysis, the conversion ratio of glycine is 98%, imido
In base sodium diacelate mother solution, the content of iminodiacetic acid disodium salt is 25.67%.
The synthesis of PMIDA, its concrete operations are as follows:
1060 grams of iminodiacetic acid disodium salts obtained above are added reactor, are evacuated to 400mmHg,
313.6 grams of Phosphorous chloride .s of dropping afterwards, and control reflux temperature, temperature control when starting to drip Phosphorous chloride.
System is at 65 DEG C, and half an hour is warming up to 80 DEG C after dropping, and now the concentration of iminodiacetic acid is 14.8%.
At ambient pressure, it is warming up to 120 DEG C, in 60 minutes, drips the formalin 174.5 grams of 37%, and
Temperature of controlling well is 115 DEG C～120 DEG C, then insulation 2 hours, with salt acid for adjusting pH to 0.3～1, obtains
To PMIDA aqueous solution 1536 grams, wherein the content of PMIDA is 22.04%, and yield is 97%.Obtain double sweet
Phosphine mixture, it is not necessary to purification.
PMIDA is oxidized to glyphosate, and its concrete operations are as follows:
Being added in autoclave by PMIDA mixture obtained above, being subsequently adding specific surface area is
1100m2The activated carbon of/g totally 4 grams, stirring, it is warming up to 100 DEG C, then leads to the speed of 500mL/min
Entering oxygen, reaction pressure controls at 0.80MPa, and the response time is 1 hour, by turning of detection PMIDA
Rate is more than 99%.Stop being passed through oxygen, be depressurized to normal pressure, filter activity charcoal under the conditions of keeping 80 DEG C,
Activated carbon washs with 90 DEG C of water, and cleaning mixture merges with filtrate, and the activated carbon recycled obtained is to next batch
Reaction.The filtrate obtained and embodiment 3 take the mother solution after glyphosate merge, reduce pressure under the conditions of 60 DEG C dense
It is reduced to glyphosate: water is 1:5, is cooled to 15 DEG C, stir crystallization in 3 hours, filter the mother solution after glyphosate
It is recycled to the oxidation solution after next group filter activity charcoal to concentrate together.Glyphosate is through 70 DEG C of vacuum drying, i.e.
For product glyphosate 247.6 grams (in terms of iminodiacetic acid), solids content is 97.6%, and yield is 93%.
Embodiment 5 utilizes glycine crystallization mother liquid joint production to produce glyphosate
Utilizing glycine crystallization mother liquid joint production to produce glyphosate, described process units, including depending on
The glycine crystallization mother liquid collecting tank 1 of secondary setting, neutralization retort 2, synthetic reaction tank 3, oxidation high pressure are anti-
Answer still 4, segregation apparatus 5, vacuum concentration equipment 6 and crystallization apparatus 7, described crystallization apparatus 7 and described point
Be connected from device 5, also include drying device 8 and chloracetate preparation tank 9, described drying device 8 with
Described segregation apparatus 5 is connected, and described chloracetate preparation tank 9 is connected with described neutralization retort 2；
Described synthetic reaction tank 3 is additionally provided with vacuum extractor；
Take the 1014 grams of (Glycine Levels of glycine crystallization mother liquid collected in glycine crystallization mother liquid collecting tank 1
Being 14%, iminodiacetic acid content is 16%) send in neutralization retort 2, then to neutralizing retort 2
The sodium hydrate aqueous solution of middle addition 40% 310 grams, is neutralized reaction, and heating decompression is by the ammonia in system
Gas is got rid of totally completely.
It addition, the monoxone weighing 200 grams is placed in chloracetate preparation tank 9, add the water of 600 grams,
The most slowly sodium hydrate aqueous solution 208 grams of dropping 40%, controls neutral temperature and is less than 60 DEG C, dropping
After, obtain sodium chloroacetate aqueous solution.
Then slowly it is added drop-wise to the sodium chloroacetate aqueous solution obtained in chloracetate preparation tank 9 neutralize retort
In 2, keeping reaction temperature is 25 DEG C～30 DEG C, stirs 6 hours, the glycine obtained after neutralizing reaction
Sodium is fully converted to iminodiacetic acid sodium, obtains iminodiacetic acid sodium aqueous solution 2120 grams, by analysis,
The conversion ratio of glycine is 96%, and in iminodiacetic acid sodium mother solution, the content of iminodiacetic acid disodium salt is
24.17%.
Iminodiacetic acid sodium mother solution obtained above is sent in synthetic reaction tank 3, is evacuated to
400mmHg, then 627.2 grams of Phosphorous chloride .s of dropping, when starting to drip Phosphorous chloride., temperature controls at 65 DEG C,
Half an hour is warming up to 80 DEG C after dropping, and now the concentration of iminodiacetic acid is 14.5%.Then synthesize
Retort 3 is recovered to normal pressure, is warming up to 120 DEG C, drips the formalin 349 of 37% in 60 minutes
Gram, and to control temperature be 115 DEG C～120 DEG C, then insulation 2 hours, with salt acid for adjusting pH to 0.3～
1, obtain PMIDA aqueous solution 3067 grams, wherein the content of PMIDA is 21.84%, and yield is 95%,
To PMIDA mixture, it is not necessary to purification.
PMIDA aqueous solution obtained above is sent in oxidation autoclave 4, be subsequently adding specific surface area
For 1000m2The activated carbon of/g totally 6.2 grams, stirring, it is warming up to 100 DEG C, then with the speed of 500mL/min
Degree is passed through oxygen, and reaction pressure controls at 0.80MPa, and the response time is 1 hour, by detection PMIDA
Conversion ratio more than 99%.Stop being passed through oxygen, be depressurized to normal pressure, reactant liquor sent in segregation apparatus 5,
Filter activity charcoal under the conditions of keeping 80 DEG C, the activated carbon leached washs with 90 DEG C of water, and cleaning mixture closes with filtrate
And, the activated carbon recycled obtained to next batch reacts.Cleaning mixture after merging is sent into dense with filtrate
In compression apparatus 6, under the conditions of 60 DEG C, it is evaporated to glyphosate: water is 1:4, is then re-fed into crystallization dress
Put in 7, be cooled to 15 DEG C, stir crystallization in 3 hours, filtered by segregation apparatus 5, after filtering glyphosate
Recycling Mother Solution concentrate after enrichment facility 6 merges with next group filtrate.The glyphosate crystals obtained
Send in drying device 8 through 65 DEG C of vacuum drying, be product glyphosate 490.2 grams (with imino-diacetic
Acetometer), solids content is 97.6%, and yield is 93%.
Finally illustrate, above example only in order to technical scheme to be described and unrestricted, although
With reference to preferred embodiment, the present invention is described in detail, it will be understood by those within the art that,
Technical scheme can be modified or equivalent, without deviating from technical solution of the present invention
Objective and scope, it all should be contained in the middle of scope of the presently claimed invention.
Claims (9)
1. utilize the method that glycine crystallization mother liquid produces glyphosate, it is characterised in that include being carried out as follows
Step:
(1) in glycine crystallization mother liquid, add inorganic base, be neutralized reaction, make the glycine in mother solution
It is fully converted to glycinate and Iminodiacetate with iminodiacetic acid, then adds chloracetate,
Described glycinate reacts with chloracetate, and described glycinate is fully converted to Iminodiacetate,
Obtain Iminodiacetate mother solution；Described glycine crystallization mother liquid is that hydroxyacetonitrile method produces glycine
The mother solution of residual eventually；
(2) the Iminodiacetate mother solution that step (1) obtains is reacted with Phosphorous chloride., by imino group
Diacetin is converted into iminodiacetic acid hydrochlorid, then adds formaldehyde, regulation pH value to 0.3-1,
Obtain N-phosphonomethyliminoacidetic acidetic；Described Phosphorous chloride. and the reaction of Iminodiacetate mother solution
Carrying out under vacuum, reaction temperature is 50 DEG C～100 DEG C, described Phosphorous chloride. and iminodiacetic acid
The mol ratio of salt is 1～1.5:1；Described formaldehyde and iminodiacetic acid hydrochlorid react and carry out at ambient pressure,
Temperature controls at 115-120 DEG C, and described formaldehyde is 1～2:1 with the mol ratio of iminodiacetic acid hydrochlorid；
(3) the N-phosphonomethyliminoacidetic acidetic that step (2) obtains is carried out oxidation reaction, obtain
Glyphosate.
Method the most according to claim 1, it is characterised in that in described step (1), described is sweet
Propylhomoserin crystalline mother solution is that hydroxyacetonitrile method produces the solution of glycine final residue after repeatedly circulation takes salt
Mother solution, mainly contains the iminodiacetic acid of glycine, 10%～18% of 10%～20% and remaining in described mother solution
The water of amount.
Method the most according to claim 1 and 2, it is characterised in that in described step (1), sweet ammonia
Adding inorganic base in acid crystal mother solution, be neutralized reaction, described inorganic base is sodium hydroxide, hydroxide
One or more in potassium, calcium hydroxide, barium hydroxide, calcium oxide, sodium carbonate and potassium carbonate.
Method the most according to claim 1, it is characterised in that in described step (1), described sweet ammonia
Hydrochlorate and chloracetate reaction temperature control at 50 DEG C～100 DEG C, and described glycinate rubs with chloracetate
That ratio is 1:1～1.5.
Method the most according to claim 1, it is characterised in that in described step (3), described oxidation
Reaction is with oxygen as oxygen source, and the speed that is passed through of described oxygen is 200～1000ml/min, described oxidation reaction
Pressure be 0.3～1.5MPa, the temperature of described oxidation reaction is 70 DEG C～110 DEG C, the response time be 30～
60min。
Method the most according to claim 1, it is characterised in that in described step (3), described oxidation
Catalyst used by reaction is activated carbon, and the specific surface area of described activated carbon is at 700-1300m2/ g, described
The weight proportion of activated carbon and N-phosphonomethyliminoacidetic acidetic be 0.005～0.01:1.
Method the most according to claim 6, it is characterised in that the heating-up temperature of described oxidation reaction is
70 DEG C～110 DEG C, the temperature of filter activity charcoal is 80 DEG C～85 DEG C, the activated carbon Recycling of filtration.
Method the most according to claim 1, it is characterised in that after oxidation reaction terminates, through purification
Obtaining glyphosate with crystallization treatment, described purification and crystallization treatment are first to concentrate, and thickening temperature is less than
70 DEG C, the weight ratio being concentrated into system glyphosate and water is 1:3～7, then carries out crystallisation by cooling, and temperature is
0 DEG C～20 DEG C, crystallization time is 1～3 hour, and gained glyphosate crystals is dried, described drying temperature
It it is 60 DEG C～80 DEG C.
9. utilize the method that glycine crystallization mother liquid joint production produces glyphosate, it is characterised in that institute
The process units stated, including the glycine crystallization mother liquid collecting tank (1) set gradually, neutralize retort (2),
Synthetic reaction tank (3), oxidation autoclave (4), segregation apparatus (5), vacuum concentration equipment (6) and
Crystallization apparatus (7), described crystallization apparatus (7) is connected with described segregation apparatus (5), also includes being dried
Device (8) and chloracetate preparation tank (9), described drying device (8) and described segregation apparatus (5) phase
Connection, described chloracetate preparation tank (9) is connected with described neutralization retort (2), and described synthesis is anti-
Tank (3) is answered to be additionally provided with vacuum extractor；
The glycine crystallization mother liquid collected in glycine crystallization mother liquid collecting tank (1) is sent into and is neutralized retort by a
(2), in, to neutralizing, retort (2) adds inorganic base, be neutralized reaction, make the sweet ammonia in mother solution
Acid and iminodiacetic acid are fully converted to glycinate and Iminodiacetate, then by chloracetate system
In standby tank (9), the chloracetate of preparation joins in neutralization retort (2), described glycinate and chloroethene
Hydrochlorate reacts, and described glycinate is fully converted to Iminodiacetate, obtains Iminodiacetate
Mother solution；
The Iminodiacetate mother solution that step a is obtained by b is sent in synthetic reaction tank (3), is evacuated to
After 400mmHg, add Phosphorous chloride., carry out synthetic reaction and obtain iminodiacetic acid hydrochlorid, then will
Synthetic reaction tank (3) recovers to normal pressure, adds formalin in synthetic reaction tank (3), obtained
Iminodiacetic acid hydrochlorid and formaldehyde carry out synthetic reaction, obtain N-phosphonyl methyl imino diethyl
Acid；
The N-phosphonomethyliminoacidetic acidetic that step b is obtained by c is sent in oxidation autoclave (4),
And add catalyst activity charcoal, and in oxidation autoclave (4), it is passed through oxygen carries out oxidation reaction, instead
After should terminating, being sent in segregation apparatus (5) by the reactant liquor of gained and be separated off activated carbon, gained filtrate is sent
Enter in enrichment facility (6) and concentrate, stop when the weight ratio to filtrate glyphosate Yu water is 1:3～7 concentrating,
It is re-fed in crystallization apparatus (7) carrying out crystallisation by cooling, sends in segregation apparatus (5) after terminating and separate
Go out glyphosate crystals, gained glyphosate crystals is sent in drying device (8) and dries.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1484647A (en) * | 2001-01-12 | 2004-03-24 | �����ɷ� | Method for producing N-phosphonomethyl iminodiacetic acid |
| CN1990460A (en) * | 2005-12-31 | 2007-07-04 | 重庆三峡英力化工有限公司 | Comprehensive treatment of glycine crystallization mother liquid |
| CN101508701A (en) * | 2008-12-10 | 2009-08-19 | 上海泰禾(集团)有限公司 | Method for preparing glyphosate by oxidizing N-(Phosphonomethyl)iminodiacetic acid with active carbon as catalyst oxygen |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1484647A (en) * | 2001-01-12 | 2004-03-24 | �����ɷ� | Method for producing N-phosphonomethyl iminodiacetic acid |
| CN1990460A (en) * | 2005-12-31 | 2007-07-04 | 重庆三峡英力化工有限公司 | Comprehensive treatment of glycine crystallization mother liquid |
| CN101508701A (en) * | 2008-12-10 | 2009-08-19 | 上海泰禾(集团)有限公司 | Method for preparing glyphosate by oxidizing N-(Phosphonomethyl)iminodiacetic acid with active carbon as catalyst oxygen |
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