CN106631846A - Preparation method of N-phosphonomethyl aminodiacetic acid intermediate - Google Patents
Preparation method of N-phosphonomethyl aminodiacetic acid intermediate Download PDFInfo
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- CN106631846A CN106631846A CN201611173276.5A CN201611173276A CN106631846A CN 106631846 A CN106631846 A CN 106631846A CN 201611173276 A CN201611173276 A CN 201611173276A CN 106631846 A CN106631846 A CN 106631846A
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- acid
- pmida
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- hydrochloric acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/26—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing carboxyl groups by reaction with HCN, or a salt thereof, and amines, or from aminonitriles
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The invention provides a preparation method of an N-phosphonomethyl aminodiacetic acid intermediate. One part of substituting acid including byproduct hydrochloric acid and the like of trichloracetic aldehyde is used as a source of hydrochloric acid and is mixed with the other part of normal acid for being used as reaction acid for acidifying. By adopting the method provided by the invention, the production cost of the N-phosphonomethyl aminodiacetic acid is greatly reduced; meanwhile, waste acid generated in a production process of the trichloracetic aldehyde and an NLD-02 flame retardant is treated and the cost needed by biochemical treatment is reduced.
Description
Technical field
The present invention relates to a kind of technology of preparing of the intermediate material in PMIDA production process.
Background technology
Glyphosate is a kind of efficient, low toxicity, the organic phosphine herbicide of safety, and the preventing and treating to perennial malignant weed has very much
Effect, is one of herbicide for being most widely used at present.PMIDA is a kind of production glyphosate（N- (phosphonomethyl) glycines）
One of raw material.And during PMIDA is prepared, need first to make iminodiacetic acid intermediate, then by imino-diacetic
Acetic acid carries out condensation reaction and obtains PMIDA.
A kind of number of patent application N-(phosphonomethyl) iminodiacetic acid wastewater that has been 2012104561561 disclosure of the invention is applied mechanically and prepared in the middle of glyphosate
The technique of body PMIDA, it is characterised in that course of reaction is：Quantitative iminodiacetic acid and sour water（Or washings）Anti-
After answering the mixing in kettle, control temperature is less than 80 DEG C of ＜（It is preferred that 60 DEG C of ＜）Phosphorus trichloride is added dropwise, and grasps vacuum for -0.01
To -0.1MPa（It is preferred that -0.01MPa arrives -0.03MPa）, drip off complete, insulation 0.5-10 hours（It is preferred that 0.5-2 hours）, it is warming up to
90-120℃（It is preferred that 105-112 DEG C）, flowing back when formaldehyde is added dropwise, completion of dropping is incubated 0.5-5 hours（It is preferred that 1-2 hours)；
Quantitative clear water is added in reactor, solution normal ph heel row bleeds off pressure and filters to obtain PMIDA in measure kettle.The technique that the invention is related to
Parameter is too many, and precise control is difficult in production.
Number of patent application has been the disclosure of the invention of 200510060452X, and a kind of N- phosphonomethyliminoacidetic acidetics are given birth to
Produce the recovery separation method of hydrochloric acid in waste liquid.The step of method, is as follows：1) it is the production of N- phosphonomethyliminoacidetic acidetics is useless
Liquid heats normal pressure using steam or vacuum distillation method is reclaimed；2) Recycling of waste liquid is changed using corrosion-resistant filling rectifying column, economic benefits and social benefits
Hot device, reboiler, the unit equipment of condenser carry out continuous rectification separation, go out acid, tower top by charging, bottom of towe in tower and go out aldehyde company
Continuous rectifying obtains acid and aldehyde；Or batch fractionating separation is carried out using the unit equipment of rectifying still, rectifying column, condenser, pass through
Control reflux ratio and steam aldehyde for 2-10, be terminal as aldehyde ＜ 500ppm in acid in kettle；Or using level Four reverse osmosis membrane
Separate.The equipment investment of the invention is big, the high expensive of spent acid output.
The content of the invention
Goal of the invention：
A kind of preparation side of the PMIDA intermediate iminodiacetic acid that low cost, resource make full use of, impurity content is few is provided
Method.
Technical scheme：
The conventional manufacturing process of iminodiacetic acid：Basic fluxing raction is carried out with alkali and iminodiacetonitrile, alkaline hydrolysis finishes rear salt adding
Acid or sulfurous acid carry out first step acidification reaction, and then intensification separated goes out part water, and iminodiacetic acid is obtained after filtration
Sodium salt solution, finally adds again hydrochloric acid to carry out after second acidification reaction, refiltering so as to obtain iminodiacetic acid solid.It is above-mentioned
Acidification reaction needs the hydrochloric acid for using to be usually hydrogen to carry out synthetic reaction and obtains, the cost of synthesis device and raw material with chlorine
It is very high.
In the acidification reaction of the present invention, using a part acid is substituted（The by-product hydrochloric acid of production trichloroacetaldehyde, wherein HCl contains
Amount about 31%；Or the by-product hydrochloric acid of production pyrophosphate based flame retardant, wherein HCl contents more than 30%；Or production PMIDA
Mother liquor, wherein HCl contents are 10 ~ 15%）It is normally sour with another part as the source of hydrochloric acid（Made by normal synthetic reaction
Hydrochloric acid）It is used in mixed way, together as acidification reaction acid.It is preferred that addition replacement is sour mixed with normal acid in first step acidification reaction
Conjunction is used, and then decolouring removal of impurity process is carried out to reaction solution using activated carbon so that subsequent intensification is distilled and the later stage
Reaction is substantially unaffected, with reaction effect as normal acids.
But, above-mentioned three kinds substitute acid and all otherwise can not can cause reaction system not separately as acidification reaction hydrochloric acid
Stablize, the quality of reaction intermediate iminodiacetic acid and yield decline a lot, and PMIDA impurity multimass is poor.Can only be with part
Normal acid is used in mixed way, and the ratio for mixing is suitable, and normal acid is as follows with the sour proportion in spent acid after preferred mixing：
。
When normal acid is substituted using PMIDA mother liquor, because acid content therein is relatively low, power consumption point is needed after acid adding
Go out more moisture, but energy consumption less than the increase of synthetic hydrochloric acid cost.
When three kinds of spent acid are mixed together, the usage amount of normal acid is 70-75%, and the ratio of mixed acid is not more than
Cross 30%.In this proportion, using any combinations of three kinds of spent acid all without stable system is affected, otherwise occur and obtain
Iminodiacetic acid quality variation, and then affect PMIDA quality and yield.
Beneficial effect：
By the use of mixed acid, while iminodiacetic acid yield and PMIDA yield is not affected, PMIDA purity can
Reach more than 98%.The production cost of PMIDA can be greatly reduced with the method, while having processed production trichloroacetaldehyde, NLD-
During 02 fire retardant, the mother liquor of PMIDA produce spent acid, reduce the discharge of spent acid, saved needed for biochemical treatment into
Sheet 50% or so, alleviates environmental pressure.
Specific embodiment：
Implement example one
Take 105g iminodiacetonitriles plus 416g（wt）20% sodium hydroxide solution carries out alkaline hydrolysis deamination, and trichloroacetaldehyde is added after terminating
By-product hydrochloric acid, adjusts pH=5 ~ 7, plus activated carbon, and heat up distillation, separates water, filters, and obtains iminodiacetic acid sodium salt 560g.
Take 105g iminodiacetonitriles plus 416g（wt）20% sodium hydroxide solution carries out alkaline hydrolysis deamination, and trichlorine is added after terminating
Acetaldehyde by-product hydrochloric acid, adjusts pH=5 ~ 7, plus activated carbon, and heat up distillation, separates water, filters, and obtains iminodiacetic acid sodium salt
560g.Continue plus trichloroacetaldehyde by-product hydrochloric acid, adjust pH=0 ~ 3, be cooled to 15 ~ 20 DEG C of crystallizations, iminodiacetic acid (salt) is obtained after filtration
Acid.
Implement example two
Take 105g iminodiacetonitriles plus 416g（wt）20% sodium hydroxide solution carries out alkaline hydrolysis deamination, and NLD-02 resistances are added after terminating
Combustion agent by-product hydrochloric acid, adjusts pH=5 ~ 7, plus activated carbon, and heat up distillation, separates water, filters, and obtains iminodiacetic acid sodium salt
560g。
Take 105g iminodiacetonitriles plus 416g（wt）20% sodium hydroxide solution carries out alkaline hydrolysis deamination, and NLD- is added after terminating
02 fire retardant, adjusts pH=5 ~ 7, plus activated carbon, and heat up distillation, separates water, filters, and obtains iminodiacetic acid sodium salt 560g.After
Continuous plus trichloroacetaldehyde by-product hydrochloric acid, adjusts pH=0 ~ 3, is cooled to 15 ~ 20 DEG C of crystallizations, and iminodiacetic acid is obtained after filtration.
Claims (4)
1. a kind of preparation method of PMIDA intermediate, it is anti-that the conventional manufacturing process of intermediate iminodiacetic acid is related to acidifying
Should, it is characterised in that：Using the by-product hydrochloric acid or the by-product of production pyrophosphate based flame retardant of part production trichloroacetaldehyde
The mother liquor of hydrochloric acid or production PMIDA is sour as an alternative, is used in mixed way with the normal acid of another part, together as acidification reaction
With acid.
2. the preparation method of PMIDA intermediate as claimed in claim 1, it is characterised in that：Add in first step acidification reaction
Plus substitute and sour be used in mixed way with normal acid.
3. the preparation method of PMIDA intermediate as claimed in claim 1, it is characterised in that：After mixing in normal acid and spent acid
Hydrochloric acid proportion it is as follows：
。
4. the preparation method of PMIDA intermediate as claimed in claim 1, it is characterised in that：Make when three kinds of spent acid are mixed together
Used time, the usage amount of normal acid is 70-80%, the ratio not more than 30% of mixed acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611173276.5A CN106631846A (en) | 2016-12-18 | 2016-12-18 | Preparation method of N-phosphonomethyl aminodiacetic acid intermediate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611173276.5A CN106631846A (en) | 2016-12-18 | 2016-12-18 | Preparation method of N-phosphonomethyl aminodiacetic acid intermediate |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101591255A (en) * | 2008-05-28 | 2009-12-02 | 北京紫光英力化工技术有限公司 | A kind of process for cleanly preparing of iminodiethanoic acid |
| CN102952159A (en) * | 2012-11-14 | 2013-03-06 | 江苏泰仓农化有限公司 | Process for preparing glyphosate intermediate N-Phosphonomethyl iminodiacetic acid by applying N-Phosphonomethyl iminodiacetic acid waste water |
| CN105524107A (en) * | 2014-09-30 | 2016-04-27 | 北京紫光英力化工技术有限公司 | New process for clean production of pmida and cyclic utilization of byproducts |
-
2016
- 2016-12-18 CN CN201611173276.5A patent/CN106631846A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101591255A (en) * | 2008-05-28 | 2009-12-02 | 北京紫光英力化工技术有限公司 | A kind of process for cleanly preparing of iminodiethanoic acid |
| CN102952159A (en) * | 2012-11-14 | 2013-03-06 | 江苏泰仓农化有限公司 | Process for preparing glyphosate intermediate N-Phosphonomethyl iminodiacetic acid by applying N-Phosphonomethyl iminodiacetic acid waste water |
| CN105524107A (en) * | 2014-09-30 | 2016-04-27 | 北京紫光英力化工技术有限公司 | New process for clean production of pmida and cyclic utilization of byproducts |
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Application publication date: 20170510 |