CN103613615B - A kind of preparation method of PMIDA - Google Patents
A kind of preparation method of PMIDA Download PDFInfo
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- CN103613615B CN103613615B CN201310680201.6A CN201310680201A CN103613615B CN 103613615 B CN103613615 B CN 103613615B CN 201310680201 A CN201310680201 A CN 201310680201A CN 103613615 B CN103613615 B CN 103613615B
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- sodium chloride
- sodium
- pmida
- acid
- iminodiacetic acid
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Abstract
The present invention provides the preparation method of a kind of PMIDA to be: Iminodiacetic acid sodium salt and hydrochloric acid reaction, obtains the solution containing iminodiacetic acid one sodium and sodium chloride；After the described solution containing iminodiacetic acid one sodium and sodium chloride is concentrated, heat up and filter, obtain solid sodium chloride and filtrate；Described filtrate being mixed with hydrochloric acid and phosphorous acid, heating, be subsequently adding formaldehyde, reaction obtains PMIDA.Due to iminodiacetic acid one sodium, in water, solubility is relatively big and the change of sodium chloride solubility with temperature is inconspicuous, the sodium chloride that the acidifying of bis hydrochloric acid obtains is separated, decrease sodium chloride content, it is to avoid sodium chloride separates out in subsequent reactions, improve reaction yield；Also reduce the viscosity of raw material simultaneously, make raw material mix evenly.Secondly as the sodium chloride in system reduces, when separating PMIDA, washing produces waste water minimizing.Test result indicate that, PMIDA yield prepared by the method for the invention reaches more than 93%.
Description
Technical field
The present invention relates to PMIDA production field, particularly to the preparation method of PMIDA.
Background technology
PMIDA (N-phosphoryl methyl iminodiacetic acid) a kind of for synthesizing glyphosate before
Body, is also to produce wide spectrum to go out the primary raw material of natural disposition post-emergence herbicide.The side of its synthesizing glyphosate
Formula is:
One kettle way is prepared the method for PMIDA and is generally divided into two kinds: hydrochloric acid neutralisation and phosphorus trichloride
Neutralisation.
Wherein, particularly as follows: first hydrochloric acid neutralisation, is neutralized with hydrochloric acid Iminodiacetic acid sodium salt
Salt generates iminodiacetic acid；Iminodiacetic acid and phosphorous acid, mixed in hydrochloric acid, heating, so
Rear dropping formaldehyde, condensation reaction obtains PMIDA (N-phosphoryl methyl iminodiacetic acid).Instead
Answer equation as follows:
Phosphorus trichloride neutralisation is particularly as follows: first, with in phosphorus trichloride and iminodiacetic acid two
Sodium salt generates iminodiacetic acid and phosphorous acid and hydrochloric acid；Iminodiacetic acid and phosphorous acid,
Mixed in hydrochloric acid, heating, then drip formaldehyde, condensation reaction obtains PMIDA (N-phosphoryl methyl
Iminodiacetic acid).Reaction equation is as follows:
No matter use which kind of method above-mentioned to prepare PMIDA, all can produce substantial amounts of sodium chloride, and
And iminodiacetic acid (salt) acid solubility is less.If sodium chloride separates out in late phase reaction, will necessarily
Parcel iminodiacetic acid, affects reaction and carries out, and reduces yield；And during PMIDA crystallization also
Need, by substantial amounts of water washing and desalting, therefore to too increase the generation amount of waste water.
Summary of the invention
Present invention solves the technical problem that the preparation method being to provide a kind of PMIDA, yield
Height, produces waste water few.
The invention discloses the preparation method of a kind of PMIDA, comprise the following steps:
(A) Iminodiacetic acid sodium salt and hydrochloric acid reaction, obtains containing iminodiacetic acid one
Sodium and the solution of sodium chloride；
(B), after the described solution containing iminodiacetic acid one sodium and sodium chloride being concentrated, rise
Temperature filters, and obtains solid sodium chloride and filtrate；
(C) described filtrate is heated with mixed in hydrochloric acid, be subsequently adding phosphorous acid and formaldehyde, mixed
Close reaction, obtain PMIDA.
Preferably, in described step (A), described Iminodiacetic acid sodium salt is by imino-diacetic
Acetonitrile hydrolysis or diethanol amine oxidation obtain.
Preferably, in described step (A), described in be acidified to pH value be 5.0～7.0.
Preferably, in described step (B), the temperature after described intensification is maintained at 50～90 DEG C.
Preferably, in described step (C), the temperature of described heating is 100～120 DEG C.
Preferably, in described step (C), the time of described reaction is 2～4 hours.
Preferably, in described step (C), the mass percentage concentration of described hydrochloric acid is 25%～32%.
Preferably, the phosphorous acid in described step (C) and the imino-diacetic in described step (A)
The mol ratio of acetic acid disodium is 1:(1～5).
Preferably, the formaldehyde in described step (C) and the iminodiacetic acid (salt) in described step (A)
The mol ratio of acid disodium is 1:(1～3).
Preferably, in described step (C), after described reaction, also include crystallisation by cooling and separation
Solid.
Compared with prior art, the preparation method of PMIDA of the present invention is: iminodiacetic acid two
Sodium and hydrochloric acid reaction, obtain the solution containing iminodiacetic acid one sodium and sodium chloride；By described
After solution containing iminodiacetic acid one sodium and sodium chloride concentrates, heat up and filter, obtain chlorination
Sodium solid and filtrate；Described filtrate is mixed with hydrochloric acid and phosphorous acid, heating, be subsequently adding first
Aldehyde, reaction obtains PMIDA.The present invention utilize iminodiacetic acid one sodium in water solubility with
Temperature raises and increases and the sodium chloride solubility with temperature unconspicuous characteristic of change, first by amino
The sodium chloride that the acidifying of oxalic acid disodium hydrochloric acid obtains is separated, and decreases in reaction system
Sodium chloride content, it is to avoid sodium chloride separates out in the reaction be subsequently generated PMIDA, improves anti-
Answer yield；Also reduce the viscosity of raw material simultaneously, make raw material mix evenly.Secondly as
Sodium chloride in system reduces, and when separating PMIDA, washing produces waste water minimizing.Additionally test knot
Fruit shows, PMIDA yield prepared by the method for the invention reaches more than 93%.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet that the present invention prepares PMIDA；
Fig. 2 is the liquid chromatogram of the product of embodiment 1 preparation；
Fig. 3 is the liquid chromatogram of standard PMIDA.
Detailed description of the invention
In order to be further appreciated by the present invention, below in conjunction with embodiment to the preferred embodiment of the invention
It is described, but it is to be understood that these describe simply as further illustrating inventive feature
With advantage rather than limiting to the claimed invention.
The embodiment of the invention discloses the preparation method of a kind of PMIDA, comprise the following steps:
(A) Iminodiacetic acid sodium salt and hydrochloric acid reaction, obtains containing iminodiacetic acid one
Sodium and the solution of sodium chloride；
(B), after the described solution containing iminodiacetic acid one sodium and sodium chloride being concentrated, rise
Temperature filters, and obtains solid sodium chloride and filtrate；
(C) described filtrate is mixed with hydrochloric acid and phosphorous acid, heating, be subsequently adding formaldehyde,
Reaction obtains PMIDA.
The present invention, with Iminodiacetic acid sodium salt as initiation material, prepares PMIDA.Described imido
The source of base oxalic acid disodium is not particularly limited, commercially available acquisition or preferably by imino group
Diacetonitrile hydrolysis or diethanol amine oxidation obtain.Described hydrolysis by iminodiacetonitrile obtains imido
The method of base oxalic acid disodium is: iminodiacetonitrile is hydrolyzed in sodium hydroxide solution,
After ammonia, obtain Iminodiacetic acid sodium salt.Described oxidation by diethanol amine obtains imino group
The method of oxalic acid disodium is: diethanol amine under low pressure catalytic dehydrogenation aoxidizes, and obtains imino group
Oxalic acid disodium.
In the present invention, first iminodiacetic acid disodium salt acid is reacted, obtain containing imido
Base SDA and the solution of sodium chloride.The mass percentage concentration of described hydrochloric acid is preferably
25～33%.Described reaction is preferably 5.0～7.0 to pH value, can complete.Described reactional equation
Formula is:
After obtaining the solution containing iminodiacetic acid one sodium and sodium chloride, after being concentrated, rise
Temperature filters, and obtains solid sodium chloride and filtrate.Described concentration is preferably reduced pressure concentration, described dense
The effect of contracting is to make sodium chloride reach supersaturation.Temperature after described intensification preferably remains in
50～90 DEG C.Due to described iminodiacetic acid one sodium solubility in described temperature range relatively
Greatly, and the change of the solubility with temperature of sodium chloride is inconspicuous, after therefore heating up, and imino-diacetic
Acetic acid one sodium maintains higher solubility, and sodium chloride reaches supersaturation, constantly separates out,
Again through filtering, most sodium chloride is filtered off, and i.e. can get solid sodium chloride and filtrate.
After obtaining described filtrate, by itself and mixed in hydrochloric acid.Described filtrate mainly contains imino group
SDA, described iminodiacetic acid one sodium neutralizes with hydrochloric acid, obtains imino-diacetic
Acetic acid and sodium chloride.After described neutralization, add phosphorous acid mixing, heating, be subsequently adding formaldehyde
Condensation reaction, obtains PMIDA, and the time of described reaction is preferably 2～4 hours.Described phosphorous
Acid is preferably 1:(1～5 with the mol ratio of the Iminodiacetic acid sodium salt in above-mentioned steps), more excellent
Elect 1:1.1～1.5 as.Iminodiacetic acid sodium salt in described formaldehyde and above-mentioned steps mole
Ratio preferably 1:(1～3), more preferably 1:1～2.After described hybrid reaction, the most also pass through
Crystallisation by cooling and separation solid, obtain PMIDA.The temperature of described not crystallisation by cooling is preferably
The time of 10～15 DEG C of crystallisation by cooling is preferably 1～2h.The equation of described reaction is:
The PMIDA yield preparing the method for the invention is tested, and result shows, double sweet
The yield of phosphine reaches more than 93%, and yield is higher.
The present invention by utilizing the dissolubility property of iminodiacetic acid one sodium salt and sodium chloride,
Remove a part of salt before condensation reaction, greatly reduce the content of sodium chloride in reactant mixture,
Avoid reaction and crystallization process in salt out, from but reaction be smoothed out, decrease simultaneously
Washings consumption also improves yield.
In order to be further appreciated by the present invention, the PMIDA present invention provided below in conjunction with embodiment
Preparation method illustrate, protection scope of the present invention is not limited by the following examples.
Embodiment 1
By the iminodiacetic acid disodium salt 179.6g of the 44.5% of generation after Diethanolamine Dehydrogenation
(0.45mol) put in four-hole boiling flask, be heated to 70 DEG C of dissolvings, under stirring condition, drip 31%
Hydrochloric acid is neutralized to pH value 5.0, and reduced pressure concentration steams 90g water, is warming up to 80 DEG C and filters while hot,
Filter cake 20mL hot wash, is dried, obtains 14.3g solid, wherein iminodiacetic acid
One sodium salt mass content 0.10%, remaining is sodium chloride.
Filtrate proceeds to one equipped with reflux condenser, thermometer, agitator, constant pressure funnel
In four-hole bottle, add 45.7g phosphorous acid (weight/mass percentage composition 97%, 0.54mol), 111.9
Hydrochloric acid (weight/mass percentage composition 31%, 0.95mol), drips 47.0g between temperature control 115-120 DEG C
Formaldehyde (content 37%, 0.58mol) is incubated 2h after adding, and is cooled to 10 DEG C, insulation crystallization
2h, filters, and filter cake 10mL water washs, the dry white solid 97.2g that to obtain, content 98.5%,
Chlorion 0.04%, yield 93.7%.
Fig. 1 is the schematic flow sheet that the present invention prepares PMIDA.
Detecting the white solid obtained, Fig. 2 is the liquid phase of the product of embodiment 1 preparation
Chromatogram, Fig. 3 is the liquid chromatogram of standard PMIDA, from Fig. 2 and Fig. 3, implements
Example 1 has prepared PMIDA.
Embodiment 2
The Iminodiacetic acid sodium salt generated after iminodiacetonitrile sodium hydroxide solution is hydrolyzed
Salt 426.5g(content 41.5%, 1mol) put in four-hole boiling flask, heating for dissolving, stirs bar
Dripping 36% hydrochloric acid under part and be neutralized to pH value 5.2, reduced pressure concentration steams 250g water, is warming up to
85 DEG C are filtered while hot, filter cake 20mL hot wash, are dried, obtain 19.8g solid, its
Middle iminodiacetic acid one sodium salt mass content 0.11%, remaining is sodium chloride.
Filtrate proceeds to one equipped with reflux condenser, thermometer, agitator, constant pressure funnel
In four-hole bottle, add 97.2g phosphorous acid (weight/mass percentage composition 97%, 1.15mol), 294.5
Hydrochloric acid (mass content 31%, 2.15mol), drips 105.4g formaldehyde between temperature control 115-120 DEG C
(content 37%, 1.3mol) is incubated 2h after adding, and is cooled to 10 DEG C, insulation crystallization 2h,
Filtering, filter cake 10mL water washs, and is dried to obtain white solid 217.3g, content 98.3%, chlorine
Ion 0.05%, yield 94.1%.
The explanation of above example is only intended to help to understand that the method for the present invention and core thereof are thought
Think.It should be pointed out that, for those skilled in the art, without departing from this
On the premise of bright principle, it is also possible to the present invention is carried out some improvement and modification, these improve and
Modify in the protection domain also falling into the claims in the present invention.
Described above to the disclosed embodiments, makes professional and technical personnel in the field be capable of
Or the use present invention.Those skilled in the art are come by the multiple amendment to these embodiments
Saying and will be apparent from, generic principles defined herein can be without departing from the present invention's
In the case of spirit or scope, realize in other embodiments.Therefore, the present invention will not be by
It is limited to the embodiments shown herein, and is to fit to and principles disclosed herein and new
The widest scope that grain husk feature is consistent.
Claims (9)
1. a preparation method for PMIDA, comprises the following steps:
(A) Iminodiacetic acid sodium salt and hydrochloric acid reaction, obtains containing iminodiacetic acid one sodium
Solution with sodium chloride；
(B), after the described solution containing iminodiacetic acid one sodium and sodium chloride being concentrated, heat up
Filter, obtain solid sodium chloride and filtrate；
(C) described filtrate is mixed with hydrochloric acid and phosphorous acid, heating, be subsequently adding formaldehyde, instead
PMIDA should be obtained；
In described step (B), the temperature after described intensification is maintained at 50～90 DEG C.
Preparation method the most according to claim 1, it is characterised in that described step (A)
In, described Iminodiacetic acid sodium salt is hydrolyzed by iminodiacetonitrile or diethanol amine oxidation obtains.
Preparation method the most according to claim 1, it is characterised in that described step (A)
In, described in be acidified to pH value be 5.0～7.0.
Preparation method the most according to claim 1, it is characterised in that described step (C)
In, the temperature of described heating is 100～120 DEG C.
Preparation method the most according to claim 4, it is characterised in that described step (C)
In, the time of described reaction is 2～4 hours.
6. according to the preparation method described in Claims 1 to 5 any one, it is characterised in that institute
Stating in step (C), the mass percentage concentration of described hydrochloric acid is 25%～32%.
Preparation method the most according to claim 6, it is characterised in that described step (C)
In phosphorous acid and described step (A) in the mol ratio of Iminodiacetic acid sodium salt be 1:(1～5).
Preparation method the most according to claim 6, it is characterised in that described step (C)
In formaldehyde and described step (A) in the mol ratio of Iminodiacetic acid sodium salt be 1:(1～3).
Preparation method the most according to claim 7, it is characterised in that described step (C)
In, also include crystallisation by cooling after described reaction and separate solid.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310680201.6A CN103613615B (en) | 2013-12-12 | 2013-12-12 | A kind of preparation method of PMIDA |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310680201.6A CN103613615B (en) | 2013-12-12 | 2013-12-12 | A kind of preparation method of PMIDA |
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| CN103613615A CN103613615A (en) | 2014-03-05 |
| CN103613615B true CN103613615B (en) | 2016-08-17 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105524107B (en) * | 2014-09-30 | 2017-12-29 | 北京紫光英力化工技术有限公司 | A kind of PMIDA clean manufacturing and accessory substance novel process for recycling |
| CN104672279A (en) * | 2015-03-28 | 2015-06-03 | 山东大学 | Improved pmida energy-saving synthesis method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1242762A (en) * | 1996-11-01 | 2000-01-26 | 孟山都公司 | Use of monosodium iminodiacetic acid solutions for preparing N-phosphonomethyliminodiacetic acid |
| CN101823973A (en) * | 2009-03-02 | 2010-09-08 | 浙江新安化工集团股份有限公司 | Method for separating iminodiacetic acid |
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2013
- 2013-12-12 CN CN201310680201.6A patent/CN103613615B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1242762A (en) * | 1996-11-01 | 2000-01-26 | 孟山都公司 | Use of monosodium iminodiacetic acid solutions for preparing N-phosphonomethyliminodiacetic acid |
| CN101823973A (en) * | 2009-03-02 | 2010-09-08 | 浙江新安化工集团股份有限公司 | Method for separating iminodiacetic acid |
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