CN106928077B - The preparation method of methylglycine diacetic acid - Google Patents
The preparation method of methylglycine diacetic acid Download PDFInfo
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- CN106928077B CN106928077B CN201710147108.7A CN201710147108A CN106928077B CN 106928077 B CN106928077 B CN 106928077B CN 201710147108 A CN201710147108 A CN 201710147108A CN 106928077 B CN106928077 B CN 106928077B
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/02—Formation of carboxyl groups in compounds containing amino groups, e.g. by oxidation of amino alcohols
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
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Abstract
The invention belongs to compounding agent fields, and in particular to a kind of preparation method of methylglycine diacetic acid.Preparation method of the invention obtains methylglycine diacetonitrile by raw material of iminodiacetic acid, acetaldehyde and hydrogen cyanide, and methylglycine diacetonitrile is instilled aqueous slkali hydrolysis, obtains target product methylglycine diacetic acid；This method reaction time is short, easy to operate, and reaction process by-product is seldom, and the waste water of generation is few, high-efficiency environment friendly, is suitble to large-scale continuous production, and the methylglycine diacetic acid reaction yield prepared can reach 90% or more, impurity is few, and NTA is less than 0.1%.
Description
Technical field
The invention belongs to compounding agent fields, and in particular to a kind of preparation method of methylglycine diacetic acid.
Background technique
General slurry is not pure water, contains each metal ion species to some extent.Wherein, the water hardness is constituted
Calcium, magnesium plasma and iron, manganese plasma will produce serious influence to cleaning function.As fabric turns yellow, graying, feel is hardened
Deng.In order to eliminate influence caused by the washing of underwater gold category ion pair, water softener will generally be added in detergent.Therein one
Kind is exactly compounding agent, and the use of compounding agent can save active matter, and avoid leaving sediment on substrate, make substrate
It is bright in luster.With common compounding agent, as amino polyphosphate, multi-carboxylate or aminopolycanboxylic acid's salt (such as ethylenediamine tetra-acetic acid,
EDTA it) compares, methylglycine diacetic acid (MGDA) has the advantages that nontoxic and is readily biodegradable, and can be used for producing cleaning
The adhesive of agent, polishing agent and solidification matrix.
Methylglycine diacetic acid, English name Methylglycine-N, Ndiacetic acid, abbreviation MGDA.It is a kind of
Non-toxic and readily biodegradable compounding agent, for producing the adhesive of detergent, production polishing agent and solidification matrix, than
Common compounding agent EDTA more easily biological-degradable.
MGDA is the biology easily decomposability chelating of German BASF institute development and production, product nameQuasi- OECD
When the Biodegradable test of criterion, resolution ratio within 28 days up to 98% and be identified as ' the easy decomposability of biology ', chelating
Agent industry quite payes attention to Biodegradable type product.
In MGDA preparation method, from the point of view of reaction raw materials, the common synthetic method of MGDA can be divided into two major classes.One kind is
Strecher is carried out with hydrogen cyanide, formaldehyde by alanine to react, then obtains product through hydrolysis；Another kind of is by iminodiacetonitrile
Strecher is carried out with hydrogen cyanide, acetaldehyde to react, then obtains product through hydrolysis.From the point of view of reaction medium, it can be situated between in alkalinity
It carries out, can also be carried out in acid medium in matter.Preparation MGDA is reacted by Strecher by alanine, is described for the first time
In WO9429421, typical reaction formula following reaction formula, patent US5817864 report can replace hydrogen cyanide in alkalinity with Cymag
It is reacted in medium, but by-product is more, and is not readily separated purification.
In order to reduce the content of harmful by-products NTA in product, BASF AG uses many methods, such as:
The graded hydrolysis method that 200680015457.3 patent neutral and alkali hydrolysis temperatures are gradually increased, 201280015487.X control alanine
Reacting dose, US:5849950 reacts in acid medium；But reaction is usually required using additional acid (such as in acid medium
The concentrated sulfuric acid) to reduce pH, the content etc. of harmful by-products NTA in product is reduced by using complicated technical solution, these
Factor limits MGDA and is extremely difficult to simply production, high yield, low by-product.
201180013685.8 report and begin through ethoxylation by amine and form amino alcohol, subsequent oxidative dehydrogenation preparation
The method of MGDA, mentions that by-products content is low, and product is not required to purify in this method, but wherein the ethoxylation of amine is usually being greater than
Carried out at 120 DEG C of temperature and certain pressure, the step of oxidative dehydrogenation in be also that typically at a temperature of pressurization and 140-220 DEG C
It carries out, the program increases energy consumption to the more demanding of device, increases cost.
As it can be seen that there are the content of harmful by-products NTA height, complex process, high production cost, energy in above-mentioned preparation method
Consume the problems such as big.
Summary of the invention
In view of this, the present invention is the invention discloses a kind of preparation method of methylglycine diacetic acid with imino-diacetic
Acetic acid, acetaldehyde and hydrogen cyanide are raw material to prepare methylglycine diacetic acid, and the reaction time is short, easy to operate, reaction process pair
Product is seldom, and the waste water for reacting generation is few, is suitble to large-scale continuous production.
Methylglycine diacetic acid (MGDA) molecular formula:
The preparation method of methylglycine diacetic acid, using iminodiacetic acid, acetaldehyde and hydrogen cyanide as Material synthesis methyl
Glycine diacetonitrile, methylglycine diacetonitrile are hydrolyzed to obtain methylglycine diacetic acid again.
It is many in imido grpup diacetonitrile product currently on the market according to the related patents of imido grpup diacetonitrile method synthesis MGDA
Impurity generates inhibiting effect, allows to effectively participate in synthetic reaction only 90~95%, yield also only has 86%, and imino group
The yield that oxalic acid (IDA) synthesizes MGDA is greater than 90%, so iminodiacetic acid (salt) acid system total recovery wants high by 4~7%, cost is more
It is low), and imido grpup diacetonitrile method has high concentration ammonia-containing water containing cyanogen when separating MGDN crystal, it is extremely difficult to it handles, and imido
Base diethyl acid system does not generate hc effluent, more environmentally friendly.
Further, the molar ratio of the iminodiacetic acid, acetaldehyde and hydrogen cyanide is 0.95~1.05:1.00~1.05:
1.00~1.10.
As a preference, the molar ratio of the iminodiacetic acid, acetaldehyde and hydrogen cyanide is 1.00:1.00~1.05:
1.00~1.10.
As a preference, the hydrogen cyanide is liquid or gaseous state.
Further, the preparation method specifically includes the following steps:
1) acetaldehyde and hydrogen cyanide reaction are added in iminodiacetic acid (salt) aqueous acid, obtains the molten of the diacetonitrile containing methylglycine
Liquid；
2) solution of the diacetonitrile containing methylglycine described in step 1) is added in sodium hydroxide solution and is reacted, must contained
The solution of methylglycine diacetic acid.
Further, in step 1) hydrogen cyanide mass percent >=99%.
Further, iminodiacetic acid aqueous solution, first will with sodium hydroxide before acetaldehyde and hydrogen cyanide is added in step 1)
Iminodiacetic acid solution ph is adjusted to 6~7, and temperature is controlled at 20~30 DEG C.
Before acetaldehyde and hydrogen cyanide is added, adjusting PH with sodium hydroxide is 6~7, and reacting can just go on smoothly under this condition,
High income under this condition, impurity is few, and NTA is less than 0.1%.
As a preference, the sodium hydroxide for adjusting iminodiacetic acid solution ph is solid or liquid.
Further, the temperature reacted in step 1) is 60~70 DEG C.
As a preference, being warming up to 60~70 DEG C in step 1), 20~40min of insulation reaction is obtained containing methylglycine
The solution of diacetonitrile.
Further, the mass percent of the sodium hydroxide solution in step 2) is 20~50%.
Further, in the sodium hydroxide solution in step 2) and step 1) molar ratio of acetaldehyde be 2.0~2.2:1.00~
1.05。
Further, the reaction temperature in step 2) is 25~50 DEG C.
As a preference, the adding manner of the solution of the diacetonitrile containing methylglycine is to be added dropwise in step 2).
Further, the preparation method further comprise the steps of: 3) by described in step 2) containing methylglycine diacetic acid
Solution is warming up to boiling reflux, and 3~5h of heat preservation drives ammonia substantially completely out of, and it is sweet to get methyl that hydrogen peroxide, active carbon decoloring is added
Propylhomoserin diethyl acid solution.
The beneficial effects of the present invention are:
1. in the preparation method of MGDA of the invention, obtaining methyl by raw material of iminodiacetic acid, acetaldehyde and hydrogen cyanide
Methylglycine diacetonitrile is instilled aqueous slkali hydrolysis, obtains target product MGDA, this method reaction time by glycine diacetonitrile
Short, easy to operate, reaction process by-product is seldom, and the waste water for reacting generation is few, high-efficiency environment friendly, is suitble to extensive continuous raw
It produces.
2. the MGDA reaction yield of the method for the present invention preparation can reach 90% or more.
Specific embodiment
It detailed description of a preferred embodiment of the present invention will be given below.The reality of actual conditions is not specified in preferred embodiment
Proved recipe method, usually according to normal condition, illustrated embodiment are but not to be to preferably be illustrated to the contents of the present invention
The contents of the present invention are only limitted to illustrated embodiment.So those skilled in the art are according to foregoing invention content to embodiment party
Case carries out nonessential modifications and adaptations, still falls within protection scope of the present invention.
Embodiment 1
135.8g IDA (1.0mol) is added in flask, 270g water, 50%NaOH80g, stirring and dissolving, PH about 6.5, control
30 DEG C of temperature processed, while hydrogen cyanide 28.6g (99%, 1.05mol) and acetaldehyde 110g (40%, 1.0mol), 1~2h drop is added dropwise
It is complete, 70 DEG C are warming up to, 30min is kept the temperature, then reaction solution is added drop-wise in 287g30%NaOH (2.15mol), temperature is added dropwise in control
30~35 DEG C of degree, about 2~3h is dripped off, and after dripping off, 30 DEG C of heat preservation 3min then heat to boiling, and reflux about 4h is until return pipe
Tail gas PH7~8 terminates, and is cooled to 80 DEG C, and 2g hydrogen peroxide is added, and reacts 30min, adds active carbon 2g, keeps the temperature 30min, mistake
Filter content 30% MGDA solution 842g, can continue concentration be made 40% MGDA solution, yield 93%, NTA content
0.07%.
Embodiment 2
135.8g IDA (1.0mol) is added in flask, 270g water, 50%NaOH80g, stirring and dissolving, PH about 6.5, control
30 DEG C of temperature processed, gas hydrogen cyanide 28.6g (1.05mol) and acetaldehyde 115.5g (40%, 1.05mol) are successively rapidly joined, is risen
Temperature keeps the temperature 30min, then reaction solution is added drop-wise in 287g30%NaOH (2.15mol) to 70~80 DEG C, controls dropping temperature
30~35 DEG C, after dripping off, 30 DEG C of heat preservation 3min then heat to boiling, and reflux about 4h terminates up to return pipe tail gas PH7~8,
It is cooled to 80 DEG C, 3g hydrogen peroxide is added, react 30min, add active carbon 2g, keep the temperature 30min, filter to obtain content 28.9%
MGDA solution 845g can continue the MGDA solution that concentration is made 40%, yield 90.08%, NTA content 0.09%.
3 comparative example of embodiment
135.8g IDA (1.0mol) is added in flask, 270g water, 50%NaOH80g, stirring and dissolving, PH about 6.5, control
30 DEG C of temperature processed, gas hydrogen cyanide 27.3g (1.00mol) and acetaldehyde 121g (40%, 1.10mol) are successively rapidly joined, is heated up
To 70~80 DEG C, 30min is kept the temperature, then reaction solution is added drop-wise in 287g30%NaOH (2.15mol), controls dropping temperature 30
~35 DEG C, after dripping off, 30 DEG C of heat preservation 3min then heat to boiling, and reflux about 4h is until return pipe tail gas PH7~8 end, drop
3g hydrogen peroxide is added to 80 DEG C in temperature, reacts 30min, adds active carbon 2g, keep the temperature 30min, filters to obtain content 25.3%
MGDA solution 849g, yield 79.1%, NTA content 0.1%.
4 comparative example of embodiment
135.8g IDA (1.0mol) is added in flask, 270g water, 50%NaOH80g, stirring and dissolving, PH about 6.5, control
30 DEG C of temperature processed, gas hydrogen cyanide 24.33g (0.90mol) and acetaldehyde 115.5g (40%, 1.05mol) are successively rapidly joined, is risen
Temperature keeps the temperature 30min, then reaction solution is added drop-wise in 287g30%NaOH (2.15mol) to 70~80 DEG C, controls dropping temperature
30~35 DEG C, after dripping off, 30 DEG C of heat preservation 3min then heat to boiling, and reflux about 4h terminates up to return pipe tail gas PH7~8,
It is cooled to 80 DEG C, 3g hydrogen peroxide is added, react 30min, add active carbon 2g, keep the temperature 30min, filter to obtain content 22.0%
MGDA solution 838g, yield 68%, NTA content 0.05%.
5 comparative example of embodiment
146.4g IDA (1.1mol) is added in flask, 270g water, 50%NaOH80g, stirring and dissolving, PH about 6.5, control
30 DEG C of temperature processed, while hydrogen cyanide 28.6g (99%, 1.05mol) and acetaldehyde 110g (40%, 1.0mol), 1~2h drop is added dropwise
It is complete, 70 DEG C are warming up to, 30min is kept the temperature, then reaction solution is added drop-wise in 287g30%NaOH (2.15mol), temperature is added dropwise in control
30~35 DEG C of degree, about 2~3h is dripped off, and after dripping off, 30 DEG C of heat preservation 3min then heat to boiling, and reflux about 4h is until return pipe
Tail gas PH7~8 terminates, and is cooled to 80 DEG C, and 2g hydrogen peroxide is added, and reacts 30min, adds active carbon 2g, keeps the temperature 30min, mistake
Filter content 26.76% MGDA solution 851g, yield 84%, NTA content 0.08%.
6 comparative example of embodiment
135.8g IDA (1.0mol) is added in flask, 270g water, 50%NaOH80g, stirring and dissolving, PH about 5, control
30 DEG C of temperature, while hydrogen cyanide 28.6g (99%, 1.05mol) and acetaldehyde 110g (40%, 1.0mol) is added dropwise, 1~2h is dripped off,
80 DEG C are warming up to, 30min is kept the temperature, then reaction solution is added drop-wise in 287g30%NaOH (2.15mol), controls dropping temperature 30
~35 DEG C, about 2~3h is dripped off, and after dripping off, 30 DEG C of heat preservation 3min then heat to boiling, and reflux about 4h is until return pipe tail gas
PH7~8 terminates, and is cooled to 80 DEG C, and 2g hydrogen peroxide is added, and reacts 30min, adds active carbon 2g, keeps the temperature 30min, filters
The MGDA solution 842g of content 26.1% can continue the MGDA solution that concentration is made 40%, yield 81.06%, NTA content
0.1%.
7 comparative example of embodiment
135.8g IDA (1.0mol) is added in flask, 270g water, 50%NaOH80g, stirring and dissolving, PH about 6.5, control
40 DEG C of temperature processed, while hydrogen cyanide 28.6g (99%, 1.05mol) and acetaldehyde 110g (40%, 1.0mol), 1~2h drop is added dropwise
It is complete, 80 DEG C are warming up to, 30min is kept the temperature, then reaction solution is added drop-wise in 287g30%NaOH (2.15mol), temperature is added dropwise in control
30~35 DEG C of degree, about 2~3h is dripped off, and after dripping off, 30 DEG C of heat preservation 3min then heat to boiling, and reflux about 4h is until return pipe
Tail gas PH7~8 terminates, and is cooled to 80 DEG C, and 2g hydrogen peroxide is added, and reacts 30min, adds active carbon 2g, keeps the temperature 30min, mistake
Filter content 27.2% MGDA solution 842g, can continue concentration be made 40% MGDA solution, yield 84.47%, NTA content
0.15%.
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to compared with
Good embodiment describes the invention in detail, those skilled in the art should understand that, it can be to skill of the invention
Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this
In the scope of the claims of invention.
Claims (5)
1. the preparation method of methylglycine diacetic acid, which is characterized in that specifically includes the following steps:
1) acetaldehyde and hydrogen cyanide reaction are added in iminodiacetic acid (salt) aqueous acid, obtains the solution of the diacetonitrile containing methylglycine；
The molar ratio of the iminodiacetic acid, acetaldehyde and hydrogen cyanide is 0.95~1.05:1.00~1.05:1.00~1.10；
2) solution of the diacetonitrile containing methylglycine described in step 1) is added in sodium hydroxide solution and is reacted, obtained containing methyl
The solution of glycine oxalic acid；The molar ratio of acetaldehyde described in the sodium hydroxide solution is 2.0~2.2:1.00~1.05；
Iminodiacetic acid aqueous solution is before being added acetaldehyde and hydrogen cyanide in step 1), first with sodium hydroxide by iminodiacetic acid
Solution ph is adjusted to 6.5, and temperature is controlled at 20~30 DEG C.
2. preparation method according to claim 1, which is characterized in that the mass percent of hydrogen cyanide in step 1) >=
99%.
3. preparation method according to claim 1, which is characterized in that the temperature reacted in step 1) is 60~70 DEG C.
4. preparation method according to claim 1, which is characterized in that the quality percentage of the sodium hydroxide solution in step 2)
Than being 20~50%.
5. preparation method according to claim 1, which is characterized in that the reaction temperature in step 2) is 25~50 DEG C.
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| CN112010769B (en) * | 2020-09-01 | 2023-01-31 | 河南清水源科技股份有限公司 | Preparation method of green chelating agent methylglycine diacetic acid sodium salt |
| CN115710194A (en) * | 2022-10-13 | 2023-02-24 | 天宝动物营养科技股份有限公司 | Preparation method and production system of methylglycine diacetic acid trialkali metal salt |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5817864A (en) * | 1995-05-29 | 1998-10-06 | Basf Aktiengesellschaft | Process for the preparation of glycine-N, N-diacetic acid derivatives |
| US5849950A (en) * | 1995-05-29 | 1998-12-15 | Basf Aktiengesellschaft | Preparation of glycine-N,N-diacetic acid derivatives |
| CN102993034A (en) * | 2011-09-19 | 2013-03-27 | 重庆紫光化工股份有限公司 | Preparation method of methyl-glycine diacetate tri-sodium |
| CN103547561A (en) * | 2011-05-23 | 2014-01-29 | 巴斯夫欧洲公司 | Method for producing aminopolycarboxylates |
-
2017
- 2017-03-13 CN CN201710147108.7A patent/CN106928077B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5817864A (en) * | 1995-05-29 | 1998-10-06 | Basf Aktiengesellschaft | Process for the preparation of glycine-N, N-diacetic acid derivatives |
| US5849950A (en) * | 1995-05-29 | 1998-12-15 | Basf Aktiengesellschaft | Preparation of glycine-N,N-diacetic acid derivatives |
| CN103547561A (en) * | 2011-05-23 | 2014-01-29 | 巴斯夫欧洲公司 | Method for producing aminopolycarboxylates |
| CN102993034A (en) * | 2011-09-19 | 2013-03-27 | 重庆紫光化工股份有限公司 | Preparation method of methyl-glycine diacetate tri-sodium |
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