JPH0710817B2 - Method for obtaining iminodiacetic acid - Google Patents
Method for obtaining iminodiacetic acidInfo
- Publication number
- JPH0710817B2 JPH0710817B2 JP10869886A JP10869886A JPH0710817B2 JP H0710817 B2 JPH0710817 B2 JP H0710817B2 JP 10869886 A JP10869886 A JP 10869886A JP 10869886 A JP10869886 A JP 10869886A JP H0710817 B2 JPH0710817 B2 JP H0710817B2
- Authority
- JP
- Japan
- Prior art keywords
- ida
- alkali metal
- crystals
- obtaining
- nta
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明はニトリロ三酢酸（NTAと略称する）のアルカリ
金属塩が混在しているイミノ二酢酸（IDAと略称する）
のアルカリ金属塩水溶液よりNTAを含まないIDAを効率良
く分離取得する方法に関する。The present invention relates to iminodiacetic acid (abbreviated as IDA) in which an alkali metal salt of nitrilotriacetic acid (abbreviated as NTA) is mixed.
The present invention relates to a method for efficiently separating and obtaining IDA not containing NTA from the alkali metal salt aqueous solution.
（従来技術） IDAはキレート作用を利用した種々の用途の他、農薬原
料等幅広く使用されている。(Prior Art) IDA is widely used as a raw material for agricultural chemicals in addition to various uses utilizing a chelating action.
IDAの工業的な製造法としては、従来より例えば特公昭4
6−40611や特開昭56−164150等の方法が知られている
が、これらの方法にてIDAを製造すると一般に比較的多
量の副生物としてのNTAアルカリ金属塩を含むIDAアルカ
リ金属塩水溶液が得られる。Conventional industrial methods for producing IDA include, for example, Japanese Patent Publication No.
Methods such as 6-40611 and JP-A-56-164150 are known, but when IDA is produced by these methods, an IDA alkali metal salt aqueous solution containing a relatively large amount of NTA alkali metal salt as a by-product is generally obtained. can get.
このNTAアルカリ金属塩を含むIDAアルカリ金属塩水溶液
よりIDAを取得する常法の方法はこの水溶液に硫酸また
は塩酸を加えて、IDAの溶解度が最小となる等電点であ
るpH2.4として溶解度差により、IDAを析出させ取得する
方法であるが、pH2.4付近ではIDAの溶解度に比してNTA
の溶解度が非常に小さいため液中にNTAが多量にある場
合製品（IDA）中にNTAが混入してしまう。そこでこれを
防ぐため、共存するNTAを溶解するに必要な多量の水を
加えるので、製品（IDA）の取得率が極端に悪くなる。
又それにともない廃水が多量に発生し、その処理の為に
コストがアップしてしまう。The conventional method of obtaining IDA from an IDA alkali metal salt aqueous solution containing this NTA alkali metal salt is to add sulfuric acid or hydrochloric acid to this aqueous solution, and the solubility difference of IDA is set to pH 2.4 which is the isoelectric point at which the solubility of IDA is minimized. It is a method of precipitating and obtaining IDA by using NTA.
Since the solubility of is very small, if there is a large amount of NTA in the liquid, NTA will be mixed in the product (IDA). Therefore, in order to prevent this, a large amount of water necessary to dissolve the coexisting NTA is added, and the acquisition rate of the product (IDA) becomes extremely poor.
In addition, a large amount of waste water is generated along with it, and the cost increases due to the treatment.
したがって従来の方法は経済上の負担は大きく満足すべ
きものとは言い難い。Therefore, it cannot be said that the conventional method has a large economic burden and should be satisfactory.
（発明の課題） 本発明者らは、かかる現状に鑑み、IDAを高収率に晶析
分離し、経済的に有利に実施し得る方法について鋭意研
究した結果、本発明の方法を完成するに至った。(Problems of the invention) In view of the present situation, the present inventors have conducted earnest research on a method capable of crystallizing and separating IDA in a high yield and economically advantageous, and as a result, to complete the method of the present invention. I arrived.
（課題の解決手段） すなわち本発明は、通常は高pH領域での晶析は困難とさ
れている、NTAアルカリ金属塩を含むIDAアルカリ金属塩
水溶液を直接、あるいは濃縮後、50〜５℃まで冷却する
ことによりIDAアルカリ金属塩・水和物の結晶として晶
析させ、NTAアルカリ金属塩は液中に残し、NTAを含ま
ないIDAアルカリ金属塩が取得され、更に、この結晶を
常法により水に溶解後硫酸または塩酸にて中和すること
によりNTAが混入しないIDAを高収率で取得できることを
見出し、本発明を完成するに至った。(Means for Solving the Problems) That is, according to the present invention, the IDA alkali metal salt aqueous solution containing the NTA alkali metal salt, which is generally considered to be difficult to crystallize in a high pH region, is used directly or after concentration to 50 to 5 ° C. Crystallized as crystals of IDA alkali metal salt hydrate by cooling, leaving NTA alkali metal salt in the liquid, IDA alkali metal salt free of NTA is obtained, and further, this crystal is water by a conventional method. It was found that IDA free from NTA contamination can be obtained in a high yield by dissolving in water and neutralizing with sulfuric acid or hydrochloric acid, thus completing the present invention.
即ち、本発明はニトリロ三酢酸アルカリ金属塩を含有す
るイミノ二酢酸アルカリ金属塩の飽和もしくはこれに近
い水溶液をpH10以上にて温度50〜５℃とし、イミノ二酢
酸アルカリ金属塩水和物の結晶を析出させてこれを分離
取得し、水に溶解後硫酸または塩酸にてイミノ二酢酸の
結晶を析出させてこれを分離取得することを特徴とする
イミノ二酢酸の取得法を提供せんとするものである。That is, according to the present invention, a saturated or near aqueous solution of an alkali metal iminodiacetic acid containing nitrilotriacetic acid salt is brought to a temperature of 50 to 5 ° C. at a pH of 10 or higher to obtain crystals of an alkali metal iminodiacetic acid salt. It is intended to provide a method for obtaining iminodiacetic acid, which is characterized by precipitating and separating and acquiring this, and then dissolving in water and precipitating crystals of iminodiacetic acid with sulfuric acid or hydrochloric acid to separate and acquire this. is there.
以下に本発明の方法について更に詳しく説明する。The method of the present invention will be described in more detail below.
図面はpH14でのIDA−Na2,NTA−Na3の溶解度を示すグラ
フである。本発明者らの知見によれば、IDA−Na2は温度
が上昇するにしたがって溶解度も増すが、低温では結晶
水をもつため溶解度が下がる。一方、NTA−Na3は一般的
な溶解度の挙動と異なり、温度の低下とともに溶解度が
増し非常に溶解度が大きいことが判明した。The drawing is a graph showing the solubilities of IDA-Na 2 and NTA-Na 3 at pH 14. According to the findings of the present inventors, the solubility of IDA-Na 2 increases as the temperature rises, but the solubility decreases at low temperatures because it has water of crystallization. On the other hand, it was found that NTA-Na 3 has a very large solubility, which is different from the general behavior of the solubility and increases as the temperature decreases.
本発明はこの性質を利用してNTAが混入しないIDAを高収
率で取得するものである。The present invention utilizes this property to obtain IDA in a high yield that is free from NTA contamination.
pH10以上の高pH領域でIDAアルカリ金属塩の飽和または
これに近い水溶液を50〜５℃に冷却することにより、ID
Aアルカリ金属塩・xH2Oの結晶水をもった結晶が析出
し、これを分離することにより、NTAアルカリ金属塩の
混入しないIDAアルカリ金属塩・xH2Oの結晶が取得でき
る。Saturation of IDA alkali metal salt or a solution close to it in a high pH range of pH 10 or higher is cooled to 50 to 5 ° C.
Crystals of A alkali metal salt / xH 2 O having crystal water are deposited, and by separating them, IDA alkali metal salt / xH 2 O crystals free of NTA alkali metal salt can be obtained.
この際のpHは10以上とすることによりIDA−Na2の型とし
結晶水をもたせることにより溶解度を下げ、分離しやす
い大きな結晶を得ることが出来る。又分離温度が50℃付
近では図面でわかるようにIDA−Na2の溶解度が急激に上
昇し、この温度以上では結晶取得量が少なくなる。５℃
以下では、溶解度はほとんど変化なく、更に低くする意
味がなくなるし、母液が冷却により流動性が悪くなり操
作上困難となる。したがってpH10以上、分離温度50℃〜
５℃とする。At this time, by setting the pH to 10 or more, it becomes a type of IDA-Na 2 and by having water of crystallization, the solubility is lowered and large crystals which can be easily separated can be obtained. Further, as shown in the figure, the solubility of IDA-Na 2 rises sharply when the separation temperature is around 50 ° C, and the amount of crystals obtained decreases above this temperature. 5 ° C
In the following, the solubility is hardly changed, and there is no point in lowering the solubility, and the mother liquor is cooled to have poor fluidity, which makes operation difficult. Therefore, pH 10 or higher, separation temperature 50 ℃ ~
Set to 5 ° C.
次に分離時一度に５℃まで冷却すると高濃度スラリーと
なる操作上困難となるので、IDA−Na2スラリー濃度が20
％前後まで冷却し分離し、この後この操作を１〜２回繰
返す。取得した結晶を中和で生成する芒硝を溶解するに
必要な水を加え加温して溶解する。この後98％硫酸を徐
々に加え、IDAの等電点であるpH2.4付近まで中和。温度
は33℃まで冷却し、熟成後分離することにより高収率で
IDAを回収することが出来る。このときのスラリー濃度
は20〜25wt％が好ましい。この結晶を水に溶解後硫酸ま
たは塩酸にてIDAの等電点付近迄中和して高収率でIDAを
回収することができる。Next, cooling to 5 ℃ at the time of separation will result in a high-concentration slurry, which is difficult to operate, so the IDA-Na 2 slurry concentration should be 20%.
%, And the mixture is separated, after which this operation is repeated 1-2 times. The crystals obtained are neutralized, and water necessary for dissolving Glauber's salt produced by neutralization is added and heated to dissolve. After this, 98% sulfuric acid was gradually added to neutralize the pH to around ID2.4, which is the isoelectric point of IDA. The temperature is cooled to 33 ° C, and after aging, separation is performed to obtain a high yield.
IDA can be collected. The slurry concentration at this time is preferably 20 to 25 wt%. The crystals can be dissolved in water and then neutralized with sulfuric acid or hydrochloric acid to near the isoelectric point of IDA to recover IDA in high yield.
以下本発明の方法について代表的な例を示し更に具体的
に説明するが、これは単なる例示であり、本発明はこれ
らのみに限定されないことは勿論のこと、これらによっ
て何ら制限されないことは言うまでもない。Hereinafter, a representative example of the method of the present invention will be described in more detail, but this is merely an example, and it goes without saying that the present invention is not limited to these and is not limited at all. .
実施例 常法〔特公昭46−40611号参照〕により50wt％グリシン
ソーダ81g（0.40モル）,50wt％グリコロニトリル44g
（0.39モル）を混合後60分撹拌を続ける。次いてこの反
応液と48％水酸化ナトリウム液34g（0.41モル）を加
え、80〜90℃で30分間加水分解し、IDA−Na2水溶液64.5
g（0.364モル）が生成し、副生物としてNTA−Na34.7g
（0.018モル）が副生した。このときのpHは14である。Example According to a conventional method [see Japanese Examined Patent Publication No. 4640611], 81 g (0.40 mol) of 50 wt% glycine soda and 44 g of 50 wt% glycolonitrile.
After stirring (0.39 mol), stirring is continued for 60 minutes. Next, add 34 g (0.41 mol) of this reaction solution and 48% sodium hydroxide solution, hydrolyze at 80 to 90 ° C for 30 minutes, and then use IDA-Na 2 aqueous solution 64.5
g (0.364 mol) is produced, and NTA-Na 3 4.7 g as a by-product
(0.018 mol) was a by-product. The pH at this time is 14.
この反応液600gを常圧で加熱濃縮し、水214gを留去し
た。これを33℃まで冷却し、145gの結晶を分離、この
液を更に５℃まで冷却し、100gの結晶を分離し合計245g
の結晶（IDA−Na2−xH2O）を取得した。析出した結晶は
比較的粒度が粗く、過生が良かった。600 g of this reaction solution was heated and concentrated under atmospheric pressure, and 214 g of water was distilled off. This was cooled to 33 ° C and 145 g of crystals were separated. This liquid was further cooled to 5 ° C and 100 g of crystals were separated to give a total of 245 g.
It was obtained crystals (IDA-Na 2 -xH 2 O ). The precipitated crystals had a relatively coarse grain size and were overgrown.
この結晶246gに水164gを加え、溶解し、98％硫酸を加
え、pH2.4にして、33℃で結晶を分離し、IDA76.7g取得
した。IDA−Na2反応液（27wt％水溶液）からの回収率は
86％であった。Water (164 g) was added to the crystals (246 g) and dissolved, 98% sulfuric acid was added to adjust the pH to 2.4, and the crystals were separated at 33 ° C. to obtain IDA (76.7 g). The recovery rate from the IDA-Na 2 reaction solution (27 wt% aqueous solution) is
It was 86%.
比較例 実施例と同様の組成であるIDA−Na227wt％水溶液600gに
水1080g（NTAを溶解するための必要量）を加え直接、98
％硫酸を徐々に加えpH2.4に中和して、析出した結晶を3
3℃で結晶を分離し、IDA8.8g取得した。IDA-Na227wt％
水溶液からの回収率は７％であった。Comparative Example 1080 g of water (a necessary amount for dissolving NTA) was directly added to 600 g of an IDA-Na 2 27 wt% aqueous solution having the same composition as that of the example, and 98
% Sulfuric acid was gradually added to neutralize the pH to 2.4 and the precipitated crystals were
Crystals were separated at 3 ° C to obtain 8.8 g of IDA. IDA-Na 2 27wt%
The recovery rate from the aqueous solution was 7%.
図面はpH14でのIDA-Na2、NTA-Na3の水に対する溶解度を
表わすグラフである。縦軸は溶解度（g/100gH2O）横軸
は温度（℃）である。The drawing is a graph showing the solubility of IDA-Na 2 and NTA-Na 3 in water at pH 14. The vertical axis represents the solubility (g / 100gH 2 O) and the horizontal axis represents the temperature (° C).
Claims (1)
ミノ二酢酸アルカリ金属塩の飽和もしくはこれに近い水
溶液をpH10以上にて温度50〜５℃とし、イミノ二酢酸ア
ルカリ金属塩水和物の結晶を析出させてこれを分離取得
し、水に溶解後硫酸または塩酸にてイミノ二酢酸の結晶
を析出させてこれを分離取得することを特徴とするイミ
ノ二酢酸の取得法。1. A saturated aqueous solution of an alkali metal minodiacetate containing nitrilotriacetic acid salt or a solution close to this is brought to a temperature of 50 to 5 ° C. at a pH of 10 or more to form crystals of an hydrated alkali metal iminodiacetic acid salt. A method for obtaining iminodiacetic acid, which comprises precipitating and separating and obtaining this, dissolving in water, precipitating crystals of iminodiacetic acid with sulfuric acid or hydrochloric acid, and separating and obtaining this.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10869886A JPH0710817B2 (en) | 1986-05-14 | 1986-05-14 | Method for obtaining iminodiacetic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10869886A JPH0710817B2 (en) | 1986-05-14 | 1986-05-14 | Method for obtaining iminodiacetic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62265255A JPS62265255A (en) | 1987-11-18 |
| JPH0710817B2 true JPH0710817B2 (en) | 1995-02-08 |
Family
ID=14491366
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10869886A Expired - Fee Related JPH0710817B2 (en) | 1986-05-14 | 1986-05-14 | Method for obtaining iminodiacetic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0710817B2 (en) |
-
1986
- 1986-05-14 JP JP10869886A patent/JPH0710817B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62265255A (en) | 1987-11-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US2654779A (en) | Method of preparation of guanidino fatty acids | |
| US5312973A (en) | Process for producing n-phosphono-methyl-imino-diacetic acid | |
| EP0469541B1 (en) | Method of crystallizing phenylalanine | |
| JPH0710817B2 (en) | Method for obtaining iminodiacetic acid | |
| JPS6257180B2 (en) | ||
| US1582472A (en) | Manufacture of glutamic acid and salts thereof | |
| JP3362468B2 (en) | Process for producing N-mixed saturated fatty acyl neutral amino acids | |
| US2414303A (en) | Recovery of cysteine | |
| US8871170B2 (en) | Polyhalite IMI process for KNO3 production | |
| JP3823330B2 (en) | Method for isolating N-phosphonomethylglycine | |
| US1947563A (en) | Process for manufacturing and recovering glutamic acid and its compounds | |
| JP2915515B2 (en) | Process for producing O-methylisourea sulfate | |
| JPS588028A (en) | Separation of dipentaerythritol | |
| RU2285667C1 (en) | Method of production of the high purity magnesium nitrate hexahydrate from the technical solution of magnesium nitrate | |
| KR880000038B1 (en) | Process for refining of alpha-l-aspartyl-l-phenylalanine | |
| US3355485A (en) | Preparation of sodium cyclohexyl sulfamate free of sulfate ions | |
| JP2896259B2 (en) | Method for isolating phenylalanine | |
| EP0427401A1 (en) | Conversion of iminodiacetic acid crystal liquors to concentrated solutions of monoalkalimetal or monoammonium iminodiacetate | |
| JP3162366B2 (en) | Method for isolating phenylalanine | |
| JPS6157295B2 (en) | ||
| JP3606396B2 (en) | Method for producing nickel hypophosphite | |
| JPH0687803A (en) | Glycine production method | |
| US1255390A (en) | Process to separate glutaminic acid from other amino acids. | |
| KR100625553B1 (en) | Manufacturing method of N2- (1 (S) -carboxy-3-phenylpropyl) -L-lysyl-L-proline | |
| JPS588384B2 (en) | Separation method of glycine and iminodiacetic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |