CN1663945A - Method for reclaiming diglycolamidic acid from acidified mother liquor of diglycolamidic acid - Google Patents
Method for reclaiming diglycolamidic acid from acidified mother liquor of diglycolamidic acid Download PDFInfo
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- CN1663945A CN1663945A CN 200410065872 CN200410065872A CN1663945A CN 1663945 A CN1663945 A CN 1663945A CN 200410065872 CN200410065872 CN 200410065872 CN 200410065872 A CN200410065872 A CN 200410065872A CN 1663945 A CN1663945 A CN 1663945A
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- iminodiethanoic
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- iminodiethanoic acid
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Abstract
The invention discloses a method for reclaiming diglycolamidic acid from acidified mother liquor of diglycolamidic acid, which comprises charging calcium salts into iminodiacetic acid acidulation mother liquid, wherein the mole ration of the iminodiacetic acid and the calcium salts is 1:1.0-1:1.8, adjusting and controlling pH between the range of 10.0-11.67, carrying out complex reaction at the temperature of 70-90 deg. C, filtering the reaction solution, obtaining iminodiacetic acid calcium and charging hydrochloric acid, so as to obtain iminodiacetic acid, finally cooling down for crystallization. The mol ratio of iminodiacetic acid calcium and HCL is 1:2-1:5.
Description
Technical field
The present invention relates to a kind of method that from acidified mother solution of iminodiacetic acid, reclaims iminodiethanoic acid.
Background technology
Iminodiethanoic acid is the important intermediate of fine chemistry industry.Its maximum consumption is to produce herbicide glyphosate.Because the huge legendary turtle cooperation usefulness of iminodiethanoic acid and metal ion, it also is widely used in electroplating, the process water processing in electroless plating, electronics, medical treatment, pharmacy, nuclear power field.The production method of iminodiethanoic acid is according to using different starting raw materials that a variety of technologies are arranged.But most of technologies all are at first to generate iminodiacetic acid sodium salt, obtain the iminodiacetic acid (salt) acid product with hcl acidifying again.Because solubleness still contains a certain amount of iminodiethanoic acid in the acidified mother liquor.Recovery method to iminodiethanoic acid in the mother liquor has a lot of research reports both at home and abroad, as adopt substep condensing crystal method, ion exchange method, electrodialytic technique and add recovery methods such as alkali metal sulfates, these methods be not technology complexity be exactly that cost is higher.
Summary of the invention
The objective of the invention is deficiency at above recovery method, a kind of novel method that reclaims iminodiethanoic acid from acidified mother solution of iminodiacetic acid is proposed, cheap, the convenience of drawing materials of the employed cost of material of novel method, recovery method technology is simple, be convenient to operation, is a kind of comparatively desirable, simple and practical recovery method.
The present invention adds calcium salt in acidified mother solution of iminodiacetic acid, make their form complex compound sediment under certain condition, after complex compound sediment is separated again acidifying obtain iminodiethanoic acid.
The calcium salt that adds in acidified mother solution of iminodiacetic acid makes the iminodiethanoic acid in they and the mother liquor form huge legendary turtle compound precipitation, will obtain the recovery method of iminodiacetic acid (salt) acid product behind the sedimentation acidified.Because iminodiethanoic acid has very strong complexing action, choose low-cost complexing agent calcium hydroxide, utilize complexing agent and iminodiethanoic acid generation complex reaction to generate iminodiethanoic acid calcium, thereby the most iminodiethanoic acids in the acidified mother liquor are come out with sedimentary isolated in form, use the hcl acidifying calcium salt again, crystallisation by cooling obtains the iminodiacetic acid (salt) acid product.
Enforcement of the present invention may further comprise the steps and condition:
Add calcium salt in acidified mother solution of iminodiacetic acid, add-on is: the mol ratio of iminodiethanoic acid and calcium salt is 1: 1.0～1: 1.8.
With the pH value adjustment of solution, be controlled in 10.0～11.67 scopes.
70 ℃～90 ℃ temperature of reaction, iminodiethanoic acid and calcium ion carry out complex reaction.
Add hcl acidifying in the iminodiethanoic acid calcium that obtains and generate iminodiethanoic acid behind reacting liquid filtering, crystallisation by cooling can obtain the iminodiacetic acid (salt) acid product, and the add-on of hydrochloric acid is that the mol ratio of iminodiethanoic acid calcium and HCl is 1: 2～1: 5 during acidifying.
More optimize and more particularly: the calcium salt that adds in acidified mother solution of iminodiacetic acid, the application recommends to adopt Ca (OH) cheap and that obtain easily
2Its concrete steps are:
1, in acidified mother solution of iminodiacetic acid, adds certain Ca (OH)
2, Ca (OH)
2Add-on be: iminodiethanoic acid and Ca (OH) in the mother liquor
2Mol ratio be 1: 1.25～1: 1.5 for best.
2, along with Ca (OH)
2Adding, the pH value of solution raises gradually, when pH value surpasses 12, the Ca in the solution
2+Can form Ca (OH)
2Precipitation and separating out, thus the rate of recovery of iminodiethanoic acid influenced.The pH value of complex reaction should be controlled at 10.50～11.50 for best.
3, iminodiethanoic acid and Ca
2+Complex reaction, the completeness of reaction is relevant with temperature of reaction and reaction times, 70 ℃～90 ℃ of optimal reaction temperatures, especially 80 ℃.Optimum reacting time 2.0h～2.5h.
4, add hcl acidifying in the iminodiethanoic acid calcium that obtains and generate iminodiethanoic acid behind reacting liquid filtering, crystallisation by cooling can obtain the iminodiacetic acid (salt) acid product.The add-on of hydrochloric acid is that mol ratio the best of iminodiethanoic acid calcium and HCl is 1: 4 during acidifying; The acidification reaction temperature is 75 ℃～85 ℃; Reaction times is in 0.5h～1.5h scope.
Advantage of the present invention: in acidified mother solution of iminodiacetic acid, add quantitative calcium salt, make it generate complex compound sediment under certain reaction time and temperature condition and be separated, this complex compound is made the iminodiacetic acid (salt) acid product and is obtained reclaiming by adding hcl acidifying.The rate of recovery of iminodiethanoic acid is greater than 85%, and the content that reclaims the iminodiacetic acid (salt) acid product is greater than 95%.This recovery method technology is simple, and the prices of raw and semifnished materials are cheap, and cost recovery is low.
Embodiment
Embodiment 1: (imido-oxalic acid 6g descends together to get 100ml iminodiethanoic acid saturated solution.) in the 250ml beaker, stir, slowly add 3.5g Ca (OH)
2, with hydrochloric acid conditioning solution pH value to 11.67.Change solution over to the 250ml three-necked flask, at 80 ℃ of following stirring reaction 1h, leave standstill, cool off, suction filtration obtains iminodiethanoic acid calcium wet cake 7.25g, content 80.0%, calcium salt yield 79.1%.
Embodiment 2: get 100ml iminodiethanoic acid saturated solution and stir in the 250ml beaker, slowly add 3.5gCa (OH)
2, with hydrochloric acid conditioning solution pH value to 11.67.Change solution over to the 250ml three-necked flask, at 90 ℃ of following stirring reaction 1h, leave standstill, cool off, suction filtration obtains iminodiethanoic acid calcium wet cake 6.75g, content 81.4%, calcium salt yield 71.2%.
Embodiment 3: get 100ml iminodiethanoic acid saturated solution and stir in the 250ml beaker, slowly add 3.5gCa (OH)
2, with hydrochloric acid conditioning solution pH value to 11.67.Change solution over to the 250ml three-necked flask, at 80 ℃ of following stirring reaction 2h, leave standstill, cold, suction filtration obtains iminodiethanoic acid calcium wet cake 7.85g, content 82.2%, calcium salt yield 83.7%.
Embodiment 4: get 100ml iminodiethanoic acid saturated solution and stir in the 250ml beaker, slowly add 3.5gCa (OH)
2, with hydrochloric acid conditioning solution pH value to 11.67.Change solution over to the 250ml three-necked flask, at 80 ℃ of following stirring reaction 2.5h, leave standstill, cool off, suction filtration obtains iminodiethanoic acid calcium wet cake 8.25g, content 79.5%, calcium salt yield 85.0%.
Embodiment 5: get 100ml iminodiethanoic acid saturated solution and stir in the 250ml beaker, slowly add 6.32gCa (OH)
2, with hydrochloric acid conditioning solution pH value to 10.50.Change solution over to the 250ml three-necked flask,, leave standstill, cool off, obtain iminodiethanoic acid calcium wet cake 9.12g, content 81.6%, calcium salt yield 96.5% at 80 ℃ of following stirring reaction 2h.
Embodiment 6: get 100ml iminodiethanoic acid saturated solution and stir in the 250ml beaker, slowly add 3.5gCa (OH)
2, with hydrochloric acid conditioning solution pH value to 10.00.Change solution over to the 250ml three-necked flask, at 70 ℃ of following stirring reaction 2h, leave standstill, cool off, suction filtration obtains iminodiethanoic acid calcium wet cake 8.8g, content 80.3%, calcium salt yield 91.6%.
Embodiment 7: get 100ml iminodiethanoic acid saturated solution and stir in the 250ml beaker, slowly add 4.38gCa (OH)
2, with hydrochloric acid conditioning solution pH value to 11.50.Change solution over to the 250ml three-necked flask, at 80 ℃ of following stirring reaction 2h, leave standstill, cool off, suction filtration obtains iminodiethanoic acid calcium wet cake 9.10g, content 80.5%, calcium salt yield 95.0%.
Embodiment 8: get 100ml iminodiethanoic acid saturated solution and stir in the 250ml beaker, slowly add 5.25gCa (OH)
2, with hydrochloric acid conditioning solution pH value to 11.00.Change solution over to the 250ml three-necked flask, at 80 ℃ of following stirring reaction 2h, leave standstill, cool off, suction filtration obtains iminodiethanoic acid calcium wet cake 9.28g, content 81.0%, calcium salt yield 97.4%.
Embodiment 9: get 100ml iminodiethanoic acid saturated solution and stir in the 250ml beaker, slowly add 7.0gCaCl
2, regulate pH value to 11.00 with sodium hydroxide solution.Change solution over to the 250ml three-necked flask, at 80 ℃ of following stirring reaction 2h, leave standstill, cool off, suction filtration obtains iminodiethanoic acid calcium wet cake 9.15g, content 80.8%, calcium salt yield 95.8%.
Embodiment 10: get 26g iminodiethanoic acid calcium (content 80.0%, down together) in the 100ml three-necked flask, add the stirring of 30ml water and also be warming up to about 60 ℃, drip the acidifying of 42ml concentrated hydrochloric acid, be warming up to 85 ℃ of reaction 0.5h again.Cooling, crystallization, suction filtration obtain iminodiethanoic acid 14.95g content 95.2%, yield 88.0%.
Embodiment 11: get 26g iminodiethanoic acid calcium in the 100ml three-necked flask, add 30ml water and stir and be warming up to about 60 ℃, drip the acidifying of 21ml concentrated hydrochloric acid, be warming up to 80 ℃ of reaction 0.5h again.Cooling, crystallization, suction filtration obtain iminodiethanoic acid 14.2g.Content 95.0%, yield 83.4%.
Embodiment 12 gets 26g iminodiethanoic acid calcium in the 100ml three-necked flask, adds 30ml water and stirs and be warming up to about 60 ℃, and the acidifying of Dropwise 5 2ml concentrated hydrochloric acid is warming up to 80 ℃ of reaction 1h again.Cooling, crystallization, suction filtration obtain iminodiethanoic acid 14.6g.Content 95.1%, yield 85.8%.
Embodiment 13: get 26g iminodiethanoic acid calcium in the 100ml three-necked flask, add 30ml water and stir and be warming up to about 60 ℃, drip the acidifying of 42ml concentrated hydrochloric acid, be warming up to 80 ℃ of reaction 1.5h again.Cooling, crystallization, suction filtration obtain iminodiethanoic acid 15.3g.Content 95.4%, yield 90.2%.
Embodiment 14: get 26g iminodiethanoic acid calcium in the 100ml three-necked flask, add 30ml water and stir and be warming up to about 60 ℃, drip the acidifying of 42ml concentrated hydrochloric acid, be warming up to 90 ℃ of reaction 0.5h again.Cooling, crystallization, suction filtration obtain iminodiethanoic acid 14.52g.Content 95.8%, yield 86.0%.
Embodiment 15: get 26g iminodiethanoic acid calcium in the 100ml three-necked flask, add 30ml water and stir and be warming up to about 60 ℃, drip the acidifying of 42ml concentrated hydrochloric acid, be warming up to 75 ℃ of reaction 0.5h again.Cooling, crystallization, suction filtration obtain iminodiethanoic acid 14.5g.Content 95.5%, yield 85.6%.
Embodiment 16: get 26g iminodiethanoic acid calcium in the 100ml three-necked flask, add 30ml water and stir and be warming up to about 60 ℃, drip the acidifying of 42ml concentrated hydrochloric acid, be warming up to 60 ℃ of reaction 0.5h again.Cooling, crystallization, suction filtration obtain iminodiethanoic acid 14.1g.Content 95.2%, yield 83.0%.
Claims (2)
1, a kind of method that from acidified mother solution of iminodiacetic acid, reclaims iminodiethanoic acid, Step By Condition is as follows:
Add calcium salt in acidified mother solution of iminodiacetic acid, add-on is: the mol ratio of iminodiethanoic acid and calcium salt is 1: 1.0～1: 1.8;
With the pH value adjustment of solution, be controlled in 10.0～11.67 scopes;
In 70 ℃～90 ℃ temperature of reaction, the complex reaction of iminodiethanoic acid and calcium ion;
Add hcl acidifying in the iminodiethanoic acid calcium that obtains and generate iminodiethanoic acid behind reacting liquid filtering, crystallisation by cooling can obtain the iminodiacetic acid (salt) acid product, and the add-on of hydrochloric acid is that the mol ratio of iminodiethanoic acid calcium and HCl is 1: 2～1: 5 during acidifying.
According to the described method that from acidified mother solution of iminodiacetic acid, reclaims iminodiethanoic acid of claim 1, it is characterized in that 2, described calcium salt is to adopt Ca (OH)
2, its concrete steps are:
In acidified mother solution of iminodiacetic acid, add Ca (OH)
2, Ca (OH)
2Add-on be: iminodiethanoic acid and Ca (OH) in the mother liquor
2Mol ratio be 1: 1.25～1: 1.5;
The pH value of complex reaction is controlled at 10.50～11.50;
Iminodiethanoic acid and Ca
2+The complex reaction temperature be 80 ℃;
Add hcl acidifying in the iminodiethanoic acid calcium that obtains and generate iminodiethanoic acid behind reacting liquid filtering, crystallisation by cooling obtains the iminodiacetic acid (salt) acid product; The add-on of hydrochloric acid is that the mol ratio of iminodiethanoic acid calcium and HCl is 1: 4 during acidifying;
The acidification reaction temperature is 75 ℃～85 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410065872 CN1280262C (en) | 2004-12-24 | 2004-12-24 | Method for reclaiming diglycolamidic acid from acidified mother liquor of diglycolamidic acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410065872 CN1280262C (en) | 2004-12-24 | 2004-12-24 | Method for reclaiming diglycolamidic acid from acidified mother liquor of diglycolamidic acid |
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| CN1663945A true CN1663945A (en) | 2005-09-07 |
| CN1280262C CN1280262C (en) | 2006-10-18 |
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101054189B (en) * | 2006-04-12 | 2011-07-06 | 浙江龙游绿得农药化工有限公司 | Method of preparing sea crystal from byproduct salt of refining iminodiacetic acid |
| CN101538216B (en) * | 2008-03-17 | 2012-11-28 | 中国科学院过程工程研究所 | Method for desalting acidified mother solution of iminodiacetic acid using nanofiltration technology |
| CN105985251A (en) * | 2015-02-04 | 2016-10-05 | 北京紫光英力化工技术有限公司 | Clean production process for amino acids such as iminodiacetic acid |
-
2004
- 2004-12-24 CN CN 200410065872 patent/CN1280262C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101054189B (en) * | 2006-04-12 | 2011-07-06 | 浙江龙游绿得农药化工有限公司 | Method of preparing sea crystal from byproduct salt of refining iminodiacetic acid |
| CN101538216B (en) * | 2008-03-17 | 2012-11-28 | 中国科学院过程工程研究所 | Method for desalting acidified mother solution of iminodiacetic acid using nanofiltration technology |
| CN105985251A (en) * | 2015-02-04 | 2016-10-05 | 北京紫光英力化工技术有限公司 | Clean production process for amino acids such as iminodiacetic acid |
| CN105985251B (en) * | 2015-02-04 | 2018-09-18 | 北京紫光英力化工技术有限公司 | A kind of amino acids process for cleanly preparing such as iminodiacetic acid |
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| Publication number | Publication date |
|---|---|
| CN1280262C (en) | 2006-10-18 |
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