CN1356308A - Process for preparing chelating agent of iminobisuccinate - Google Patents
Process for preparing chelating agent of iminobisuccinate Download PDFInfo
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- CN1356308A CN1356308A CN 01140417 CN01140417A CN1356308A CN 1356308 A CN1356308 A CN 1356308A CN 01140417 CN01140417 CN 01140417 CN 01140417 A CN01140417 A CN 01140417A CN 1356308 A CN1356308 A CN 1356308A
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- alkali metal
- metal hydroxide
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- maleic anhydride
- iminobisuccinate
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Abstract
A process for preparing the chelating agent of iminobisuccinate includes proportionally mixing maleic acid anhydride, alkali-metal hydroxide and/or water to generate maleic acid and alkali-metal salt, regualting pH value, reaction at 100-150 deg.C and 1-5 MPa to generate iminobi succinate, distilling to remove the unreacted ammonia, and adding alkali-metal hydroxide and water to obtain the solution of iminobisuccinate. Its advantages include controllable output rate, high output rate of product, high conversino rate of maleic acid anhydride (97% or more), and durable stability.
Description
The present invention relates to a kind of preparation method of chelating agent of iminobisuccinate.The technology of preparing that belongs to metal chelator.
Iminobisuccinate is the strong chelating agent of heavy metal ion, alkaline-earth metal ions, can be used for cleaning, association with pulp bleaching, electroplate liquid, textile industry of washing composition, stain remover, water conditioner, boiler, heat exchanger, pipeline etc.It is compared with phosphoric acid salt, citric acid, EDTA, has good degradation property and to the metal chelating strong characteristics of making a concerted effort, is called as green chemical.
About the preparation method of iminobisuccinate, English Patent (GB 1 306 331) report: synthesize in 60～155 ℃ of reactions mol ratio 2: 3～2: 5 with toxilic acid and ammonia, add hydrochloric acid or sodium hydroxide solution after the reaction again.USSR (Union of Soviet Socialist Republics) patent (SU 0 639 863) report: in the presence of metal hydroxides, synthesize in 110～130 ℃ mol ratio 2: 0.8～2: 1 with toxilic acid and ammonia.Japanese Patent (JP 6/,329 606) has been reported three one-step preparing methods: 1. maleic acid derivatives and ammonia react in the aqueous solution, 2. add basic metal or alkaline earth metal hydroxides, 3. ripening process.Another piece Japanese Patent (JP 6/,329 607) has also been reported three-step approach: 1. maleic acid derivatives and ammonia react, 2. add basic metal worker alkaline earth metal hydroxides, and 3. add maleic acid derivatives again and further react.United States Patent (USP) (US 6 107 518) report: with maleic anhydride, alkali metal hydroxide, ammonia and water in mol ratio 2: 01～4: 1.1～6: 5～30 in 70～170 ℃, the reaction of 1～80 normal atmosphere 0.1～100 hour, steam unreacted ammonia then, obtain the product of content 5～60% at last.
In the preparation process of aforesaid method, all operate with major control quality of material ratio, condition is wayward, and yield is lower.
The object of the present invention is to provide a kind of preparation method of chelating agent of iminobisuccinate.This method reaches the purpose of control reaction yield by the pH value of control reaction system.Condition is easy to control and reaction yield height.
For achieving the above object, the present invention is realized by following technical proposals: with maleic anhydride, alkali metal hydroxide, ammoniacal liquor is raw material, and the mol ratio 1: 0.01～1.99 of pressing maleic anhydride and alkali metal hydroxide, the mol ratio of maleic anhydride and water 1: 2～30, mix the back and generate toxilic acid and an alkali metal salt, regulate after the pH, add in the reactor, at 100～150 ℃ of reaction generation iminobisuccinates under 1.0～5.0MPa pressure.Steam wherein unreacted ammonia after the reaction, add alkali metal hydroxide and water again, obtain the iminobisuccinate solution product of desired concn, it is characterized in that, can add earlier after the alkali metal hydroxide, by with the pH value in ammonia or the ammoniacal liquor regulation system; Or add ammonia or ammoniacal liquor earlier, and regulate the pH value with alkali metal hydroxide again, realize the control reaction yield; When maleic anhydride and alkali metal hydroxide mol ratio were lower than 0.8, the pH of system preferably was controlled at 7～8, when maleic anhydride and alkali metal hydroxide mol ratio 0.8～1.5 the time, the pH value preferably is controlled at 8～10.
Below the present invention is described further.
Alkali metal hydroxide of the present invention is lithium hydroxide, sodium hydroxide or potassium hydroxide, is preferably sodium hydroxide.When maleic anhydride mixes with alkali metal hydroxide and water, can add in no particular order.But notice that temperature should not surpass 70 ℃, when temperature surpasses more than 70 ℃, the part toxilic acid is converted to fumaric acid, therefore can influence the yield of product.When regulating the pH value with ammonia or ammoniacal liquor, notice that maleic anhydride and alkali metal hydroxide mol ratio are best between 1: 0.8～1.5, the pH value is controlled between 8～10.Temperature of reaction is at 100～150 ℃.Reaction pressure can be self pressure.Also can add rare gas elementes such as air, nitrogen or carbonic acid gas in reactor, at this moment reaction pressure is controlled at 1.0～5.0MPa.Under above-mentioned reaction conditions, the transformation efficiency of maleic anhydride can reach more than 97%.After the reaction, steam wherein unreacted ammonia, service temperature is at 50～170 ℃, and distillation pressure is at 0.001MPa～5.0MPa.After steaming ammonia, add alkali metal hydroxide and water again, obtain the iminobisuccinate solution product of desired concn.The add-on of alkali metal hydroxide should be according to the add-on decision of alkali metal hydroxide before the reaction, and should make alkali-metal total mole number in the product is 4 times of imino-diacetic succsinic acid.The add-on of water is decided on its requirement to production concentration, and production concentration is in 10～60% (weight ratios) generally speaking.Except that unreacted toxilic acid, also contain minor by-products fumaric acid, oxysuccinic acid, aspartic acid etc. in the product.But unreacted toxilic acid and by product do not influence the direct use of product.
The invention has the advantages that by the yield of pH raising product in the adjustment and control system, the transformation efficiency of its maleic anhydride generally can reach more than 97%.Do not contain ammonia in the product iminobisuccinate, can steady in a long-termly preserve, nonpoisonous and tasteless.
Embodiment:
Example 1:
In 5 liter enamel kilns, add 490g (5 moles) maleic anhydride, 510g water, under agitation slowly add 500 gram 40%NaOH solution (5 moles).Begin to add fashionable, maleic anhydride and NaOH reaction, temperature rises rapidly.With the temperature of the water-bath hierarchy of control below 70 ℃.After adding NaOH, the total amount of water is 810g (45 moles) in the system.The conduit that will be connected to liquid ammonia steel bottle then inserts in the liquid, by needle valve control, blasts ammonia in liquid, when pH=10 till.When blasting ammonia, notice that the temperature of the hierarchy of control is lower than 70 ℃.After blasting ammonia, liquid is all joined in the autoclave of 2 liters, charge into nitrogen to 1.0MPa.At rotating speed is to be heated to 120 ℃ under 300 rev/mins of stirrings, reacts 5 hours.The Gao Shida 1.9MPa of reaction pressure.Reaction is transferred in the still kettle after finishing, and adds 500g water and 500g 40%NaOH solution, is evacuated to 35kPa with water pump, steams about 200g ammoniacal liquor under 70～90 ℃.Product is diluted with water to 2000g, filter, solid content is 43.1% product.By analysis, the transformation efficiency of toxilic acid is 97.7%, and the yield of imino-diacetic sodium succinate is 84.6%, and the sodium fumarate yield is 4.0%, and the yield of Asparagus cochinchinensis ammonia acid sodium is 9.2%.
Example 2:
By the schedule of operation of example 1, but control pH=8.Equally, product is diluted with water to 2000g, solid content is 43.5% product.By analysis, the transformation efficiency of toxilic acid is 96.6%, and the yield of imino-diacetic sodium succinate is 82.2%, and the fumaric acid yield is 5.0%, and the yield of aspartic acid is 10.7%.
Example 3:
In 5 liter enamel kilns, add 490g (5 moles) maleic anhydride, 630g water, under agitation slowly add 750 gram 40%NaOH solution (7.5 moles).After adding NaOH, the total amount of water is 1080g (60 moles) in the system.By the method for example 1, regulate pH=8 with ammonia.Reaction is transferred in the still kettle after finishing, and adds 400g water and 250g 40%NaOH solution, steams about 280g ammoniacal liquor.Product is diluted with water to 2000g, filter, solid content is 42.9% product.By analysis, the transformation efficiency of toxilic acid is 97.4%, and the yield of imino-diacetic sodium succinate is 80.1%, and the fumaric acid yield is 4.6%, and the yield of aspartic acid is 11.3%.
Claims (1)
1. the preparation method of a chelating agent of iminobisuccinate, this method is with maleic anhydride, alkali metal hydroxide, ammoniacal liquor is raw material, and the mol ratio 1: 0.01～1.99 of pressing maleic anhydride and alkali metal hydroxide, the mol ratio of maleic anhydride and water 1: 2～30, mix the back and generate toxilic acid and an alkali metal salt, regulate after the pH, add in the reactor, at 100～150 ℃ of reaction generation iminobisuccinates under 1.0～5.0MPa pressure, steam wherein unreacted ammonia after the reaction, add alkali metal hydroxide and water again, obtain the iminobisuccinate solution product of desired concn, it is characterized in that: can add earlier after the alkali metal hydroxide, by with the pH value in ammonia or the ammoniacal liquor regulation system; Or add ammonia or ammoniacal liquor earlier, and regulate the pH value with alkali metal hydroxide again, realize the control reaction yield; When maleic anhydride and alkali metal hydroxide mol ratio were lower than 0.8, the pH of system preferably was controlled at 7～8, when maleic anhydride and alkali metal hydroxide mol ratio 0.8～1.5 the time, the pH value preferably is controlled at 8～10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01140417 CN1126733C (en) | 2001-12-06 | 2001-12-06 | Process for preparing chelating agent of iminobisuccinate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01140417 CN1126733C (en) | 2001-12-06 | 2001-12-06 | Process for preparing chelating agent of iminobisuccinate |
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| CN1356308A true CN1356308A (en) | 2002-07-03 |
| CN1126733C CN1126733C (en) | 2003-11-05 |
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| CN 01140417 Expired - Fee Related CN1126733C (en) | 2001-12-06 | 2001-12-06 | Process for preparing chelating agent of iminobisuccinate |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100341847C (en) * | 2005-02-07 | 2007-10-10 | 刘启民 | Degradable chelate surfactant and producing method |
| CN103320139A (en) * | 2013-06-09 | 2013-09-25 | 沈阳大学 | Environment-friendly eluent for treating heavy-metal-polluted soil |
| CN104447370A (en) * | 2014-04-03 | 2015-03-25 | 石家庄开发区德赛化工有限公司 | Preparation method of imino disuccinate chelator |
| CN105461579A (en) * | 2015-12-24 | 2016-04-06 | 石家庄铁道大学 | Preparation method of imino-disuccinic acid and salt thereof |
| CN111362820A (en) * | 2020-04-16 | 2020-07-03 | 河北协同环保科技股份有限公司 | Low-ammonia synthesis method of iminodisuccinate |
-
2001
- 2001-12-06 CN CN 01140417 patent/CN1126733C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100341847C (en) * | 2005-02-07 | 2007-10-10 | 刘启民 | Degradable chelate surfactant and producing method |
| CN103320139A (en) * | 2013-06-09 | 2013-09-25 | 沈阳大学 | Environment-friendly eluent for treating heavy-metal-polluted soil |
| CN103320139B (en) * | 2013-06-09 | 2016-06-15 | 沈阳大学 | A kind of environment-friendly type leacheate for administering heavy-metal contaminated soil |
| CN104447370A (en) * | 2014-04-03 | 2015-03-25 | 石家庄开发区德赛化工有限公司 | Preparation method of imino disuccinate chelator |
| WO2015149599A1 (en) * | 2014-04-03 | 2015-10-08 | 石家庄开发区德赛化工有限公司 | Method for preparing iminodisuccinate chelating agent |
| US9834503B2 (en) | 2014-04-03 | 2017-12-05 | Hebei Think-Do Environment Co., Ltd. | Method for preparing iminodisuccinate chelating agent |
| CN105461579A (en) * | 2015-12-24 | 2016-04-06 | 石家庄铁道大学 | Preparation method of imino-disuccinic acid and salt thereof |
| CN111362820A (en) * | 2020-04-16 | 2020-07-03 | 河北协同环保科技股份有限公司 | Low-ammonia synthesis method of iminodisuccinate |
| CN111362820B (en) * | 2020-04-16 | 2022-11-01 | 河北协同环保科技股份有限公司 | Low-ammonia synthesis method of iminodisuccinate |
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| CN1126733C (en) | 2003-11-05 |
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