CN1990460A - Comprehensive treatment of glycine crystallization mother liquid - Google Patents
Comprehensive treatment of glycine crystallization mother liquid Download PDFInfo
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- CN1990460A CN1990460A CN 200510135493 CN200510135493A CN1990460A CN 1990460 A CN1990460 A CN 1990460A CN 200510135493 CN200510135493 CN 200510135493 CN 200510135493 A CN200510135493 A CN 200510135493A CN 1990460 A CN1990460 A CN 1990460A
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- iminodiethanoic
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Abstract
The invention discloses three ways of effectively treating catalyized mother liquid of glycine. First, separates components in mother liquid with ion-exchange resin. Second, precipitates components in mother liquid by adjusting acidity of mother liquid in salt, then separates and recovers. Third, converses glycine in mother liquid through chemical reaction into iminodiacetic acid, then seprates it through catalization. The invention produces social and economic benefit.
Description
Technical field
The present invention relates to the synthetic of glycine, particularly the treatment process of the synthetic middle crystalline mother solution of glycine.
Background technology
Glycine is the important source material of industry such as chemical industry, medicine, agricultural chemicals, has purposes widely.At present, have several different methods to produce glycine, wherein, the alpha-halogen acid system is domestic main industrialized preparing process, and it is to be raw material with Mono Chloro Acetic Acid, ammonia, reacts in solvent phase in the presence of catalyzer urotropine (vulkacit H).Adopt the alpha-halogen acid system, solvent phase can be a water, but this water method is produced the method for glycine many defectives are arranged, for example exist catalyzer not reclaim, consumption is big, catalytic efficiency is low, the intact raw material of unreacted can not reuse, and owing to reasons such as system alkalescence are strong and moisture, easily generates the hydrolyzate oxyacetic acid, cause waste, contaminate environment; Inorganic salt separation difficulty such as the ammonium chloride that produces in the reaction, post-processing difficulty is big, building-up reactions endpoint difficulty or the like.In addition, reported also in the document that solvent is the method for preparing glycine of pure phase, but it still exists the reaction times longer, and reacts bad control, and catalyst efficiency is lower, detect through NMR, there are two kinds of by products of 5%-7% to generate, thus still there is the lower defective of yield, and difficult solvent recovery, defectives such as solvent consumption is big are not suitable for the big production of industry.
There is bibliographical information to adopt hydroxyacetonitrile, amide and carbon dioxide reaction to prepare the method for glycine in recent years successively.This method can roughly be divided into following three classes again:
1) method that adopts alkali lye to carry out aftertreatment is referring to for example JP-A-06-065168, JP-A-05-320106, JP-A-53-031616, US5225592A, JP-A-02-250854, WO92/06069, JP-A-53-028115, CN1107139A.But there is by-product object height in the product in the described technology of these patent documentations, and product and inorganic salt are carried secretly seriously mutually, and finished color is darker, the decolouring difficulty, so quality product is difficult to reach customer requirements.
2) method that adopts acid solution to carry out aftertreatment, for example JP-A-2-286651, JP-A-04-066559, JP-A-02-306946, JP-A-53-028116, US 2384816A.When adopting mineral acid or organic acid derivatives to be hydrolyzed, the general basic metal aqueous solution such as sodium hydroxide or potassium hydroxide of adopting of neutralization neutralizes, exist product purity low equally, inorganic salt are carried secretly, the three wastes are handled difficult problem, and the product color that obtains is darker.
3) method that adopts strong base anion resins to carry out aftertreatment, for example JP-A-03-190851.The purity of this method reaction yield and glycine is undesirable.Aforesaid method adopts ammonia to react, need under the condition of High Temperature High Pressure, carry out, and severe reaction conditions, facility investment is big, and the separation problem of inorganic salt is effectively solved as yet.
At the deficiencies in the prior art, the present inventor has carried out deep research, has invented directly to carry out intermittence or continuous reaction with hydroxyacetonitrile and excess of ammonia, high yield, highly selective obtains the commercial run of aminoacetonitriles, the ammonia of gained is separated liquid can high conversion under the determined processing condition of the present invention, and highly selective obtains glycine, particularly efficiently solves the processing of glycine crystallization mother liquid, reduce the material consumption energy consumption, cleaner production, three wastes resource utilization has improved the yield and the quality of product.
Summary of the invention
Describe in detail for the existing patent of invention of glycine new process of production.
The method that the purpose of this invention is to provide effective processing glycine crystallization mother liquid, recycle reduces the material consumption energy consumption, improves process for cleanly preparing.
Mainly contain glycine, iminodiethanoic acid and small amounts of inorganic salt in the glycine crystallization mother liquid.And existing technology still can not be handled these mother liquors efficiently, cleanly, directly burns or discharges and will cause serious environmental protection pressure.
The present inventor provides three kinds of approach of effectively handling this mother liquor through research repeatedly.
1) the pH value of adjusting mother liquor is adsorbed by anion and cation exchange resin, thereby glycine is effectively separated with iminodiethanoic acid, and glycine can be used as product and reclaims, and iminodiethanoic acid is used to prepare related derivatives as byproduct.
2) according to the different addings a certain amount of mineral acid of glycine in the mother liquor with the iminodiethanoic acid proportion, the dissolubility difference in the different acidity system according to iminodiethanoic acid inorganic acid salt and glycine inorganic acid salt, Crystallization Separation goes out glycine inorganic acid salt or iminodiethanoic acid inorganic acid salt, this can be directly used in the preparation related derivatives, the residue mother liquor can directly be applied mechanically back in the glycine preparation section after treatment, thereby the complete closed cycle of whole glycine alkaline hydrolysis technical process, non-wastewater discharge.
3) add quantitative mineral alkali in the mother liquor and make salt, add Mono Chloro Acetic Acid again glycine all is converted into iminodiethanoic acid, add after sulfuric acid removes calcium sulfate, the iminodiethanoic acid sulfate precipitation is separated out, and this can be used as byproduct and sells.
The inventive method can adopt for example following specific embodiments:
1. use anion and cation exchange resin to handle mother liquor.
1.1 use storng-acid cation exchange resin.
Glycin mother liquid is regulated the pH value to 1-5, be preferably 1.5-3.0.Storng-acid cation exchange resin is adorned post through after the activation treatment.Content according to alpha-H in the glycin mother liquid (glycine with iminodiethanoic acid in the glycine molecule amount), with the 10-100% of glycin mother liquid according to the ion-exchange total amount of storng-acid cation exchange resin, be preferably 50-90%, be written into exchange column.Be neutral with distilled water flushing to effluent liquid in the process, collect the effluent liquid in this process, concentrate and obtain iminodiethanoic acid.Be the weak ammonia of 1-20% then with concentration, preferred concentration is 3-10%, and the flushing cationic exchange coloum is collected this part elutriant, concentrates and obtains glycine.Zeo-karb is reusable with the dilute hydrochloric acid immersion regeneration back of 5-10%.
1.2 use strongly basic anion exchange resin.
Glycin mother liquid is regulated the pH value to 3-10, be preferably 4-8.Strongly basic anion exchange resin is adorned post through after the activation treatment.Content according to alpha-H in the glycin mother liquid (glycine with iminodiethanoic acid in the glycine molecule amount), with the 10-100% of glycin mother liquid according to the ion-exchange total amount of strongly basic anion exchange resin, be preferably 50-90%, be written into exchange column.Be neutral with distilled water flushing to effluent liquid in the process, collect the effluent liquid in this process, concentrate and obtain glycine.Be the dilute hydrochloric acid of 1-20% then with concentration, preferred concentration is 3-10%, and the flushing anion-exchange column is collected this part elutriant, concentrates and obtains iminodiethanoic acid.Anionite-exchange resin is reusable with the sodium hydroxide solution immersion regeneration back of 5-10%.
2. in glycin mother liquid, add a certain amount of mineral acid, the inorganic acid salt crystallization of glycine or iminodiethanoic acid is separated out.
According to the amount of alpha-H in the glycin mother liquid (glycine with iminodiethanoic acid in the glycine molecule amount), add mineral acid, these acid can be sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, carbonic acid, Lewis acid etc., are preferably sulfuric acid, hydrochloric acid.The mol ratio of mineral acid and alpha-H is 0.5-10: 1, be preferably 0.5-4.0: 1.Stir at normal temperatures after adding mineral acid, when the mol ratio of glycine in the glycin mother liquid and iminodiethanoic acid 〉=4, the crystallization of glycine inorganic acid salt is separated out, and filters to give recovery set usefulness.Main imido-oxalic acid inorganic acid salt in the residue mother liquor, this can be directly used in derivatives such as preparation pmida98.When the mol ratio of glycine in the glycin mother liquid and iminodiethanoic acid＜3, the crystallization of iminodiethanoic acid inorganic acid salt is separated out, and filters, and this can be used as byproduct and is used to prepare related derivatives.Filtrate is glycine inorganic acid salt solution, can directly apply mechanically back in the process for preparing glycine in and operation.So far the omnidistance closed cycle of glycine alkaline hydrolysis technology does not have discharging of waste liquid, reaches the target of cleaner production fully.
3. by chemical reaction the glycine in the glycin mother liquid is converted into iminodiethanoic acid, reaches the purpose that mother liquor is handled.
According to the amount of glycine in the mother liquor and iminodiethanoic acid, add mineral alkali, mineral alkali can be sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, calcium oxide, calcium hydroxide etc., is optimized for sodium hydroxide, calcium hydroxide.Glycine and iminodiethanoic acid total mole number: mineral alkali=1: 1-5 is optimized for 1: 1.5-3.5.Control reaction temperature is optimized for 20-60 ℃ at 10-100 ℃.Add Mono Chloro Acetic Acid, glycine and Mono Chloro Acetic Acid mol ratio are 1: 0.5-2 is optimized for 1: 0.9-1.5, at 10-60 ℃ of reaction 24h, optimizing temperature of reaction is 20-40 ℃.To 0.5-3.0, be optimized for 0.5-2.0 with mineral acid neutralization reaction liquid pH value, controlled temperature is optimized for 20-50 ℃ at 10-80 ℃ in the process.Mineral acid can be sulfuric acid, hydrochloric acid, phosphoric acid, carbonic acid, Lewis acid etc., is optimized for sulfuric acid, hydrochloric acid.Crystallization removes the inorganic salt that dereaction obtains, and filtrate concentrating obtains the iminodiethanoic acid inorganic acid salt, and this product can be directly used in the preparation related derivatives.
The inventive method has following advantage:
One provides the method for multiple effective processing glycine crystallization mother liquid, and perfect production technique has improved the production added value.
Its two, use anion and cation exchange resin to handle mother liquor, do not have the input of other industrial chemicals substantially, with low cost, easy and simple to handle.Use adds sour salifiable mode and handles mother liquor, technology is simple, efficiently, material cost is cheap, rate of recovery height, the problem that does not have waste material to discharge, clean environment firendly, and the efficient recovery glycine, the by-product iminodiethanoic acid inorganic acid salt that obtains being possessed of higher values has high economic benefit and environmental benefit.Change the glycine in the mother liquor treatment process of iminodiethanoic acid into by chemical reaction, make the depleted glycin mother liquid create the higher iminodiethanoic acid of economic worth, technology is easy, and condition is easy to control, yield height.
Its three, more than these treatment processs all well solved the problem of an atom yield, make glycine synthetic process really accomplish green cleaner production, have high environmental benefit and economic benefit.
Its four, above technology is simple, and is easy and simple to handle, the equipment less investment, the added value height meets the demand of industrialized production fully.
Specific embodiment
The present invention can be further described with indefiniteness embodiment hereinafter.
Embodiment 1 uses storng-acid cation exchange resin to handle mother liquor
100mL storng-acid cation exchange resin (732#, the exchange capacity 1.1-1.5mmol.L-) exchange column of packing into that to handle with dilute hydrochloric acid is till being neutral and not having chlorion with distilled water drip washing to elutant.(alpha-H:23.95%, Gly:16.96% IDA:12.4%), are adjusted to 2 with sulfuric acid with the pH value to mother liquor 40g, and upper prop with 150mL distilled water wash-out, is collected concentrated iminodiethanoic acid 4.5g (content 98.6%), the rate of recovery 89.4% of obtaining of elutriant.Use 100mL3% ammoniacal liquor wash-out ion exchange column again, collect elutriant, concentrate and obtain glycine 6g (content 99%), the rate of recovery 88%.Zeo-karb is reusable with dilute hydrochloric acid immersion regeneration back.
Embodiment 2 uses strongly basic anion exchange resin to handle mother liquor
100mL strongly basic anion exchange resin (717#, the exchange capacity 0.3-0.35mmol.L-) exchange column of packing into that to handle with dilute solution of sodium hydroxide is till being neutral and not having chlorion with distilled water drip washing to elutant.(alpha-H:23.95%, Gly:16.96% IDA:12.4%), are adjusted to 8 with sodium hydroxide solution with the pH value to mother liquor 15g, and upper prop with 150mL distilled water wash-out, is collected concentrated glycine 2.0g (content 98.5%), the rate of recovery 78% of obtaining of elutriant.Use 100mL5% hydrochloric acid wash-out ion exchange column again, collect elutriant, concentrate and obtain iminodiethanoic acid 1.5g (content 98.0%), the rate of recovery 80%.Anionite-exchange resin is reusable with diluted sodium hydroxide solution immersion regeneration back.
Embodiment 3 adds the acid treatment glycine crystallization mother liquid
Take by weighing glycine crystallization mother liquid 500g (alpha-H:20.71%, Gly:17.32%, IDA:6.02%) place 1000mL to be with the four-hole bottle of stirring, thermometer, add 98% sulfuric acid 80g down in room temperature (20-25 ℃), crystal is separated out in stirring, the filtration drying 135g (Gly.1/2H2SO4 content 99%) that weighs, glycine (Gly) rate of recovery 94.3%, this salt can directly apply mechanically back in the glycine alkaline hydrolysis technology in and operation.Main component is an iminodiethanoic acid vitriol in the filtrate, and this can be directly used in the preparation related derivatives, to the not influence of the finished product quality.
Embodiment 4 adds the acid treatment glycine crystallization mother liquid
Take by weighing glycine crystallization mother liquid 500g (alpha-H:20.71%, Gly:17.32%, IDA:6.02%) place 1000mL to be with the four-hole bottle of stirring, thermometer, add 31% hydrochloric acid 170g down in room temperature (20-25 ℃), crystal is separated out in stirring, the filtration drying 120g (Gly.HCl content 99%) that weighs, glycine (Gly) rate of recovery 92.3%, this salt can directly apply mechanically back in the glycine alkaline hydrolysis technology in and operation.Main component is the Iminodiacetate hydrochlorate in the filtrate, and this can be directly used in the preparation related derivatives, to the not influence of the finished product quality.
Embodiment 5 adds the acid treatment glycine crystallization mother liquid
Take by weighing glycine crystallization mother liquid 500g (alpha-H:23.95%, Gly:16.96%, IDA:12.4%) place 1000mL to be with the four-hole bottle of stirring, thermometer, add 98% sulfuric acid 120g down in room temperature (20-25 ℃), crystal is separated out in stirring, the filtration drying 80g (IDA.1/2H2SO4 content 99%) that weighs, iminodiethanoic acid (IDA) rate of recovery 94%, this salt can be directly used in preparation pmida98 product.Main component is a glycine in the filtrate, can be directly and in the glycine alkaline hydrolysis technology in and operation engage sleeves usefulness, to the not influence of major product glycine quality.The glycine rate of recovery 100%.
Embodiment 6 adds the acid treatment glycine crystallization mother liquid
Take by weighing glycine crystallization mother liquid 500g (alpha-H:23.95%, Gly:16.96%, IDA:12.4%) place 1000mL to be with the four-hole bottle of stirring, thermometer and reflux exchanger, add 31% hydrochloric acid 250g down in room temperature (20-25 ℃), stir, and decompression heating (0.09Mpa, 60 ℃) concentrated water outlet 120g, crystal is separated out in cooling, the filtration drying 75g (IDA.HCl content 99%) that weighs, iminodiethanoic acid (IDA) rate of recovery 94%, this salt can be directly used in preparation pmida98 product.Main component is a glycine in the filtrate, can be directly and in the glycine alkaline hydrolysis technology in and operation engage sleeves usefulness, to the not influence of major product glycine quality.The glycine rate of recovery 100%.
Embodiment 7 uses calcium hydroxide to prepare the art breading mother liquor of iminodiethanoic acid
Take by weighing glycine crystallization mother liquid 500g (alpha-H:23.95%, Gly:16.96%, IDA:12.4%) place the 1000mL band to stir, in the there-necked flask of thermometer and reflux exchanger, add 200g calcium hydroxide, ammonia is extracted in the heating decompression out, add the 120g Mono Chloro Acetic Acid in batches, keep 25-30 ℃ to continue to stir after 24 hours, transfer pH value to 0.5 with 50% sulfuric acid, filter out calcium sulphate solid, this solid making beating washing after-filtration gets calcium sulfate 500g, and water lotion and last filtrate merge, decompression dewaters, concentrate and separate out crystal iminodiethanoic acid vitriol, 370g (IDA content 50%), glycine transformation efficiency 85%, (IDA) rate of recovery 90%, and this salt can be directly used in preparation pmida98 product.
Embodiment 8 uses sodium hydroxide to prepare the art breading mother liquor of iminodiethanoic acid
Take by weighing glycine crystallization mother liquid 50g (alpha-H:23.95%, Gly:16.96%, IDA:12.4%) place the 100mL band to stir, in the there-necked flask of thermometer and reflux exchanger, add 6.2g sodium hydroxide, ammonia is extracted in the heating decompression out, be added dropwise to 12g yellow soda ash neutral sodium chloroacetate solution, keep 25-30 ℃ to continue to stir after 6 hours, transfer pH value to 0.8 with 31% hydrochloric acid, decompression dewaters, and concentrates to separate out crystal Iminodiacetate hydrochlorate, 20g (IDA content 70%), glycine transformation efficiency 80%, (IDA) rate of recovery 90%, and this salt can be directly used in preparation pmida98 product.
Claims (6)
1, a kind of method of handling the glycin mother liquid novel process, this method comprises the steps:
1) the pH value of adjusting mother liquor is adsorbed by anion and cation exchange resin, thereby glycine is effectively separated with iminodiethanoic acid, and glycine can be used as product and reclaims, and iminodiethanoic acid is used to prepare related derivatives as byproduct.
2) according to the different addings a certain amount of mineral acid of glycine in the mother liquor with the iminodiethanoic acid proportion, the dissolubility difference in the different acidity system according to iminodiethanoic acid inorganic acid salt and glycine inorganic acid salt, Crystallization Separation goes out glycine inorganic acid salt or iminodiethanoic acid inorganic acid salt, this can be directly used in the preparation related derivatives, the residue mother liquor can directly be applied mechanically back in the glycine preparation section after treatment, thereby the complete closed cycle of whole glycine alkaline hydrolysis technical process, non-wastewater discharge.
3) add quantitative inorganic salt in the mother liquor and make salt, add Mono Chloro Acetic Acid again glycine all is converted into iminodiethanoic acid, add after sulfuric acid removes calcium sulfate, the iminodiethanoic acid sulfate precipitation is separated out, and this can be used as byproduct and sells.
2, according to the process of claim 1 wherein that mineral alkali can be sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, calcium hydroxide.
3, according to the process of claim 1 wherein glycine and iminodiethanoic acid total mole number: mineral alkali is 1: 1-5.
4, according to the process of claim 1 wherein that temperature of reaction is 10-100 ℃.
5, according to the process of claim 1 wherein that glycine and Mono Chloro Acetic Acid mol ratio are 1: 0.5-2.
6, according to the process of claim 1 wherein that mineral acid can be sulfuric acid, hydrochloric acid, phosphoric acid, carbonic acid, Lewis acid etc.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101759578B (en) * | 2009-12-29 | 2012-08-22 | 重庆大学 | Method for recovering useful ingredients in waste glycin mother liquor |
| CN103351314A (en) * | 2013-07-29 | 2013-10-16 | 刘长飞 | Cleaner production process for combined glycine and calcium sulfate |
| CN103641855A (en) * | 2013-11-19 | 2014-03-19 | 重庆紫光化工股份有限公司 | Method for producing N-phosphonomethylglycine by utilizing crystallization mother liquor |
| CN103641854A (en) * | 2013-11-19 | 2014-03-19 | 重庆紫光化工股份有限公司 | Method for producing glyphosate by comprehensively utilizing glycine crystallization mother liquor |
| CN106631909A (en) * | 2016-09-22 | 2017-05-10 | 精晶药业股份有限公司 | Agmatine hydrochloride preparation method |
| CN106883134A (en) * | 2015-12-15 | 2017-06-23 | 秦皇岛华恒生物工程有限公司 | A kind of fermentation method produces the desalination method of L alanine feed liquids |
| CN111635344A (en) * | 2020-06-08 | 2020-09-08 | 九江中星医药化工有限公司 | Post-treatment method of homocystine reaction solution |
| CN114539081A (en) * | 2022-03-07 | 2022-05-27 | 扬州大学 | Method for separating and purifying glycine by using N, N-dibutylethanolamine |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4299978A (en) * | 1979-04-04 | 1981-11-10 | Showa Denko Kabushiki Kaisha | Process for separating iminodiacetic acid from aqueous glycine solution |
| US5254729A (en) * | 1990-05-31 | 1993-10-19 | Mitsui Toatsu Chemicals, Inc. | Method for purifying glycine |
| US6916638B2 (en) * | 1999-12-27 | 2005-07-12 | Asahi Kasei Kabushiki Kaisha | Process for producing glycine |
-
2005
- 2005-12-31 CN CN2005101354930A patent/CN1990460B/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101759578B (en) * | 2009-12-29 | 2012-08-22 | 重庆大学 | Method for recovering useful ingredients in waste glycin mother liquor |
| CN103351314A (en) * | 2013-07-29 | 2013-10-16 | 刘长飞 | Cleaner production process for combined glycine and calcium sulfate |
| CN103641855A (en) * | 2013-11-19 | 2014-03-19 | 重庆紫光化工股份有限公司 | Method for producing N-phosphonomethylglycine by utilizing crystallization mother liquor |
| CN103641854A (en) * | 2013-11-19 | 2014-03-19 | 重庆紫光化工股份有限公司 | Method for producing glyphosate by comprehensively utilizing glycine crystallization mother liquor |
| CN103641855B (en) * | 2013-11-19 | 2016-03-30 | 重庆紫光化工股份有限公司 | Glycine crystallization mother liquid is utilized to produce the method for N-(phosphonomethyl) glycine |
| CN103641854B (en) * | 2013-11-19 | 2016-08-24 | 重庆紫光化工股份有限公司 | A kind of method comprehensively utilizing glycine crystallization mother liquid production glyphosate |
| CN106883134A (en) * | 2015-12-15 | 2017-06-23 | 秦皇岛华恒生物工程有限公司 | A kind of fermentation method produces the desalination method of L alanine feed liquids |
| CN106631909A (en) * | 2016-09-22 | 2017-05-10 | 精晶药业股份有限公司 | Agmatine hydrochloride preparation method |
| CN106631909B (en) * | 2016-09-22 | 2018-11-09 | 精晶药业股份有限公司 | A kind of preparation method of gamatine hydrochloride |
| CN111635344A (en) * | 2020-06-08 | 2020-09-08 | 九江中星医药化工有限公司 | Post-treatment method of homocystine reaction solution |
| CN114539081A (en) * | 2022-03-07 | 2022-05-27 | 扬州大学 | Method for separating and purifying glycine by using N, N-dibutylethanolamine |
| CN114539081B (en) * | 2022-03-07 | 2024-04-02 | 扬州大学 | Method for separating and purifying glycine by utilizing N, N-dibutyl ethanolamine |
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