CN107382758A - A kind of method that glycine is reclaimed in the concentrating spent liquor from glycine - Google Patents
A kind of method that glycine is reclaimed in the concentrating spent liquor from glycine Download PDFInfo
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- CN107382758A CN107382758A CN201710434016.7A CN201710434016A CN107382758A CN 107382758 A CN107382758 A CN 107382758A CN 201710434016 A CN201710434016 A CN 201710434016A CN 107382758 A CN107382758 A CN 107382758A
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- glycine
- amide
- spent liquor
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- concentrating spent
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/38—Separation; Purification; Stabilisation; Use of additives
- C07C227/40—Separation; Purification
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The present invention relates to technical field of chemical separation, more particularly to a kind of method that glycine is reclaimed in concentrating spent liquor from glycine.It the described method comprises the following steps:Glycine concentrating spent liquor is extracted, stood, is then separated, the solid fraction of gained is glycine.
Description
Technical field
The present invention relates to technical field of chemical separation, and glycine is reclaimed from glycine concentrating spent liquor more particularly to one kind
Method.
Background technology
Amion acetic acid also known as glycine, it is mainly used in the neck such as nitrogen fertilizer industry, medicine, pesticide synthesis and biochemical research
Domain, it is highly important industrial products.At present, the production of amion acetic acid mainly uses Chloroacetic Aminolysis, i.e., in normal temperature and pressure
Under the conditions of, using monoxone, liquefied ammonia as raw material, synthesized under methenamine catalysis, then analyse, filter by alcohol, refining, drying
Glycine is made.
A considerable amount of extracting mother liquids can be produced in the extractive crystallization workshop section of glycine production process, its main component is first
Alcohol, water, ammonium chloride, glycine etc..Liquid of the extracting mother liquid after methanol is reclaimed in rectifying is referred to as glycine waste liquid.Pass through multiple-effect
After evaporative crystallization method, reduction vaporization, smoke evaporative or spontaneous nucleation, the moisture in glycine waste liquid is reduced, and then ammonium chloride is analysed
Go out, obtain a kind of concentrating spent liquor, the concentrating spent liquor is referred to as glycine concentrating spent liquor, and its main component is water, inorganic matter ammonium chloride
And organic matter glycine, methenamine, amide-type etc..Because Glycine Levels therein are higher, economic value is good, if directly
Run in and put, huge pollution can be not only caused to environment, and the wasting of resources can be caused.
The glycine in glycine concentrating spent liquor is reclaimed there is presently no correlation process method.
The content of the invention
In order to solve the deficiencies in the prior art, the invention provides one kind to reclaim glycine side from glycine concentrating spent liquor
Method.
A kind of method that glycine is reclaimed in concentrating spent liquor from glycine, comprises the following steps:To glycine concentrating spent liquor
Extracted, stood, glycine during standing in the form of precipitation separate out, it is to be precipitated completely after, separated, gained
Solid fraction is glycine.
Wherein, the glycine concentrating spent liquor includes water, ammonium chloride, glycine and amide-type.The amide-type mainly wraps
Include N,N-dimethylformamide and formamide, N-METHYLFORMAMIDE, N- ethyl-formamides etc..
In an optional embodiment, into glycine concentrating spent liquor only adding amide-type is extracted.
In another optional embodiment, after adding amide-type into glycine concentrating spent liquor, monohydric alcohol is added
One or both of class and di-alcohols.
In another optional embodiment, glycine concentrating spent liquor is extracted using extractant A, the extraction
Agent A include by weight for 0~10wt% unary alcohol, be by weight 0~10wt% di-alcohols and by weight
For the amide-type more than or equal to 80wt% and less than 100wt%.
Wherein, the glycine concentrating spent liquor and the extractant A mass ratio are 1:(0.7~5).
In the above embodiment, the unary alcohol is selected from methanol or ethanol, the di-alcohols be selected from ethylene glycol,
Propane diols or butanediol, the amide-type are selected from DMF or formamide.
In the method according to the invention, it is 20~50 DEG C to control temperature when standing, and time of repose is 1.5~5h.
The separation is carried out using the method for centrifugation, suction filtration (such as vacuum filtration) or press filtration.
In the method according to the invention, in addition to by isolated liquid phase part rectifying recovery is carried out.
Composition and content of the invention by analyzing concentrating spent liquor, suitable extracting process is selected, it is dense to realize glycine
The separation of glycine and other components in contracting waste liquid, glycine separate out in solid form, after simple separation of solid and liquid, directly
Obtain to obtain glycine solid.The processing method not only reduces raffinate amount, also obtains product income, value is higher, plays
The effect turned waste into wealth, meet the requirement of sustainability of natural resources.
The beneficial effects of the invention are as follows:Directly it can be extracted using the method according to the invention from glycine concentrating spent liquor sweet
Propylhomoserin, glycine solid can obtain by simple separation of solid and liquid;The reagent used during extraction can be reclaimed by rectifying, be repeated
Use.This method cost is relatively low, equipment is simple, is adapted to popularization and application.
Embodiment
Embodiment is only the description of the invention, without forming the limitation to present invention, below in conjunction with
Specific embodiment is further described and described to the present invention.
The invention provides a kind of method that glycine is reclaimed in concentrating spent liquor from glycine, comprise the following steps:To sweet
Propylhomoserin concentrating spent liquor is extracted, stood, glycine during standing in the form of precipitation separate out, it is to be precipitated completely after, enter
Row separation, the solid fraction of gained is glycine.
Wherein, the glycine concentrating spent liquor includes water, ammonium chloride, glycine and amide-type.The amide-type mainly wraps
Include N,N-dimethylformamide, formamide and N-METHYLFORMAMIDE etc..
In an optional embodiment, into glycine concentrating spent liquor only adding amide-type is extracted.
In another optional embodiment, after adding amide-type into glycine concentrating spent liquor, monohydric alcohol is added
One or both of class and di-alcohols.
When addition for amide-type and unary alcohol when, by weight, it more than 90wt%, unary alcohol is small that amide-type, which is,
In 10wt%;For example, amide-type can be 91wt%, 91.5wt%, 93wt%, 94wt%, 95.5wt%, 96wt%,
97wt%, 98wt%, 99wt% etc..When addition for amide-type and di-alcohols when, by weight, amide-type be more than
90wt%, di-alcohols are less than 10wt%;For example, amide-type can be 90.5wt%, 92wt%, 93.2wt%,
94.5wt%, 95wt%, 96wt%, 97wt%, 98.4wt%, 99wt% etc..When addition is amide-type, unary alcohol and two
During first alcohols three, by weight, amide-type be more than 80wt%, unary alcohol be less than 10wt%, di-alcohols be less than
10wt%.For example, amide-type can be 81wt%, 82wt%, 83.5wt%, 85wt%, 87.2wt%, 89wt%, 91wt%,
92wt%, 94wt%, 95.5wt%, 97wt%, 99.5wt% etc., unary alcohol can be 0.01wt%, 0.1wt%,
0.3wt%, 0.6wt%, 0.8wt%, 1wt%, 2wt%, 3wt%, 5wt%, 7wt%, 8wt%, 9.5wt% etc., dihydric alcohol
Class can be 0.01wt%, 0.2wt%, 0.3wt%, 0.6wt%, 0.7wt%, 1.2wt%, 2wt%, 3wt%, 5wt%,
7wt%, 8wt%, 9.5wt% etc..
When addition is amide-type, unary alcohol and during di-alcohols three, the addition of unary alcohol and di-alcohols is suitable
Sequence can be arbitrary, such as first add unary alcohol, add di-alcohols, or first add di-alcohols, add one
First alcohols, added after unary alcohol and di-alcohols can also being mixed.No matter which kind of addition sequence, all should be ensured that first
What is added is amide-type.
In another optional embodiment, glycine concentrating spent liquor is extracted using extractant A, the extraction
Agent A include by weight for 0~10wt% unary alcohol, be by weight 0~10wt% di-alcohols and by weight
For the amide-type more than or equal to 80wt% and less than 100wt%.The extractant A includes amide-type, while including monohydric alcohol
One or both of class and di-alcohols.
For example, extractant A includes amide-type and unary alcohol, wherein, unary alcohol can be 0.02wt%,
0.2wt%, 0.3wt%, 0.7wt%, 0.8wt%, 1.5wt%, 2wt%, 3wt%, 4wt%, 6wt%, 7.5wt%, 9wt%
Deng, amide-type can be 81wt%, 82.5wt%, 84wt%, 85.5wt%, 87wt%, 88.6wt%, 90wt%,
92.5wt%, 94wt%, 95.5wt%, 97wt%, 99.8wt% etc..
For example, extractant A includes amide-type and di-alcohols, wherein, di-alcohols can be 0.01wt%,
0.2wt%, 0.3wt%, 0.5wt%, 0.7wt%, 1.2wt%, 2.5wt%, 3wt%, 5wt%, 7wt%, 8wt%,
9.5wt% etc., amide-type can be 80.5wt%, 82wt%, 83.2wt%, 85.5wt%, 87.2wt%, 89.5wt%,
91wt%, 93wt%, 94wt%, 95.5wt%, 97wt%, 99.9wt% etc..
For example, extractant A includes amide-type, unary alcohol and di-alcohols, wherein, unary alcohol can be
0.01wt%, 0.2wt%, 0.3wt%, 0.6wt%, 0.7wt%, 1.2wt%, 2wt%, 3wt%, 5wt%, 7wt%,
8wt%, 9.5wt% etc., di-alcohols can be 0.01wt%, 0.1wt%, 0.3wt%, 0.6wt%, 0.8wt%, 1wt%,
2wt%, 3wt%, 5wt%, 7wt%, 8wt%, 9.5wt% etc., amide-type can be 80.5wt%, 82wt%, 83wt%,
85.5wt%, 87.2wt%, 89.5wt%, 91wt%, 92wt%, 94wt%, 95.5wt%, 97wt%, 99.5wt% etc..
Wherein, the glycine concentrating spent liquor and the extractant A mass ratio are 1:(0.7~5).
In the above embodiment, the unary alcohol is selected from methanol or ethanol, the di-alcohols be selected from ethylene glycol,
Propane diols or butanediol, the amide-type are selected from DMF or formamide.
Wherein the addition of unary alcohol changes with the ratio of water content in glycine concentrating spent liquor, when glycine concentrates
When water content ratio in waste liquid raises, the addition of monohydric alcohol increases therewith;Di-alcohols promotes sweet ammonia as secondary solvent
The precipitation of acid;And amide-type is balanced by changing the solid-liquid system of glycine concentrating spent liquor so that glycine crystallization separates out;Acid amides
Amide-type component in the selection Main Basiss glycine concentrating spent liquor of class, does not introduce non-glycine concentrating spent liquor component in principle
Amide reagent.Because the amide-type component in glycine concentrating spent liquor is mainly N,N-dimethylformamide, formamide, N-
NMF, while the boiling point of DMF, formamide is relatively low, is easy to recycle, therefore the extraction of the present invention
The amide-type in agent is taken to be typically chosen N,N-dimethylformamide or formamide.As can be seen here, with glycine thickened waste in system
Composition, the change of concentration in liquid, it can suitably adjust each component and its ratio of extractant of the present invention.
In the method according to the invention, it is 20~50 DEG C to control temperature when standing, and time of repose is 1.5~5h.
The separation is carried out using the method for centrifugation, suction filtration (such as vacuum filtration) or press filtration.
In the method according to the invention, in addition to by isolated liquid phase part rectifying recovery is carried out.
In the present invention, the moisture in glycine concentrating spent liquor is quickly determined by moisture teller, glycine, acid amides
The content of type organic passes through liquid chromatogram measuring.
The purity of the glycine reclaimed using the extractant of the present invention is determined by perchloric acid non-aqueous titration.
Embodiment 1
Taking 200ml glycine concentrating spent liquor, (its composition is mainly:It is the chlorination of 47wt% water, 25wt% by weight
The acid amides type organic of ammonium, 17.5wt% glycine and 10.5wt%), add extractant 200ml (methanol 5wt%, second two
Alcohol 5wt%, DMF 90wt%), after being stirred at 25 DEG C, 3h is stood, precipitation is separated out in mixed solution,
Filter residue glycine, quality 37.95g, purity 83.02% are obtained after vacuum filtration.Obtained liquid phase portion will be filtered by vacuum
Divide and reclaimed by rectifying, obtain extractant 197ml milliliters.
Embodiment 2
Taking 200ml glycine concentrating spent liquor, (its composition is mainly:It is the chlorination of 52wt% water, 22wt% by weight
The acid amides type organic of ammonium, 18.5wt% glycine and 7.5wt%), sequentially add formamide 88wt%, ethanol 7wt%
With butanediol 5wt%, three amounts to 200ml, after being stirred at 35 DEG C, stands 4h, precipitation is separated out in mixed solution, through from
Filter residue glycine, quality 38.13g, purity 87.36% are obtained after the heart.The liquid phase part that centrifugation obtains is entered by rectifying
Row recovery, obtains liquid 187ml milliliters.
Embodiment 3
Taking 200ml glycine concentrating spent liquor, (its composition is mainly:By weight for 44% water, 23% ammonium chloride,
19.5% glycine and 13.5% acid amides type organic), sequentially add DMF 92wt%, propane diols
5wt% and methanol 3wt%, three amount to 200ml, after being stirred at 30 DEG C, stand 2.5h, it is heavy to be separated out in mixed solution
Form sediment, filter residue glycine, quality 38.89g, purity 87.25% are obtained after press filtration.The liquid phase part that press filtration is obtained passes through
Rectifying is reclaimed, and obtains liquid 193ml milliliters.
Embodiment 4
Taking 200ml glycine concentrating spent liquor, (its composition is mainly:By weight for 39% water, 22% ammonium chloride,
21.5% glycine and 17.5% acid amides type organic), 200ml DMFs are added, are stirred at 30 DEG C
After mixing uniformly, 3h is stood, precipitation is separated out in mixed solution, obtains filter residue glycine after vacuum filtration, quality 43.35g is pure
Spend for 93.57%.The liquid phase part that vacuum filtration obtains is reclaimed by rectifying, obtains liquid 196ml milliliters.
Embodiment 5
Taking 200ml glycine concentrating spent liquor, (its composition is mainly:By weight for 44% water, 23% ammonium chloride,
19.5% glycine and 13.5% acid amides type organic), add extractant 200ml (methanol 3wt%, formamide
97wt%), after being stirred at 30 DEG C, 2.5h is stood, precipitation is separated out in mixed solution, the sweet ammonia of filter residue is obtained after centrifugation
Acid, quality 87.53g, purity 87.53%.The liquid phase part that centrifugation obtains is reclaimed by rectifying, obtains extractant
191ml milliliters.
Embodiment 6
Taking 200ml glycine concentrating spent liquor, (its main component is:By weight for 46% water, 23% ammonium chloride,
20% glycine and 11% acid amides type organic), DMF 92wt%, ethanol 8wt% are sequentially added,
Both amount to 200ml, after being stirred at 30 DEG C, stand 3h, separate out precipitation in mixed solution, it is sweet that filter residue is obtained after press filtration
Propylhomoserin, quality 41.56g, purity 90.82%.The liquid phase part that press filtration is obtained is reclaimed by rectifying, obtains liquid
193ml milliliters.
Embodiment 7
Taking 200ml glycine concentrating spent liquor, (its main component is:By weight for 44% water, 23% ammonium chloride,
19.5% glycine and 13.5% acid amides type organic), add extractant 200ml (propane diols 12wt%, formamide
88wt%), after being stirred at 30 DEG C, 2h is stood, precipitation is separated out in mixed solution, obtains the sweet ammonia of filter residue after vacuum filtration
Acid, quality 46.57g, purity 82.65%.The liquid phase part that vacuum filtration obtains is reclaimed by rectifying, extracted
Take agent 194ml milliliters.
Obviously, those skilled in the art can carry out the essence of various changes and modification without departing from the present invention to the present invention
God and scope.So, if these modifications and variations of the present invention belong to the scope of the claims in the present invention and its equivalent technologies
Within, then the present invention is also intended to comprising including these changes and modification.
Claims (11)
1. the method for glycine is reclaimed in a kind of concentrating spent liquor from glycine, it is characterised in that comprise the following steps:To glycine
Concentrating spent liquor is extracted, stood, and is then separated, and the solid fraction of gained is glycine.
2. according to the method for claim 1, it is characterised in that the glycine concentrating spent liquor includes water, ammonium chloride, sweet ammonia
Acid and amide-type;The amide-type includes N,N-dimethylformamide, formamide and N-METHYLFORMAMIDE.
3. according to the method for claim 1, it is characterised in that only add amide-type into glycine concentrating spent liquor and extracted
Take.
4. according to the method for claim 1, it is characterised in that after adding amide-type into glycine concentrating spent liquor, then add
Enter one or both of unary alcohol and di-alcohols.
5. according to the method for claim 1, it is characterised in that glycine concentrating spent liquor is extracted using extractant A,
The extractant A include by weight for 0~10wt% unary alcohol, be by weight 0~10wt% di-alcohols and
It is the amide-type more than or equal to 80wt% and less than 100wt% by weight.
6. according to the method for claim 3, it is characterised in that the amide-type is selected from DMF or formyl
Amine.
7. according to the method described in any one of claim 4~5, it is characterised in that the unary alcohol is selected from methanol or ethanol,
The di-alcohols is selected from ethylene glycol, propane diols or butanediol, and the amide-type is selected from DMF or formamide.
8. according to the method for claim 5, it is characterised in that the matter of the glycine concentrating spent liquor and the extractant A
Amount is than being 1:(0.7~5).
9. according to the method for claim 1, it is characterised in that it is 20~50 DEG C to control temperature when standing, time of repose
For 1.5~5h.
10. according to the method for claim 1, it is characterised in that the separation is entered using the method for centrifugation, suction filtration or press filtration
OK.
11. according to the method for claim 1, it is characterised in that also include isolated liquid phase part carrying out rectifying
Recovery.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109534360A (en) * | 2018-12-12 | 2019-03-29 | 石家庄新奥环保科技有限公司 | Liquid waste processing production line |
CN114957025A (en) * | 2022-06-27 | 2022-08-30 | 北京君德同创生物技术股份有限公司 | Method for recovering glycine from waste liquid in glycocyamine production |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1433479A (en) * | 1999-12-27 | 2003-07-30 | 旭化成株式会社 | Process for producing glycine |
CN103539687A (en) * | 2012-07-12 | 2014-01-29 | 新沂市汉菱生物工程有限公司 | Production method of glycine |
CN105753728A (en) * | 2016-03-31 | 2016-07-13 | 武汉科技大学 | Medicinal L-valine dilution crystallization method |
CN105859571A (en) * | 2015-01-19 | 2016-08-17 | 刘长飞 | Method for producing glycine by mixed solvent method |
CN106008243A (en) * | 2016-05-23 | 2016-10-12 | 河南红东方化工股份有限公司 | Environment-friendly production process for continuously synthesizing amino acetic acid |
-
2017
- 2017-06-09 CN CN201710434016.7A patent/CN107382758B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1433479A (en) * | 1999-12-27 | 2003-07-30 | 旭化成株式会社 | Process for producing glycine |
CN103539687A (en) * | 2012-07-12 | 2014-01-29 | 新沂市汉菱生物工程有限公司 | Production method of glycine |
CN105859571A (en) * | 2015-01-19 | 2016-08-17 | 刘长飞 | Method for producing glycine by mixed solvent method |
CN105753728A (en) * | 2016-03-31 | 2016-07-13 | 武汉科技大学 | Medicinal L-valine dilution crystallization method |
CN106008243A (en) * | 2016-05-23 | 2016-10-12 | 河南红东方化工股份有限公司 | Environment-friendly production process for continuously synthesizing amino acetic acid |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109534360A (en) * | 2018-12-12 | 2019-03-29 | 石家庄新奥环保科技有限公司 | Liquid waste processing production line |
CN114957025A (en) * | 2022-06-27 | 2022-08-30 | 北京君德同创生物技术股份有限公司 | Method for recovering glycine from waste liquid in glycocyamine production |
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