CN105859571A - Method for producing glycine by mixed solvent method - Google Patents
Method for producing glycine by mixed solvent method Download PDFInfo
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- CN105859571A CN105859571A CN201510023763.2A CN201510023763A CN105859571A CN 105859571 A CN105859571 A CN 105859571A CN 201510023763 A CN201510023763 A CN 201510023763A CN 105859571 A CN105859571 A CN 105859571A
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Abstract
The invention provides a clean production process of glycine. An organic mixed solvent is used for producing glycine and a by-product ammonium chloride by combined production. The organic mixed solvent comprises methanol, ethanol, and dihydric alcohol solvents or dihydric alcohol derivative solvents. The mixed solvent is added into a glycine synthesis reactor, urotropine and chloroacetic acid are added, ammonia is added, and a mixed crystal solid of glycine and ammonium chloride is obtained. The mixed crystal solid is added into a mixed solvent for separation, the mixed solvent for separation is heated to 60-80 DEG C, after glycine crystal is filtered, the mixed solvent for separation is cooled to 0-20 DEG C, and an ammonium chloride solid is separated by centrifugation.
Description
Technical field
The present invention relates to the process for cleanly preparing of a kind of glycine, utilize organic mixed solvent to produce glycine, belong to chemical production technical field.
Background technology
Glycine is the important source material of the product such as glyphosate, glycine ethyl ester hydrochloride, it is also possible to is refined into food stage glycine and uses.Domestic traditional monoxone amino solution glycine production technology is as follows: add the aqueous solution of catalyst hexamethylenamine content about 25% in the reactor being connected with cooling water, it is simultaneously added dropwise the monoxone aqueous solution of about 80% content and is passed through liquefied ammonia, under conditions of pH value about 7, reaction temperature about 80 DEG C, carrying out ammonolysis reaction.The method isolated glycine product of the analysis of the ammonolysis reaction liquid methanol alcohol containing glycine and ammonium chloride that reaction obtains after terminating.Produce the mother solution containing methanol about one ton of glycine 12--13 to be produced cubic meter, in methanol mother liquor containing about 5% ammonium chloride, the hexamethylenamine of about 1%, the glycine of about 0.8%.Producing one ton of glycine needs the steam consuming about 5 tons for reclaiming methanol, and produce one ton of glycine needs the hexamethylenamine consuming about 150 kilograms not recycle simultaneously.Produce one ton of glycine and also to consume the methanol of 60 100 kilograms.Methanol mother liquor, after methanol is reclaimed in rectification, obtains dealcoholizing waste water.Dealcoholizing waste water obtains side-product ammonium chloride for producing fertilizer application after evaporation and concentration.And remaining the most difficult containing organic black waste water such as a large amount of hexamethylenamine, glycine after reclaiming side-product ammonium chloride, not only pollute environment, also waste the resource of preciousness.
Patent US5155264 and CN1080632 are with monoxone, ammonia as raw material, in the presence of catalyst and organic amine, can isolate glycine, but the effective scheme that catalyst inside mother solution and organic amine do not reuse.Patent CN101270061, with monoxone, ammonia as raw material, can be separated glycine in the presence of hexamethylenamine and organic amine, but need to consume substantial amounts of sodium alkoxide or potassium alcoholate, and cost is high, does not has industrial value.Patent CN102030669 is with monoxone and ammonia as raw material, under catalyst action, with organic amine as acid binding agent, it is possible to realize glycine and separate with ammonium chloride.But this technics comparing is complicated, reaction end also compares difficult control.The when of utilizing recovery ammonia triethylamine hydrochloride, it is impossible to reclaim triethylamine completely, production process still there is a small amount of glycine to produce with the mixed crystal of ammonium chloride, in addition it is also necessary to further to separate simultaneously.Patent CN1176062C, describes a kind of method that alcohol phase method produces glycine, although catalyst can recycle, but the glycine that reaction obtains and the mixed crystal solid of ammonium chloride, the most well separate way, the way of electrodialysis or alcohol analysis can only be used to separate, consume the substantial amounts of energy.
Summary of the invention
The invention provides the process for cleanly preparing of a kind of glycine, utilize organic mixed solvent to produce glycine, it is also possible to combined producting ammonium chloride side-product.The organic solvent used in the present invention includes following kind:
Methanol and ethanol, and glycolic solvents (ethylene glycol, propylene glycol, butanediol)；Diol, derivatives solvent (glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether).
The present invention through the following steps that and method realize:
Step (1), monoxone synthesize glycine inside organic solvent:
Produce reactor (equipped with condenser above reactor, have solvent condensation reflux unit and the outer retracting device of solvent condensation reaction still) inner addition solvent methanol (or ethanol) of glycine, add glycolic solvents (or diol, derivatives solvent).The amount adding glycolic solvents (or diol, derivatives solvent) is 1% the 20% of methanol (or ethanol) volume.Adding glycolic solvents (or diol, derivatives solvent) in methanol (or ethanol) solvent, Main Function is the stability that can increase glycine synthetic reaction, reduces by-product and produces, improves glycine yield.
After mixed solvent adds catalyst hexamethylenamine, add solid monoxone, the most slowly lead to ammonia.First half term is led to the temperature of ammonia and is controlled between 30 DEG C-60 DEG C, and be substantially carried out is the reaction of monoxone and ammonia synthesis ammonium chloroacetate.The second half leads to ammonia, and temperature controls between 60 DEG C-75 DEG C, is the reaction of synthesis glycine.The time of logical ammonia controls between 1-3 hour, insulation reaction 0.5 hour after logical ammonia.
Monoxone is 1:2 3 with the mol ratio of ammonia.The amount of organic solvent is 3 12 times of monoxone weight.The amount that catalyst hexamethylenamine adds is between 1st/1st to two/10th of monoxone weight.
After insulation reaction terminates, reactant liquor filters out the mixed crystal solid of glycine and ammonium chloride under 45 DEG C of-70 DEG C of temperature conditionss and obtains filtrate, and filtrate is referred to as circular response mother solution.Circular response mother solution is added a small amount of hexamethylenamine, continues to put into solid monoxone, then lead to ammonia, carry out glycine synthetic reaction, obtain the mixed crystal solid of glycine and ammonium chloride.Circular response mother solution generally uses 10 20 times.
Step (2), glycine separate with ammonium chloride mixed crystal solid:
Add methanol (or ethanol) in reactor to form with glycolic solvents (or diol, derivatives solvent) and separate mixed solvent.Methanol (or ethanol) and the volume ratio of glycolic solvents (or diol, derivatives solvent): 1:1 5.
Adding glycine and the mixed crystal of ammonium chloride, agitating heating, be warming up to 60 DEG C 80 DEG C, heat filtering goes out Glycine crystals.Glycine crystals uses methanol (or ethanol) washing, obtains the crude product glycine of content 96% 97.5%.Crude product glycine, through recrystallization in aqueous, obtains the high-quality glycine product of content more than 99%.
Filter out the separation mixed solvent of Glycine crystals, cool, be cooled to 0 DEG C 20 DEG C, centrifugally filter out ammonium chloride crude product.Ammonium chloride crude product uses methanol (or ethanol) to wash, is centrifuged, and then washes with water.Washed ammonium chloride obtains side-product ammonium chloride after centrifugal.The water solution cycle of washing ammonium chloride uses, and after the glycine concentration in cleaning mixture is enriched to 20% 30%, uses the method for alcohol analysis (methanol or ethanol) to reclaim the glycine in cleaning mixture.Alcohol analysis liquid is after methanol (or ethanol) is reclaimed in rectification, and remaining aqueous solution, continuation is used for washing ammonium chloride.
Washing crude product glycine and methanol (or ethanol) solvent of ammonium chloride crude product, through Distillation recovery methanol (or ethanol).The glycolic solvents (or diol, derivatives solvent) of distillation enrichment recycles, for separation of glycine and ammonium chloride mixed crystal.
Step (3), the process of circular response mother solution:
Circular response mother solution is after 10 20 secondary responses, due to impurity enriched, darkens, and needs recycling.Decompression distillation, the mode of rectification is used to reclaim organic solvent.Remaining coloured material (main component: ammonium chloride, hexamethylenamine, glycine and byproduct of reaction etc.), first passes around catalytic oxidation treatment, is then passed through being dried, pelletize, is processed into chemical fertilizer raw material product.
Detailed description of the invention:
Further illustrate the essentiality content of the present invention with embodiments of the invention, but do not limit the present invention with this.
Embodiment one:
By monoxone 473g, methanol 1900 ml, ethylene glycol 50ml, hexamethylenamine 125g are incorporated with in the four-hole boiling flask of agitator, thermometer and reflux condenser and water-bath cooling, and stirring and dissolving maintains the temperature at less than 50 DEG C, is passed through liquefied ammonia 85 g in one hour.Then proceeding to logical ammonia, temperature controls between 60 DEG C 70 DEG C, logical ammonia 100 g in 1 hour.Insulation reaction 0.5 hour.Filtering out glycine and ammonium chloride mixed crystal solid under the conditions of 60 DEG C, mixed crystal solid uses 100 ml methanol washings, sucking filtration, and cleaning mixture is added in the reaction mother liquor filtered out.Through weighing, obtain glycine and ammonium chloride mixed crystal solid 749.64g, water capacity 25.35%.
Embodiment two:
By monoxone 473g, join in the reaction mother liquor filtered out in embodiment one, stirring and dissolving, maintain the temperature at less than 50 DEG C, in one hour, be passed through liquefied ammonia 85 g.Then proceeding to logical ammonia, temperature controls between 60 DEG C 70 DEG C, logical ammonia 100g in 1 hour.Insulation reaction 0.5 hour.Filtering out glycine and ammonium chloride mixed crystal solid under the conditions of 60 DEG C, mixed crystal solid uses the washing of 100ml methanol, sucking filtration, and cleaning mixture is added in the reaction mother liquor filtered out.Through weighing, obtain glycine and ammonium chloride mixed crystal solid 816.24g, water capacity 25.79%.
Embodiment three:
Wet product glycine in Example one and ammonium chloride mixed crystal solid 140g, join in the mixed solvent being made up of 800ml ethylene glycol and 300ml methanol, stirring, is heated to 65 DEG C, and heat filtering goes out Glycine crystals.Glycine crystals washs through 100ml methanol, sucking filtration, dried, obtains crude product glycine 39.13 g.Through analyzing, Glycine Levels 97.13%.Filter out the mixed solvent of glycine, be cooled to 10 DEG C, filter out solid ammonium chloride.Solid ammonium chloride washs through 100ml methanol, and sucking filtration obtains crude product ammonium chloride 16.12g.
Embodiment four:
Wet product glycine in Example two and ammonium chloride mixed crystal solid 140g, join in embodiment three mixed solvent, stirring, is heated to 65 DEG C, and heat filtering goes out Glycine crystals.Glycine crystals washs through 100ml methanol, sucking filtration, dried crude product glycine 56.17g.Through analyzing, Glycine Levels 97.21%.Filter out the mixed solvent of glycine, be cooled to 10 DEG C, filter out solid ammonium chloride.Solid ammonium chloride washs through 100ml methanol, and sucking filtration obtains crude product ammonium chloride 58.66g.
Claims (7)
1. the method that mixed solvent method produces glycine, can be with combined producting ammonium chloride while producing glycine, it is characterised in that the method comprises the following steps:
(1), after adding mixed solvent, and catalyst hexamethylenamine in reactor, add solid monoxone, logical ammonia, after reaction terminates, under 45 DEG C of-70 DEG C of temperature conditionss, filter out glycine and the mixed crystal of ammonium chloride and obtain circular response mother solution；
(2) adding a small amount of hexamethylenamine in circular response mother solution, continue to put into solid monoxone, then lead to ammonia, carry out glycine synthetic reaction, heat filtering obtains the mixed crystal solid of glycine and ammonium chloride；
(3) separation mixed solvent is added in reactor, add glycine and the mixed crystal of ammonium chloride, agitating heating, it is warming up to 60 DEG C 80 DEG C, heat filtering goes out crude product Glycine crystals, after Glycine crystals uses methanol (or ethanol) washing, through recrystallization in aqueous, obtain the high-quality glycine product of content more than 99%；
(4) filter out the separation mixed solvent of Glycine crystals, be cooled to 0 DEG C 20 DEG C, centrifugally filter out ammonium chloride crude product, use methanol (or ethanol) to wash, centrifugal, then wash with water, centrifugal after obtain side-product ammonium chloride；
(5) water solution cycle of washing ammonium chloride uses, and after the glycine concentration in cleaning mixture is enriched to 20% 30%, uses the method for alcohol analysis to reclaim the glycine in cleaning mixture；
(6) circular response mother solution is after 10 20 secondary responses, uses the mode of distillation to reclaim organic solvent, remaining coloured material, after catalytic oxidation treatment, through dry, pelletize, is processed into chemical fertilizer raw material product.
2. the method for claim 1, it is characterised in that: it is 1% the 20% of methanol (or ethanol) volume that mixed solvent described in step (1) adds the amount of glycolic solvents (or diol, derivatives solvent).
3. the method for claim 1, it is characterised in that: the glycine synthetic reaction described in step (1), under 45 DEG C of-70 DEG C of temperature conditionss, filter out the mixed crystal of glycine and ammonium chloride.
4. the method for claim 1, it is characterised in that: in the separation mixed solvent described in step (3), methanol (or ethanol) with the volume ratio of glycolic solvents (or diol, derivatives solvent) is: 1:1 5.
5. the method for claim 1, it is characterised in that: the temperature dissolving glycine and ammonium chloride mixed crystal described in step (3)
It is 60 DEG C 80 DEG C, and filters out glycine under the conditions of 60 DEG C 80 DEG C.
6. the method for claim 1, it is characterised in that: the separation mixed solvent described in step (4), it is cooled to 0 DEG C 20 DEG C, centrifugally filters out ammonium chloride crude product.
7. the method for claim 1, it is characterised in that: the aqueous solution of the washing ammonium chloride described in step (5), use the method for alcohol analysis to reclaim the glycine in cleaning mixture.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107382758A (en) * | 2017-06-09 | 2017-11-24 | 石家庄新奥环保科技有限公司 | A kind of method that glycine is reclaimed in the concentrating spent liquor from glycine |
| CN108558689A (en) * | 2018-05-28 | 2018-09-21 | 河南红东方化工股份有限公司 | It is a kind of industry amion acetic acid by-product ammonium chloride without haline water solution processing methods |
| CN109836344A (en) * | 2017-11-26 | 2019-06-04 | 刘长飞 | A kind of method of organic solvent production glycine |
| CN110305028A (en) * | 2019-06-21 | 2019-10-08 | 湖北泰盛化工有限公司 | A kind of device and technique of alcohol phase method washing glycine crude product |
| CN111087316A (en) * | 2018-10-24 | 2020-05-01 | 刘长飞 | Method for preparing glycine by using novel environment-friendly catalyst |
| CN111100021A (en) * | 2019-12-31 | 2020-05-05 | 江苏汉凯工程技术有限公司 | Synthesis method of glycine |
| CN111100020A (en) * | 2018-10-25 | 2020-05-05 | 刘长飞 | Method for preparing glycine by using novel catalyst in mixed solvent method |
| CN111187173A (en) * | 2020-01-13 | 2020-05-22 | 天津市天地创智科技发展有限公司 | Continuous glycine synthesis method |
| CN111196768A (en) * | 2018-11-17 | 2020-05-26 | 刘长飞 | Method for preparing glycine by utilizing same ion effect |
| CN111362819A (en) * | 2020-04-02 | 2020-07-03 | 湖北泰盛化工有限公司 | Process and device for producing glycine by alcohol phase method |
| CN113861055A (en) * | 2021-10-14 | 2021-12-31 | 湖北泰盛化工有限公司 | Material washing method of industrial grade glycine crude product |
| CN115991657A (en) * | 2022-08-23 | 2023-04-21 | 山东民基新材料科技有限公司 | Co-production method of glycine and ammonium chloride |
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Cited By (15)
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| CN107382758A (en) * | 2017-06-09 | 2017-11-24 | 石家庄新奥环保科技有限公司 | A kind of method that glycine is reclaimed in the concentrating spent liquor from glycine |
| CN109836344A (en) * | 2017-11-26 | 2019-06-04 | 刘长飞 | A kind of method of organic solvent production glycine |
| CN108558689A (en) * | 2018-05-28 | 2018-09-21 | 河南红东方化工股份有限公司 | It is a kind of industry amion acetic acid by-product ammonium chloride without haline water solution processing methods |
| CN111087316A (en) * | 2018-10-24 | 2020-05-01 | 刘长飞 | Method for preparing glycine by using novel environment-friendly catalyst |
| CN111100020A (en) * | 2018-10-25 | 2020-05-05 | 刘长飞 | Method for preparing glycine by using novel catalyst in mixed solvent method |
| CN111196768A (en) * | 2018-11-17 | 2020-05-26 | 刘长飞 | Method for preparing glycine by utilizing same ion effect |
| CN110305028A (en) * | 2019-06-21 | 2019-10-08 | 湖北泰盛化工有限公司 | A kind of device and technique of alcohol phase method washing glycine crude product |
| CN110305028B (en) * | 2019-06-21 | 2022-04-08 | 湖北泰盛化工有限公司 | Device and process for washing glycine crude product by alcohol phase method |
| CN111100021A (en) * | 2019-12-31 | 2020-05-05 | 江苏汉凯工程技术有限公司 | Synthesis method of glycine |
| CN111187173A (en) * | 2020-01-13 | 2020-05-22 | 天津市天地创智科技发展有限公司 | Continuous glycine synthesis method |
| CN111187173B (en) * | 2020-01-13 | 2023-02-28 | 天津市天地创智科技发展有限公司 | Continuous glycine synthesis method |
| CN111362819A (en) * | 2020-04-02 | 2020-07-03 | 湖北泰盛化工有限公司 | Process and device for producing glycine by alcohol phase method |
| CN113861055A (en) * | 2021-10-14 | 2021-12-31 | 湖北泰盛化工有限公司 | Material washing method of industrial grade glycine crude product |
| CN115991657A (en) * | 2022-08-23 | 2023-04-21 | 山东民基新材料科技有限公司 | Co-production method of glycine and ammonium chloride |
| CN115991657B (en) * | 2022-08-23 | 2024-03-19 | 山东民基新材料科技有限公司 | Co-production method of glycine and ammonium chloride |
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