CN103086904B - A kind of method of carrying out environment-friendly cycle method production glycine at reactor - Google Patents
A kind of method of carrying out environment-friendly cycle method production glycine at reactor Download PDFInfo
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- CN103086904B CN103086904B CN201110346328.5A CN201110346328A CN103086904B CN 103086904 B CN103086904 B CN 103086904B CN 201110346328 A CN201110346328 A CN 201110346328A CN 103086904 B CN103086904 B CN 103086904B
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Abstract
The present invention relates to a kind of method of carrying out environment-friendly cycle method production glycine at reactor, the method comprises: add methyl alcohol in a kettle., Mono Chloro Acetic Acid and urotropine, then in reactor, ammonia is passed into, react under cooling conditions, after reaction terminates, reaction soln is centrifugal, obtain glycine and ammonia chloride crystal mixture solid and mother liquor, solid is used for therefrom separation of glycine and ammonium chloride, mother liquor is used as the raw material next time reacted, it is characterized in that: reaction is carried out in a kettle., the volume of reactor is more than or equal to 5 cubic metres, reactor is in cooling state and whipped state always, in the mole number that the speed control passing into ammonia in reactor passes at ammonia per hour and reactor, the ratio of original chloroacetic mole number is 0.5-2.0.Method of the present invention breaches the technical problem that glycine is produced in methanol phase extension, achieves the coordination in reaction system speed of response, reaction times, makes do not have by product to produce in reaction process, ensures that again speed of response improves.
Description
Technical field
The invention belongs to field of fine chemical, concrete, relate to the preparation method of glycine, particularly relate to a kind of method of carrying out environment-friendly cycle method production glycine at reactor.
Background technology
The alcohol of glycine is combined to method and has many reports.People are finding always and are improving glycine synthesis yield and quality, and reduce urotropine consumption, the method reduced costs.
Such as, CN1340498A discloses a kind of process for preparing glycine, makes liquid phase reaction, isolate glycine after reaction with Mono Chloro Acetic Acid and ammonia, and step is: reacted solution crystallisation by cooling is isolated glycine/ammonium chloride mixed crystal by (1); Take out the mother liquor Returning reacting system after mixed crystal, recycled; (2) alcohol-water mixtures of the mixed crystal described in dissolves ammonium chloride wherein, isolates glycine; After taking out the mother liquor dealcoholysis after glycine, crystallisation by cooling isolates ammonium chloride; Take out the mother liquor after ammonium chloride with described deviate from alcohol mix after return mixed crystal dissolution system, recycled; (3) reaction described in is carried out under catalyzer urotropine exists, and inputs tubular reactor by after Mono Chloro Acetic Acid and urotropine dissolution with solvents, and input ammonia or ammoniacal liquor, described solvent is water, alcohol or alcohol-water mixtures simultaneously.This invention uses tubular reactor on the one hand, and the output of reaction is few, and on the other hand, product alcohol solution is separated, and creates a large amount of waste liquids, alcohol solution.
The present invention is directed to the defect that in prior art, process for preparing glycine exists, preparation technology is improved, overcome the defect of prior art, solve the problem that insoluble suitability for industrialized production is dangerous, preparation process is loaded down with trivial details for a long time, achieve the production method of the full-range energy-conserving and environment-protective of one.The object of the invention is to overcome above-mentioned defect, provide a kind of constant product quality, yield is high, and cost is low, is applicable to the process for preparing glycine of industrialization scale operation.
Summary of the invention
For solving the problem, the environment-friendly cycle method in a kind of reactor that the invention provides produces the method for glycine and ammonium chloride, the method comprises: add methyl alcohol in a kettle., Mono Chloro Acetic Acid and urotropine, then in reactor, ammonia is passed into, react under cooling conditions, after reaction terminates, reaction soln is centrifugal, obtain glycine and ammonia chloride crystal mixture solid and mother liquor, solid is used for therefrom separation of glycine and ammonium chloride, mother liquor is used as the raw material next time reacted, it is characterized in that: reaction is carried out in a kettle., the volume of reactor is more than or equal to 5 cubic metres, reactor is in cooling state and whipped state always, in the mole number that the speed control passing into ammonia in reactor passes at ammonia per hour and reactor, the ratio of original chloroacetic mole number is 0.5-2.0.
Preferably, in aforesaid method, in the mole number that the speed control passing into ammonia in reactor passes at ammonia per hour and reactor, the ratio of original chloroacetic mole number is 1.0-2.0.
Preferably, in aforesaid method, reaction system is in the cooling of cooling jacket always, even if reaction liquid is in boiling state, also continues to cool it.
Production method of the present invention is only only applicable to Methanol for glycine, is not suitable for aqueous phase or alcohol aqueous phase prepares glycine.
In method of the present invention, described methyl alcohol water content lower than 0.15wt%, preferably, lower than 0.10wt%.In whole reaction system, anhydrous implication is except the negligible methyl alcohol existed in methyl alcohol, the negligible water that may contain in Mono Chloro Acetic Acid, and Mono Chloro Acetic Acid employing is industrial Mono Chloro Acetic Acid, water content is wherein lower than 0.1%, preferably, the Mono Chloro Acetic Acid lower than 0.05% is adopted.
The above-mentioned method preparing glycine of the present invention, on the one hand, carries out amplification owing to using reactor and produces, so particularly important is controlled for the condition in reaction process, the time of especially reacting, if the overlong time of reaction, affect output, if react too fast, require that the ammonia passed into is too fast, or reaction system is heated up, so then can cause reacting bumping, serious meeting produces the danger of blast, and side reaction can be caused in addition to increase.The present invention passes into speed by controlling suitable ammonia, lowers the temperature and stir in simultaneous reactions process to reactor, and the time of reaction does not extend, and can ensure to react completely, reaction safety.
Prepare in the reaction of glycine at use urotropine, generally need water that reaction rapid reaction can be made complete, if do not have water to participate in reaction, then reaction needed raised temperature improves speed of response, otherwise the reaction times is long, so the by product of reaction will be made to increase once improve temperature, such as by product NH (CH
2cOOH)
2or by product N (CH
2cOOH)
3so other approach can only be taked to solve this problem, the two-step approach such as, used in publication number CN1410417A is prepared glycine, the preparation of this two-step approach makes the process of reacting become loaded down with trivial details, complicated operation in a large amount of industrial production, extend the production time on the contrary, although shorten the reaction times, on integrated artistic, the time does not shorten.
And method of the present invention, lower the temperature in reaction process, do not heat up, in reaction process, reactor cooling jacket is cooled, low-temp reaction avoids the generation of by product, then passing into rate adaptation speed of response by controlling ammonia, carrying out no coupling product production under ensureing the low temperature of reaction, ensure that again the speed of reacting is not affected greatly, solve the difficult problem that extension is produced.
In aforesaid method, there is in reactor agitator reaction soln is stirred, ensure that reaction evenly.
Method of the present invention breaches the technical problem that glycine is produced in methanol phase extension, achieves the coordination in reaction system speed of response, reaction times, makes do not have by product to produce in reaction process, ensures that again speed of response improves.
Embodiment
In order to understand the present invention, further illustrate the present invention with embodiment below, but do not limit the present invention.
Embodiment 1
Which step mentioned in embodiment is actually the division carried out in order to clear elaboration reaction process, and real reaction process is not that whole reaction process is actually continuous print so step by step.
The first step: by the urotropine mixture of the methyl alcohol of the Mono Chloro Acetic Acid of 1000kg, 4000L, 260Kg in 5 cubic metres of reactors, pass into ammonia, the speed passing into ammonia is the ratio passing into ammonia molar rate and original chloroacetic integral molar quantity per hour is 2, cools in reaction process with cooling jacket to reactor; The pH of reaction system reach 7.8 and keep 5 minutes constant after, no longer pass into ammonia, calculating the time passing into ammonia is 66 minutes.Keep in reaction process stirring reaction system.
Second step: reacted rear cooling jacket and continued cooling reactor, when the temperature of reaction soln reaches 40 DEG C time, solution has been passed in whizzer, the mixed crystal solid of centrifugation glycine and ammonium chloride and mother liquor.
Embodiment 2
Repeat the operation of embodiment 1, adjustment ammonia passes into the speed of solution, and the ratio passing into ammonia molar rate and original chloroacetic integral molar quantity per hour is adjusted to 4,3,2,1,0.5 respectively.
The situation of the speed and reaction effect thereof that pass into ammonia sees table, and wherein the reaction times refers to that the pH of reaction system reached for 7.8 latter 5 minutes constant times.
As can be seen from result above, for reaching reacting balance, by product is not had to produce, preferably require that the ratio passing into ammonia molar rate and original chloroacetic integral molar quantity per hour is less than or equal to 2, if reaction does not need the period, then ratio can be reduced to 0.5, but for ensureing reacting balance and Reaction time shorten, improve preparation output, ratio control is relatively good at 1-2.
Claims (5)
1. one kind in a kettle. environment-friendly cycle method produce the method for glycine and ammonium chloride, the method comprises: add methyl alcohol in a kettle., Mono Chloro Acetic Acid and urotropine, then in reactor, ammonia is passed into, react under cooling conditions, after reaction terminates, reaction soln is centrifugal, obtain glycine and ammonia chloride crystal mixture solid and mother liquor, solid is used for therefrom separation of glycine and ammonium chloride, mother liquor is used as the raw material next time reacted, it is characterized in that: reaction is carried out in a kettle., the volume of reactor is more than or equal to 5 cubic metres, reactor is in cooling state and whipped state always, in the mole number that the speed control passing into ammonia in reactor passes at ammonia per hour and reactor, the ratio of original chloroacetic mole number is 0.5-2.0.
2. method according to claim 1, in the mole number that the speed control wherein passing into ammonia in reactor passes at ammonia per hour and reactor, the ratio of original chloroacetic mole number is 1.0-2.0.
3. method according to claim 1, wherein reaction system is in the cooling of cooling jacket always, even if reaction liquid is in boiling state, also continues to cool it.
4. method according to claim 1, wherein methyl alcohol water content is lower than 0.15wt%.
5. method according to claim 1, wherein methyl alcohol water content is lower than 0.10wt%.
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| CN103086904B true CN103086904B (en) | 2016-03-02 |
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Families Citing this family (2)
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| CN111087319A (en) * | 2019-12-28 | 2020-05-01 | 中国天辰工程有限公司 | Method for continuously preparing glycine in alcohol phase |
| CN111100021A (en) * | 2019-12-31 | 2020-05-05 | 江苏汉凯工程技术有限公司 | Synthesis method of glycine |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1080632A (en) * | 1992-06-26 | 1994-01-12 | 陈明峰 | The improvement synthetic method of glycine |
| CN1340498A (en) * | 2000-08-31 | 2002-03-20 | 浙江新安化工集团股份有限公司 | Process for preparing glycine |
| RU2286335C2 (en) * | 2004-04-26 | 2006-10-27 | Торгово-коммерческая фирма "Холд" ООО "ТКФ "Холд" | Method for preparing aminoacetic acid |
| CN101701002A (en) * | 2009-10-31 | 2010-05-05 | 杨春华 | Glycocoll production method |
| CN102167668A (en) * | 2011-03-01 | 2011-08-31 | 刘长飞 | Method for producing glycin with environmentally-friendly alcohol phase chloroethanoic acid method |
-
2011
- 2011-11-04 CN CN201110346328.5A patent/CN103086904B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1080632A (en) * | 1992-06-26 | 1994-01-12 | 陈明峰 | The improvement synthetic method of glycine |
| CN1340498A (en) * | 2000-08-31 | 2002-03-20 | 浙江新安化工集团股份有限公司 | Process for preparing glycine |
| RU2286335C2 (en) * | 2004-04-26 | 2006-10-27 | Торгово-коммерческая фирма "Холд" ООО "ТКФ "Холд" | Method for preparing aminoacetic acid |
| CN101701002A (en) * | 2009-10-31 | 2010-05-05 | 杨春华 | Glycocoll production method |
| CN102167668A (en) * | 2011-03-01 | 2011-08-31 | 刘长飞 | Method for producing glycin with environmentally-friendly alcohol phase chloroethanoic acid method |
Non-Patent Citations (4)
| Title |
|---|
| 甘氨酸合成工艺的研究;胡卫国;《化工技术与开发》;20020930;第31卷(第3期);第3-5页 * |
| 甘氨酸合成的平行反应;胡卫国 等;《河北师范大学学报(自然科学版)》;20060131;第30卷(第1期);第79-82页 * |
| 甘氨酸连续化生产工艺研究;林少耕;《浙江大学硕士学位论文》;20031231;第18-25页 * |
| 醇相二步法合成甘氨酸的研究;钱益斌 等;《安徽农业科学》;20091231;第37卷(第13期);第5828-5829页 * |
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