CN1058957A - The manufacture method of glycine - Google Patents
The manufacture method of glycine Download PDFInfo
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- CN1058957A CN1058957A CN 91108179 CN91108179A CN1058957A CN 1058957 A CN1058957 A CN 1058957A CN 91108179 CN91108179 CN 91108179 CN 91108179 A CN91108179 A CN 91108179A CN 1058957 A CN1058957 A CN 1058957A
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- ammonia
- glycine
- monochloroacetic acid
- bicarbonate
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Abstract
A kind of improved glycine manufacture method.Replace liquefied ammonia formula ammoniacal liquor with bicarbonate of ammonia, and be present in the vulkacit H aqueous solution with solid phase and the dual form of liquid phase, drip the reaction of monochloroacetic acid liquid, after suitably control condition is fully reacted, reclaim with simple distillation again, the methyl alcohol of 80% above concentration or ethanol carry out alcohol and analyse, through centrifugation, the dry content that just can make is greater than 95% glycine, its yield is 85-90%, meanwhile also omit original refining step, exempt purification apparatus and be recycled to rectifying device pure more than 95% and liquid ammonia steel bottle etc., production cycle can foreshorten within 8 hours, had reduced energy consumption and production cost effectively.
Description
The present invention relates to the manufacture method of glycine, more more specifically, is to be medium with the vulkacit H aqueous solution, by monochloroacetic acid and bicarbonate of ammonia reaction, carry out that alcohol is analysed and the explanation of making the method for glycine with the 80% above alcohols thing that reclaims through simple distillation.Glycine is the important industrial chemicals of medicine industry, pesticide industry, organic synthesis and biochemical research, also can in foodstuffs industry, be used as odor control additive, asccharin goes bitter agent, in chemical fertilizer industry, be used as carbon dioxide removal agent, in textile industry, be used as tensio-active agent of textile dyeing or the like, use very wide.
Existing manufacturing glycine method is: with the vulkacit H aqueous solution is medium, by monochloroacetic acid and liquefied ammonia or ammoniacal liquor effect, utilize glycine undissolved characteristics in methyl alcohol or ethanol, through operations such as the methyl alcohol more than 95% or alcohol chromatography, overanxious, refining, dryings and make.
The shortcoming of this method is: product content is not high, and content reaches 95% product yield only between 50～64%, with separating also relatively for difficult of by product; Need just to obtain content and reach product more than 98% through above refining of secondary; The employed alcohols substrate concentration of purified product all needs more than 95%, and it is big to reclaim pure facility investment; Production cycle reaches more than 40 hour, the big and production cost height of energy consumption.
[1、2]
In order to solve the yield problem of glycine product, the someone proposes to adopt with alcohol for the water dissolution monochloroacetic acid, be dissolved in the method for the alcohol-water solution of 90% concentration as reaction medium with vulkacit H.Because glycine also is insoluble to alcoholic solvent, separates out immediately in reaction process, therefore making content is 95% above product, and it is nearly 80% that yield is increased to, and the Laboratory Production cycle foreshortened to about 16 hours.Though each side makes moderate progress, various shortcoming such as it is few that still, this method exists still that the product yield is not high, output per single reactor is low, it is refining with 95% above alcohols thing to need, the production cycle is still grown and production cost descends.
[1]
The objective of the invention is to: further improve the content and the yield of glycine product, the technology that simplifies the operation reduces facility investment, shortens the production cycle, save energy and reducing production costs.
Purpose of the present invention is reached by following approach, that is: use bicarbonate of ammonia replaces liquefied ammonia or the ammoniacal liquor in the existing technology, and exist in solution and monochloroacetic acid reacts with the dual form of solid phase and liquid phase, after the reaction conditions of suitably control production fully reacts, use again reclaim through simple distillation, concentration is that alcohol more than 80% carries out alcohol and analyses, after centrifugation, drying, just can make content greater than 95%(96～99%) required glycine product, the product actual recovery is 85～90%.
Detailed description the present invention is as follows.
The present invention specifically uses operation steps to be: be medium after being 10～40% vulkacit H of used monochloroacetic acid and water dissolution with quantity.Add solid ammonium bicarbonate, its gram molecular weight ratio with monochloroacetic acid is 2～3: 1, and take the method that in batches adds, the amount of Jia Ruing is a principle stirring first, then drip the monochloroacetic acid aqueous solution down in agitation condition, be controlled at therebetween between 5～40 ℃, the reaction process discontinuous adds all the other bicarbonate of ammonia of aequum, its principle has solid ammonium bicarbonate to exist for keeping in the medium, add before the water-soluble drop to 2/3 of monochloroacetic acid, the amount that adds bicarbonate of ammonia has no adverse effects to stirring, treat the reinforced slowly intensification of back that finishes, insulation is 1 hour between 60～70 ℃, overanxious then, the 80% above concentration alcohols thing that use is reclaimed through simple distillation carries out alcohol and analyses centrifugation then, drying just can make glycine purpose product.
Use bicarbonate of ammonia to replace liquefied ammonia or ammoniacal liquor in the existing technology, and exist in solution with the dual form of solid phase and liquid phase that to react with monochloroacetic acid be a key character of the present invention.Its reaction formula can be expressed as:
Among the present invention, the dissolving of bicarbonate of ammonia is thermo-negative reaction, avoided former technology because of local superheating produced the reaction of paying, simultaneously, bicarbonate of ammonia system is dissolving progressively, pH value can therefore be controlled at automatically help reacting 8～10 between, can't change because of the speed that drips monochloroacetic acid liquid speed, thereby increased operation elasticity greatly, reduced the generation of by product effectively.In addition, the buying of bicarbonate of ammonia, transportation all are easy to solve.
When carrying out this reaction, the water yield of dissolving vulkacit H should be being good less, so that the utilization ratio that improves synthesis reactor is to reduce cost as far as possible.Use when of the present invention, the monochloroacetic acid that the reactor of 1000 liters can drop into more than 350 kilograms is participated in reaction, thereby has improved output greatly.Determine, the consumption as the water of medium among the present invention is advisable to account for 10～40% of monochloroacetic acid amount, is preferably 15～35%.
When dropping monochloroacetic acid liquid and bicarbonate of ammonia react, should be controlled at suitable temperature range and carry out, if temperature is low excessively, then speed of response is slow excessively naturally, and temperature is too high, and then the molten damage of bicarbonate of ammonia increases, equally to reacting unfavorable.Dropwise reaction among the present invention is advisable to be controlled at 5～40 ℃, is preferably 15～35 ℃.
Use through simple and steam the low concentration alcohols thing that reclaims to carry out that alcohol analyses, do not re-refine and directly produce the glycine product be another key character of the present invention.Because this processing method has ammonium chloride and produces, few as best one can in order to make in the glycine product chlorine root, need utilize its in water solvability and remove.The present invention uses the alcohols thing of low concentration to carry out alcohol and analyses, and can reach not only to separate out glycine, but also the dissolving purpose of removing ammonium chloride.When the alcohols thing that adds low concentration to the synthetic liquid of reaction carries out after alcohol analyses, glycine product crystal system is grown up gradually, and the ammonium chloride of being carried secretly is also few, and its result is: glycine product crystal is big, and color and luster is white, and the chlorine root is few.Thereby, need not to make with extra care the product that (crude product is through being dissolved in water, adding once again pure analysing, and centrifuging is for once refining) can obtain conforming to quality requirements.Determine, alcohols thing used in the present invention is methyl alcohol or ethanol etc., and its concentration gets final product greater than 80%.
Use the present invention, it is very convenient that the glycine product separates with by product, content can reach (96～99%) more than 95%, its yield is 85～90%, also omitted the refining step of original technology simultaneously, exempted purification apparatus, be recycled to rectifying device pure more than 95% and liquid ammonia steel bottle etc., the Laboratory Production cycle can foreshorten in 8 hours, had reduced energy consumption and cost effectively.
Now the present invention is further described in detail by following examples.
Embodiment 1,
Add H to 500 milliliters the mouth flask that places water-bath, band whipping appts and thermometer
2O20 milliliter, vulkacit H 15 grams start stirring and make it dissolving.Add bicarbonate of ammonia 40 grams, drip the monochloroacetic acid aqueous solution down in 15 ℃ of temperature condition and (add H by the industrial monochloroacetic acid of 100 grams
2The O50 milliliter, thermosol forms) add bicarbonate of ammonia 60 grams after 15 minutes, add remaining bicarbonate of ammonia 80 gram after 30 minutes again.Monochloroacetic acid dropwises after 50 minutes, and the temperature of water-bath this moment is 39 ℃, and the synthetic liquid temperature of reaction is 33 ℃.Slow then heat temperature raising to reaching 60 ℃ of follow-up continuations of insurance temperature 1 hour, took advantage of heat filtering to go into big wide-necked bottle after 1 hour.Under agitation condition, add 89% ethanol, 1880 grams to this liquid, glycine crystallization just appears immediately, behind suction filtration, use Diluted Alcohol liquid secondary washing, in 80 ℃ of oven dry, get glycine product 67.5 grams after 1 hour, content is 98.75%, the chlorine root is less than 0.10%, and total preparation time is 8 hours, and product yield is 88.88%.
Embodiment 2
To capacity is to add 52.5 kilograms of distilled water in the enamel reaction still of 1000 liters, 52.5 kilograms of industrial vulkacit Hs, and heating is also stirred and is made its dissolving.Add 150 kilograms in agricultural grade bicarbonate of ammonia earlier, then begin to drip the monochloroacetic acid aqueous solution and (add H with industrial monochloroacetic acid
2The O175 kilogram, thermosol forms), 462.5 kilograms in bicarbonate of ammonia is added in gradation therebetween, and controlled temperature dropwises in 1 hour 30 minutes at 20～35 ℃ during dropwise reaction.Insulation is 1 hour after slowly being warming up to 60 ℃.The synthetic liquid of reaction adds 7 times of amounts after filtering and returns 87% concentration ethanol that is subjected to through simple distillation and carry out alcohol and analyse centrifugation, oven dry.The result makes 227.5 kilograms of glycine products, and its content reaches 98.3%, the chlorine root is less than 0.1%, and the product yield is 85.20%
Invention incorporated by reference document:
1, Zhu Shiying: " glycine study on the synthesis ", " Zhejiang chemical industry " the 3rd phase of nineteen ninety;
2, " Organic Chemicals and intermediate brief guide " first volume, Liaoning Province petrochemical technology information master station compiles, plate in 1980, the 282nd～3 page.
Claims (1)
1, a kind of is medium, the glycine manufacture method of using the monochloroacetic acid chemosynthesis with the hexamethylene tetraammonia aqueous solution, of the present invention being characterized as: use bicarbonate of ammonia, and bicarbonate of ammonia is present in the vulkacit H aqueous solution with the dual form of solid phase and liquid phase and reacts with monochloroacetic acid, analyses the synthetic liquid of reaction with the alcohols thing alcohol that reclaims through simple distillation, the product that directly makes without making with extra care, wherein:
(a), the mole ratio of employed bicarbonate of ammonia and monochloroacetic acid amount is 2～3: 1;
(b), the water yield of dissolving vulkacit H is 10～40% of a monochloroacetic acid amount;
(c), reaction is controlled under 5～40 ℃ of temperature condition and carries out;
(d), used alcohols thing is methyl alcohol or ethanol, its concentration is more than 80%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91108179 CN1058957A (en) | 1991-09-14 | 1991-09-14 | The manufacture method of glycine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91108179 CN1058957A (en) | 1991-09-14 | 1991-09-14 | The manufacture method of glycine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1058957A true CN1058957A (en) | 1992-02-26 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 91108179 Pending CN1058957A (en) | 1991-09-14 | 1991-09-14 | The manufacture method of glycine |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110697731A (en) * | 2019-11-05 | 2020-01-17 | 浙江浙能技术研究院有限公司 | Method for preparing ammonium sulfate and calcium carbonate from desulfurized gypsum |
| CN113200882A (en) * | 2021-04-30 | 2021-08-03 | 铂尊投资集团有限公司 | Glycine crystallization method without alcohol precipitation |
-
1991
- 1991-09-14 CN CN 91108179 patent/CN1058957A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110697731A (en) * | 2019-11-05 | 2020-01-17 | 浙江浙能技术研究院有限公司 | Method for preparing ammonium sulfate and calcium carbonate from desulfurized gypsum |
| CN113200882A (en) * | 2021-04-30 | 2021-08-03 | 铂尊投资集团有限公司 | Glycine crystallization method without alcohol precipitation |
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