CN108203393A - A kind of preparation method of glycine and ammonium chloride mixed crystal - Google Patents
A kind of preparation method of glycine and ammonium chloride mixed crystal Download PDFInfo
- Publication number
- CN108203393A CN108203393A CN201611187769.4A CN201611187769A CN108203393A CN 108203393 A CN108203393 A CN 108203393A CN 201611187769 A CN201611187769 A CN 201611187769A CN 108203393 A CN108203393 A CN 108203393A
- Authority
- CN
- China
- Prior art keywords
- reaction
- glycine
- methanol
- methenamine
- kettle
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/16—Halides of ammonium
- C01C1/164—Ammonium chloride
-
- 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
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
- C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of methods for preparing glycine and ammonia chloride crystal mixture, this method includes adding in methanol, monoxone and methenamine in a kettle, then ammonia is passed through into reaction kettle, cool down and reacted under conditions of stirring, reaction system is closed system, and equipped with condensing unit, the methanol liquid that condensing unit is condensed directly defeated time reaction system, reaction carries out in a kettle, the volume of reaction kettle is more than or equal to 5 cubic metres, and the quality (g) of methenamine is 6.5 7.2: 100 with the ratio of methanol volume (ml).The present invention by adjusting methenamine amount so that large capacity reactor prepares the raising of glycine yield, and yield is high, under the setting of a variety of conditions, realizes the production of glycine efficient circulation.
Description
Technical field
The invention belongs to field of fine chemical, and in particular to a kind of glycine and ammonium chloride of being prepared in absolute methanol phase
Method, the method for preparing the mixed crystal of glycine ammonium chloride in methanol phase especially by single step reaction.
Background technology
Glycine is the important source materials such as chemical industry, food, feed, and preparation method has disclosed many of report, example at present
Such as, using alcohol phase method prepare glycine important step be reacted to since reaction raw materials reaction terminate obtain glycine and chlorine
The step of changing ammonium mixture, the control of the time, charging sequence, reaction temperature of the step all directly influence the yield of mixture
And quality.
Two-step method prepares the patent of such as Qinghuaziguang Yingli Chemical Technology Co. Ltd., Beijing application of glycine,
Publication No. CN1410417A, entitled " preparation method of glycine " patent, the patent describe overcome one-step method sweet
The defects of propylhomoserin preparation, has invented the mixture that two-step method prepares glycine and ammonium chloride, two steps are respectively：(1) to chlorine
Ammonia is passed through in the mixture of acetic acid and alcohol, obtains product ammonium chloroacetate, (2) are to the mixture of ammonium chloroacetate, alcohol and methenamine
In be passed through ammonia, obtain glycine.The preparation method is needed to extract ammonium chloroacetate and be reacted again, by production process point
Into two steps, implement in production more time-consuming.In reaction process, the time of first step reaction is 0.5-1 small
When, along with cooling time, the time of second step reaction just needs 1-2 hours, along with cooling time, generally causes to react
Overlong time influences yield, and especially in second step, the concentration of the catalyst of use is too low, can not realize fast reaction.
The comparative example of glycine is prepared in the one-step method of the last comparison of CN1410417A patent specifications：It is filling
In the four-hole boiling flask for having blender, thermometer and reflux condenser, 50g (0.508mol) monoxone, 8g (0.056mol) are added in
Methenamine and 100g (3.125mol) methanol, after being stirred, rise to 65 DEG C by temperature, ammonia were slowly introducing in 2 hours,
Maintenance pH value be 7-8, keep the temperature 2-3 hour, crystallisation by cooling, filter dry content for 58.5% glycine crude product 58.61g,
Its yield in situ is 89.9%.Crude product adds the water of 1.8 times of amounts, dissolves by heating, and solution adds the ethyl alcohol of 2.5 times of amounts, and crystallisation by cooling is taken out
Filter is washed three times with ethyl alcohol, is then dried at 80 DEG C, obtains the glycine 31.54g that content is 99%, total recovery 81.88%.
Catalyst and solvent can only at most be applied mechanically five times.
On the one hand the defects of reaction is that the capacity of reaction is too small, reaction process needs to heat, and wastes energy, subsequent reactions
Cause local temperature excessively high without cooling measure again in the process, generation by-product is more, and the catalyst added in reacting
Amount is difficult to ensure that rapid reaction carries out, and causes the reaction time long, catalytic reaction effect is bad.
The method for preparing glycine of the present invention overcomes drawbacks described above, provides and a kind of prepares high quality glycine and chlorine
Change the method for ammonium mixture.
Invention content
In order to solve the above technical problems, the present invention provides a kind of sides for preparing glycine and ammonia chloride crystal mixture
Method, it is characterised in that this method comprises the following steps：Methanol, monoxone and methenamine are added in a kettle, then to anti-
It answers and ammonia is passed through in kettle, cool down and reacted under conditions of stirring, after reaction, reaction solution is centrifuged, obtain sweet ammonia
Acid and ammonia chloride crystal mixture solid and mother liquor, mother liquor are used as the raw material of next secondary response, and monoxone is added in simultaneously in mother liquor
It is passed through ammonia and carries out the second secondary response to prepare glycine and ammonium chloride, so recycle, the mother liquor conduct that preceding primary first-order equation obtains
The raw material of primary first-order equation prepares glycine and ammonium chloride afterwards, it is characterised in that：Reaction system is closed system, and equipped with condensation dress
It puts, the methanol liquid that condensing unit is condensed directly defeated time reaction system, reaction carries out in a kettle, and the volume of reaction kettle is big
In equal to 5 cubic metres, the quality (g) of methenamine is 6.5-7.2: 100 with the ratio of methanol volume (ml).
Preferably, in the above method, the quality (g) of methenamine is 6.5-7.0: 100 with the ratio of methanol volume (ml).
Preferably, in the above method, reaction system is constantly in the cooling of coolant jacket, even if reaction liquid is in boiling
State also continues to cool down it.
Preferably, in the above method, reaction system is constantly in stirring.
The production method of the present invention is suitable only for methanol and prepares glycine, is not suitable for water phase or alcohol water phase prepares sweet ammonia
Acid.
In the method for the present invention, the methanol water content is less than 0.15wt%, it is preferred that less than 0.10wt%.Entirely
It is anhydrous in reaction system to be meant that be contained in monoxone can other than methanol negligible present in methanol
With the water ignored, and monoxone is using industrial monoxone, and water content therein is less than 0.1%, it is preferred that using being less than
0.05% monoxone.
The above-mentioned method for preparing glycine of the present invention, on the one hand, be amplified production due to the use of reaction kettle, then for
Condition in reaction process controls especially important, the time especially reacted, if the overlong time of reaction, influences yield, such as
Fruit reaction is too fast, it is desirable that the ammonia being passed through is too fast or reaction system heats up, and can then cause to react bumping in this way, serious
The danger of explosion can be generated, can also side reaction be caused to increase.The present invention ensures reaction by controlling the amount of suitable catalyst
Time, while also ensure that the amount of catalyst can effectively be catalyzed reaction and carry out, reaction kettle is dropped during simultaneous reactions
Temperature is simultaneously stirred, and the time of reaction, reaction was safe there is no extending, and can ensure that the reaction was complete.Using Wu Luotuo
Product are prepared in the reaction of glycine, and rapid reaction can be caused the reaction was complete by generally requiring water, if participating in reacting without water,
Then reaction needs to increase temperature raising reaction speed, and otherwise the reaction time is long, so once improving temperature will cause instead
The by-product answered increases, such as by-product NH (CH2COOH)2Or by-product N (CH2COOH)3, so other approach can only be taken
Solve the problems, such as this, such as the two-step method used in publication number CN1410417A carries out preparing glycine, which prepares
So that the process of reaction becomes cumbersome, and it is complicated for operation in a large amount of industrial production, the production time is extended instead, although shortening
Reaction time, but time, there is no shorten on integrated artistic.
And the method for the present invention, it is to cool down during the reaction, does not heat up, to reaction kettle coolant jacket in reaction process
Cooling, low-temp reaction avoid the generation of by-product, then by the dosage of catalyst methenamine, ensure the speed of reaction not
It is influenced greatly, solves the problems, such as extension production.And the amount of catalyst will not cause to be precipitated due to the instantaneous reduction of methanol,
Generally the condensing reflux of methanol ensures that the overall process of reaction does not have methenamine precipitation again, so the amount of methenamine is set
Put is to ensure reaction speed and avoid there is a situation where that methenamine influences quality and occurs in reaction product.In the above method,
In reaction kettle there is blender to be stirred to reaction solution, ensure that reaction is uniform.
The present invention by adjusting methenamine amount so that large capacity reactor prepares the raising of glycine yield, and yield is high,
Under the setting of a variety of conditions, the production of glycine efficient circulation is realized.
Specific embodiment
In order to understand the present invention, further illustrated the present invention below with embodiment, but do not limit the present invention.
Embodiment 1
Which step mentioned in embodiment is actually the division in order to fairly set out reaction process progress, practical anti-
It is not so step by step that entire reaction process is actually continuous to answer process.
The first step：The methenamine mixture of the monoxone of 1000kg, the methanol of 4000L, 260Kg is anti-in 5 cubic metres
It answers in kettle, reaction kettle is provided with condenser, and the liquid outlet of condenser accesses in reaction kettle, is at the uniform velocity passed through ammonia and starts to react,
Reaction kettle is cooled down with coolant jacket in reaction process, the pH of reaction system reach 7.8 and keep 5 minutes it is constant after, no
It is passed through ammonia, 2.12 hours reaction time again.
Second step：After the completion of reaction with coolant jacket continue cool down reaction kettle, when the temperature of reaction solution reach 40 DEG C when
It waits, solution is passed through in centrifuge, the mixed crystal solid and mother liquor of glycine and ammonium chloride are centrifuged, under mother liquor enters
Primary first-order equation process.
Third walks：Mother liquor is added in another reaction kettle, reaction kettle is provided with condenser, the liquid outlet of condenser
It accesses in reaction kettle, the monoxone of 1000kg is added in into mother liquor, ammonia is then passed to and is reacted, with cooling in reaction process
Set cools down reaction kettle；The pH of reaction system reach 7.8 and keep 5 minutes it is constant after, be no longer passed through ammonia.
Then second step, three-step reaction are repeated.It so recycles mother liquor and carries out circular response, carry out 18 again instead
It should recycle, carry out 20 cycles altogether.
Embodiment 2
Embodiment 1 is repeated, adjusts the dosage of methenamine, adjusts the dosage of methenamine, other reaction condition phases respectively
Together.Specific experimental result is as follows：
As can be seen that the numerical value of the mass/volume of methenamine and methanol ratio not only influences reaction time, yield, may be used also
Can lead to whether contain methenamine impurity in product.The ratio of methenamine is too low, then causes the reaction time long, influences
Production capacity, and ratio is excessively high, then so that containing methenamine impurity in product, so preferable ratio is 6.5-7.
Claims (3)
- A kind of 1. method for preparing glycine and ammonia chloride crystal mixture, it is characterised in that this method comprises the following steps： Methanol, monoxone and methenamine are added in reaction kettle, ammonia is then passed through into reaction kettle, under conditions of cooling down and stirring into Row reaction, after reaction, reaction solution is centrifuged, and obtains glycine and ammonia chloride crystal mixture solid and mother liquor, mother liquor Raw material as next secondary response, in mother liquor add in monoxone and be passed through ammonia carry out the second secondary response come prepare glycine and Ammonium chloride so recycles, and the mother liquor that preceding primary first-order equation obtains prepares glycine and ammonium chloride as the raw material of rear primary first-order equation, It is characterized in that：Reaction system is closed system, and equipped with condensing unit, and the methanol liquid that condensing unit is condensed directly defeated time is anti- System is answered, reaction carries out in a kettle, and the volume of reaction kettle is more than or equal to 5 cubic metres, quality and the methanol body of methenamine Long-pending ratio is 6.5-7.0g：100ml.
- 2. according to the method described in claim 1, wherein the ratio of the quality of methenamine and methanol volume is 6.5-7.0g： 100ml。
- 3. according to the method described in claim 1, wherein methanol water content is less than 0.15wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611187769.4A CN108203393A (en) | 2016-12-20 | 2016-12-20 | A kind of preparation method of glycine and ammonium chloride mixed crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611187769.4A CN108203393A (en) | 2016-12-20 | 2016-12-20 | A kind of preparation method of glycine and ammonium chloride mixed crystal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108203393A true CN108203393A (en) | 2018-06-26 |
Family
ID=62604326
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611187769.4A Pending CN108203393A (en) | 2016-12-20 | 2016-12-20 | A kind of preparation method of glycine and ammonium chloride mixed crystal |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108203393A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2016
- 2016-12-20 CN CN201611187769.4A patent/CN108203393A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105859571A (en) | Method for producing glycine by mixed solvent method | |
| CN104829495B (en) | A kind of method that two-component solvent prepares high-purity high-yield Metformin hydrochloride | |
| CN108484421B (en) | The improved method for preparing glycine ethyl ester hydrochloride | |
| CN109232470A (en) | A kind of new process synthesizing ainothiazoly loximate | |
| CN110551023A (en) | Method for preparing alkyl diacid monobenzyl ester | |
| CN106478438A (en) | A kind of preparation method of magnesium glycinate chelate | |
| CN108947897B (en) | Novel preparation method of nicorandam | |
| CN108203393A (en) | A kind of preparation method of glycine and ammonium chloride mixed crystal | |
| CN103086903B (en) | The preparation method of a kind of glycine and ammonium chloride mixed crystal | |
| CN103382200A (en) | Preparation method of S-glycidylphthalimide | |
| CN106748910B (en) | A kind of recrystallization method and preparation method of 2- acrylamide-2-methylpro panesulfonic acids | |
| CN104744239B (en) | The preparation method of hydroxyacetic acid | |
| CN107868015A (en) | A kind of preparation method of glycine and ammonium chloride mixed crystal | |
| CN104496825B (en) | The preparation method of 2-fluorine ethylamine hydrochloride | |
| CN105753733A (en) | AHU377 crystal form and preparation method and uses thereof | |
| CN105732457B (en) | A method of preparing succimide using succinic acid fermentation liquor | |
| CN108084238A (en) | A kind of preparation method of canrenone intermediate | |
| CN106699581A (en) | Preparation method of glycine and ammonium chloride mixed crystal | |
| CN104478747A (en) | Method for producing glycine through organic solvent | |
| CN108129303A (en) | A kind of preparation method of R- (+) -2- (4- hydroxyphenoxies) methyl propionate | |
| CN111303172B (en) | Method for preparing etodolac methyl ester | |
| CN106916068A (en) | A kind of simple and convenient benzalkonium chloride production method | |
| CN103086904B (en) | A kind of method of carrying out environment-friendly cycle method production glycine at reactor | |
| JP2022547196A (en) | Continuous production equipment for 2,6-dihydroxybenzaldehyde and its use | |
| CN107043343A (en) | A kind of preparation method of L pyroglutamic acids |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20180626 |
|
| WD01 | Invention patent application deemed withdrawn after publication |