CN109206329A - A kind of preparation method of glycine - Google Patents
A kind of preparation method of glycine Download PDFInfo
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- CN109206329A CN109206329A CN201710515229.2A CN201710515229A CN109206329A CN 109206329 A CN109206329 A CN 109206329A CN 201710515229 A CN201710515229 A CN 201710515229A CN 109206329 A CN109206329 A CN 109206329A
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- reaction
- alcoholic solution
- glycine
- iodide
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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
- C07C227/04—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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/363—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
Abstract
The invention discloses a kind of preparation methods of glycine, belong to the preparation method of amino acid, including displacement and ammonification two-step reaction, the alcoholic solution of monoxone and iodide is performed under heating conditions displacement desalination reaction first, it is centrifuged or filters after reaction, respectively obtain the alcoholic solution of chloride and iodoacetic acid；Then catalyst is added in the alcoholic solution of iodoacetic acid, heats and be passed through ammonia progress aminating reaction, is centrifuged or filters after reaction, respectively obtain the alcoholic solution of glycine and the iodide containing catalyst；Reaction solution can be recycled in the present invention, the link of the cumbersome energy consumptions such as organic solvent extraction, rectifying, evaporation can be saved, the waste liquid for needing to carry out environmental protection treatment is not generated yet, and product yield and purity can be improved, have the advantages that lower production costs, easy to operate, raw material are easy to get, meet the requirement and suitable industrialized production of clean and environmental protection.
Description
Technical field
The present invention relates to a kind of preparation method of compound, especially a kind of preparation method of amino acid belongs to monoxone
Ammoniation process prepares the technology field of glycine.
Background technique
Glycine is also referred to as amion acetic acid, molecular formula NH2CH2COOH is the important basic organic of one kind and fine
Chemical products are widely used in the industries such as Organic Chemical Industry, medicine, food, pesticide, feed.For example, glycine is in pharmaceuticals industry
In can be used as the buffer of amino acid preparation, aureomycin, also can be used as other amino acid of Material synthesis, such as phenylalanine, Soviet Union's ammonia
Acid, serine etc..In terms of food, glycine makes an addition in various food frequently as food additives, for seasoning, sterilizing,
Anti-corrosion, anti-oxidant, fortification etc., it is edible after convenient for absorption of human body and synthesize other in vivo must be with nonessential amino
Acid；Glycine can be used as flavoring agent individually or with cooperations such as glutamic acid, it can also be used to synthesize wine and brewing product, also act as
The additive of cream, margarine and cheese etc., to extend the shelf-life of food.In pesticide industry, glycine is often a large amount of
Raw material as synthesizing glyphosate, the sweet phosphorus of increasing etc..In recent years, with the continuous improvement of people's living standards, medicine, food and agriculture
Requirement of the medicine industry for the demand and product quality of glycine increasingly increases, therefore to glycine industrialized producing technology
Design and optimization and improvement have important value and significance.
Current existing glycine preparation method is mainly monoxone water phase ammoniation process and alcohol phase ammoniation process, wherein monoxone
Water phase ammoniation process in industry uses more universal.Monoxone water phase ammoniation process is with methenamine (the entitled hexa-methylene four of chemistry
Amine) solution as catalyst, reacts with ammonia by chloroethene aqueous acid and generates glycine.Reaction equation are as follows: ClCH2COOH+
2NH3→NH2CH2COOH+NH4Cl.Obtain after reaction include glycine and ammonium chloride mixed liquor, into mixed liquor plus
Enter methanol to be extracted, separate ammonium chloride, glycine wet product and mother liquor are obtained after being centrifuged.Glycine wet product obtains after drying
Finished product is obtained, mother liquor recycles methanol by rectifying first, then passes through concentration and evaporation recycling ammonium chloride.Using this post-processing side
The yield of method, glycine is lower, is generally only 84~86% or so.Due to being directly to add after the reaction to reaction system
Enter methanol extraction, in order to guarantee effect of extracting, the usage amount of extractant methanol is usually larger, and which not only adds be produced into
This, and the treating capacity of centrifuge separation is increased, energy consumption is very high.The generation of centrifuge mother liquor containing a large amount of methanol also increases simultaneously
The difficulty of recovery processing, not only needs to configure the special equipments such as the big rectifying column for the treatment of capacity, concentration evaporator, and energy consumption compared with
Height also has certain pollution to environment.
Chinese patent literature CN1896049B discloses a kind of production technology of amion acetic acid.The technique is with liquid chloroacetic acid
It is reaction raw materials with ammonia, using methenamine aqueous solution as catalyst, first puts into methenamine solution in reactor when production,
Then it is slowly dropped into liquid chloroacetic acid under ammonia atmosphere, the control of reaction temperature precision is at 70~85 DEG C, pH value in reaction precision control
System improves the stability of reaction and the yield of amion acetic acid and purity 6~8.But the method for purification of the production technology is still
So using the method for being directly added into methanol extraction reaction solution, centrifuge separation brought by the use of a large amount of methanol not can solve
The problems such as treating capacity is big, methanol mother liquor recycling post-processes difficulty, high production cost, environmental pollution.
Summary of the invention
The technical problem to be solved by the invention is to provide a kind of preparation methods of glycine, are reacted using two-step, can
Be recycled reaction solution, the link of the cumbersome energy consumptions such as organic solvent extraction, rectifying, evaporation can be saved, do not generate yet need into
The waste liquid of row environmental protection treatment, and product yield and purity can be improved, and there are lower production costs, easy to operate, raw material to be easy to get,
The advantages of meeting the requirement and suitable industrialized production of clean and environmental protection.
In order to solve the above technical problems, the technical scheme adopted by the invention is that:
A kind of preparation method of glycine, includes the following steps:
A. monoxone is reacted in a heated condition with the alcoholic solution of iodide, is centrifuged or filters after reaction, respectively
Obtain chloride and iodoacetic acid；
B. catalyst is added in iodoacetic acid, and is passed through ammonia, is centrifuged or filters after reaction, respectively obtain glycine
With the alcoholic solution of the iodide containing catalyst.
Technical solution of the present invention further improvement lies in that: when continuous preparation, since the second wheel preparation, by last round of system
The alcoholic solution of iodide containing catalyst obtained in standby step B for next round preparation in, second wheel preparation and after
Preparation include the following steps:
C. by the alcoholic solution of the obtained iodide containing catalyst of monoxone and last round of preparation step B in heating condition
Lower reaction is centrifuged after reaction or filters, respectively obtains the alcoholic solution of chloride and the iodoacetic acid containing catalyst；
D. the alcoholic solution of the iodoacetic acid containing catalyst is heated and is passed through ammonia, be centrifuged or filter after reaction, point
The alcoholic solution of glycine and the iodide containing catalyst is not obtained.
Technical solution of the present invention further improvement lies in that: the iodide are ammonium iodide, sodium iodide, appointing in potassium iodide
One or more of mixing.
Technical solution of the present invention further improvement lies in that: the alcoholic solution is any one of methanol, ethyl alcohol or propyl alcohol
Or several mixing.
Technical solution of the present invention further improvement lies in that: the mass ratio that monoxone is reacted with iodide be 1:0.5~5,
Mass ratio of the iodide in the alcoholic solution of iodide is 10~50%.
Technical solution of the present invention further improvement lies in that: the catalyst is methenamine, iodoacetic acid and catalyst
Mass ratio is 1:0.02~0.15.
Technical solution of the present invention further improvement lies in that: be passed through ammonia rate be so that pH is maintained at 7.0~8.5.
Technical solution of the present invention further improvement lies in that: catalyst is first dissolved in 1/10~1/3 volume in step B
Reaction solution is formed in the alcoholic solution of iodoacetic acid, the alcohol that the iodoacetic acid of residual volume is then slowly dropped into when being passed through ammonia is molten
Liquid.
Technical solution of the present invention further improvement lies in that: taken out in step D 1/10~1/3 volume containing catalyst
The alcoholic solution of iodoacetic acid is slowly dropped into the alcoholic solution of the iodoacetic acid containing catalyst of residual volume when being passed through ammonia.
Above-mentioned technical proposal of the invention further improvement lies in that: the temperature of heating is 30~65 DEG C, and the reaction time is
30~180 minutes, it is cooled to 20~35 DEG C after reaction and is centrifuged or filters again.
By adopting the above-described technical solution, the technological progress achieved by the present invention is:
A kind of preparation method of glycine of the invention, is reacted, the first step first separates chloride using two-step
As byproduct, after the isolated glycine of second step, the alcoholic solution of the remaining iodide containing catalyst can be followed directly
Ring uses, and avoids the link cumbersome with the organic solvent extraction energy consumption such as product and rectifying, evaporation, does not also generate and need to carry out ring
Protect processing waste liquid, all products all can be used as product output or recycling and reusing, and have product yield and purity is high,
Lower production costs, easy to operate, raw material be easy to get, meet clean and environmental protection requirement and suitable industrialized production the advantages of.
The present invention first uses iodide and chloroacetate reaction, and chloride ion is precipitated in the form of chloride, while by carboxylic first
Base is converted into the form of iodoacetic acid, into following aminating reaction.The present invention solves sweet ammonia after traditional single step reaction
Acid and the big problem of chloride mix separating difficulty, avoid using recycling etc. after organic solvent extraction, rectifying, evaporation
Manage step cumbersome and equipment investment, before aminating reaction by centrifugation or filtering can easily by insoluble matter chloride from
It is separated in system, simplifies operating procedure, reduce cost recovery.
Step A of the present invention can produce side product chlorinated object, generate economic value, realize the comprehensive utilization of resource, and divide
It is simple from step, the problem of needing when traditional handicraft is finally separating extraction using a large amount of organic solvents and energy consumption is overcome,
Reduce production cost.Step A is displacement desalination reaction, and monoxone is reacted with the alcoholic solution of iodide generates chloride and iodine second
The chloride of acid, generation is ammonium chloride, sodium chloride or potassium chloride, and the solubility in alcohol is smaller, can be by being centrifuged or filtering
Mode be isolated as by-product, ammonium chloride can be used as chemical fertilizer sale, and sodium chloride and potassium chloride can be used as industrial chemicals and goes out
It sells, purity can reach 98% or more, can satisfy the requirement for directly using or selling, manufacturer is in the production sweet ammonia of major product
While sour, can output other have a byproduct of economic value, increase to take in and simultaneously reduce the wasting of resources.
The alcoholic solution for the iodide containing catalyst that step B of the present invention is obtained, which can be directly entered next round reaction cycle, to be made
With, without being separated or being reprocessed, waste liquid or other pollutants are not generated, technological operation is simplified, reduces production cost,
Solve the problems, such as that residual reaction liquid separation recycles highly difficult, complicated for operation, higher cost, pollution larger in traditional handicraft.
After being centrifuged or filtering to isolate glycine, remaining liquid is the mixed solution of the alcoholic solution of catalyst and iodide, this mixing
Solution can be directly used for step A, and the supplement or substitution of the alcoholic solution as iodide form circulating reaction.In mixed solution
Catalyst without carrying out separation removal, and cannot participate in or influence the reaction of step A, when proceeding to step B, can also save
Add the operation of catalyst, or only in considering operating error and operating process there are in the case where a small amount of loss of material, convection current
The catalyst of mistake or the solvent of volatilization make a small amount of supplement.
First catalyst is dissolved in the iodoacetic acid of part in step B of the invention, remaining iodoacetic acid during the reaction with
The mode of dropwise addition is slowly added to, and can continue alcohol of the supplement as solvent into reaction system in crystallization precipitation process, can
Keep rate of crystalline growth more controllable, granule size is more uniform, prevents fine grain from generating, overcome in product precipitation process by
A large amount of fine grains caused by solution concentration increases are led to the problem of, and improve product quality, and reduce the difficulty of product separation.
Step B of the invention is aminating reaction, is passed through ammonia rate so that the pH value of reaction solution is within 7.0~8.5
Subject to, solve the problems, such as that ammonia intake is difficult to be precisely controlled and hold when influence factor is more, hence it is evident that improve
Utilization rate, product quality and the reaction rate of ammonia.When ammonia be passed through rate it is too fast when, be easy to cause ammonia to be distributed in the solution
Unevenly, the problems such as local pH is excessively high, gas evolution is very fast, ammonia utilization rate is low, when ammonia intake is excessively slow, reaction efficiency
Lower and product quality is poor.
The process conditions of step A and step B are optimized in the present invention, improve product yield, reduce catalyst
Dosage reduces production cost, carries out reaction milder, and the crystal form of crystallization is ideal, and reaction rate is very fast, can be improved
The purity of production efficiency, product significantly improves, and can reach 98.5% or more.Step A and step B is heating reaction, reaction temperature
Degree control is at 30~65 DEG C, and preferably 30~65 DEG C, optimum reaction carries out under this temperature range, when the temperature is excessively high, urges
The solubility of agent declines, and adverse effect carries out, and is easy to cause product oxygenolysis, influences purity and color, temperature mistake
When low, reaction rate is slower, is unfavorable for the raising of production efficiency.Step A and step B uses optimal ingredient proportion, favorably
It is carried out in reaction forward, improves raw material availability, reduce reaction cost.Reaction time is suitably 30~180 minutes, preferably
It is 90~150 minutes, separation product, final products yield significantly improve again after being cooled to room temperature solution after reaction, by
85% or so originally is improved to 95% or more.
Specific embodiment
Here is certain specific embodiments of the invention, to invention is further described in detail, but not with
This limits protection scope of the present invention.
A kind of the step of preparation method of glycine, prepared by the first round, is as follows:
A. displacement reaction: monoxone is added in reaction vessel, adds the alcoholic solution of iodide, and stir evenly, iodine
Compound is the mixing of any one or more of ammonium iodide, sodium iodide, potassium iodide, and alcoholic solution is in methanol, ethyl alcohol or propyl alcohol
Any one or several mixing, the mass ratio that monoxone is reacted with iodide are 1:0.5~5, and iodide are molten in the alcohol of iodide
Mass ratio in liquid is 10~50%.Reaction solution is heated to 30~65 DEG C of temperature and carries out displacement reaction, and continues to stir, it is excellent
The temperature range of choosing is 55~65 DEG C, and the reaction time is 30~180 minutes, preferably 90~150 minutes, is stopped after reaction
Heating, after being cooled to 20~35 DEG C, is separated by solid-liquid separation by being centrifuged or filtering, and obtained solid is chloride, can after dry
For sale, liquid is the alcoholic solution of iodoacetic acid, and entering step B, the reaction was continued.
B. aminating reaction: 1/10~1/3 parts by volume is first taken out from the alcoholic solution of the obtained iodoacetic acid of step A, thereto
Catalyst methenamine is added, the mass ratio of the catalyst of the alcoholic solution and addition for whole iodoacetic acid that step A is obtained is 1:
0.02~0.15, preferably 1:0.02~0.05.Stirring is heated after being completely dissolved to catalyst, keeps the temperature at 30~65 DEG C
Aminating reaction is carried out, preferred range is 55~65 DEG C, is passed through ammonia into reaction solution during the reaction, and pass through tune
The whole rate for being passed through ammonia makes range of the pH control of reaction 7.0~8.5, by remaining iodoacetic acid while logical ammonia
Alcoholic solution be slowly added dropwise into reaction solution, and continue to stir, the reaction time is 30~180 minutes, preferably 90~150 points
Clock stops heating after reaction, after being cooled to 20~35 DEG C, is separated by solid-liquid separation by being centrifuged or filtering, obtained solid
For glycine wet product, glycine finished product will be obtained after the drying of glycine wet product, liquid is that the alcohol of the iodide containing catalyst is molten
Liquid.
It can be after first round reaction terminates to isolate product, by remaining reaction mother liquor when continuously preparing glycine
(i.e. the alcoholic solutions of the iodide containing catalyst) are recycled in next production preparation.Since the second wheel preparation,
The alcoholic solution that the iodide containing catalyst are obtained in the step B of last round of preparation reaction can be substituted next reaction cycle
In the alcoholic solutions of iodide carry out displacement with monoxone and react, the alcoholic solution of the iodide containing catalyst is without processing
Direct reuse, can also appropriate supplementing solvent a small amount of loss in operation of devolatilization and catalyst.
Second wheel preparation and later preparation step are as follows:
C., monoxone is added to the alcoholic solution for the iodide containing catalyst methenamine that last round of preparation step B is obtained
In, the mass ratio of the iodide in monoxone and reaction solution is 1:0.5~5, is stirred and heated to 30~65 DEG C, reaction 30
Stop heating after~180 minutes, cool to after 20~35 DEG C, then be separated by solid-liquid separation by centrifugation or filtering, is obtained
Solid is chloride, can be used as byproduct output after dry, and liquid is the alcoholic solution of the iodoacetic acid containing catalyst, reaction solution
In catalyst be not involved in reaction, be not also lost theoretically.
D. the alcoholic solution of the iodoacetic acid containing catalyst of 1/10~1/3 volume is heated to 30~65 DEG C, contains catalysis
The mass ratio of iodoacetic acid and catalyst methenamine is 1:0.02~0.15 in the alcoholic solution of the iodoacetic acid of agent, is passed through thereto
Ammonia, and by adjusting the rate for being passed through ammonia, make the pH control of reaction in the range of pH7.0~8.5, is passed through ammonia
Simultaneously the alcoholic solution of the iodoacetic acid containing catalyst of residual volume is slowly added dropwise in reaction solution, the reaction time be 30~
180 minutes, it is cooled to 20~35 DEG C after reaction and is separated by solid-liquid separation again by centrifugation or filtering, obtained solid is wet product
Glycine obtains glycine finished product after dry, liquid is the alcoholic solution of the iodide containing catalyst methenamine, under can entering
Continue to be recycled in the step C of one wheel preparation.
Examples 1 to 4
Examples 1 to 4 is identical as production craft step used by above-mentioned specific embodiment, different technological parameters,
Or the different types of compound chosen is as shown in Table 1 below.Wherein, " iodide " are the type of iodide, the ratio in table
Number of cases value is mass ratio when several iodide mix, and " alcohol " is the type of alcohol, when the proportional numerical value in table is that several alcohol mix
Mass ratio.
Table 1
In order to preferably verify feasibility and superiority of the invention, inventor is according to production described in Examples 1 to 4
Technique and the production of corresponding technological parameter are prepared for glycine, to the purity of the side product chlorinated object of step A and step C output with
And the glycine finished product purity of step B and step D output is detected, and respectively to the total recovery that the first round and second take turns
It is calculated, as a result as shown in Table 2 below.
Table 2
| Example 1 | Example 2 | Example 3 | Example 4 | |
| First round chloride purity (%) | 99.1 | 99.2 | 99.3 | 99.3 |
| First round glycine purity (%) | 98.6 | 98.7 | 98.9 | 98.8 |
| First round glycine total recovery (%) | 95.2 | 96.3 | 95.5 | 95.8 |
| Second wheel chloride purity (%) | 99.0 | 99.1 | 99.4 | 99.5 |
| Second wheel glycine purity (%) | 98.7 | 98.5 | 99.1 | 99.0 |
| Second wheel glycine total recovery (%) | 97.3 | 97.6 | 97.4 | 97.1 |
It can be seen that the preparation method using glycine provided by the invention according to the testing result of table 2, it is produced sweet
Propylhomoserin purity significantly improves, and can reach 98.5% or more, using the 4 purity energy of embodiment 3 and embodiment of optimizing technology parameters
The level for reaching 98.8~99.1%, higher than the requirement of high-class product 98.5% in professional standard HG/T2029-2004.Embodiment 1
~4 yield also significantly improves, and first round production total recovery can reach 95% or more, and the second wheel and later circular response are total
Yield can reach 97% or more level, the significantly larger than level of traditional processing technology 80% or so.
Claims (10)
1. a kind of preparation method of glycine, it is characterised in that include the following steps:
A. monoxone is reacted in a heated condition with the alcoholic solution of iodide, is centrifuged or filters after reaction, respectively obtains
The alcoholic solution of chloride and iodoacetic acid；
B. catalyst is added in the alcoholic solution of iodoacetic acid, heats and be passed through ammonia, be centrifuged or filter after reaction, respectively
The alcoholic solution of iodide to glycine and containing catalyst.
2. a kind of preparation method of glycine according to claim 1, it is characterised in that: when continuous preparation, from the second wheel
Preparation starts, and the alcoholic solution of the iodide obtained in the step B by last round of preparation containing catalyst is used for next round preparation
In, the second wheel preparation and later preparation include the following steps:
C. the alcoholic solution of monoxone and the obtained iodide containing catalyst of last round of preparation step B is anti-in a heated condition
It answers, is centrifuged or filters after reaction, respectively obtain the alcoholic solution of chloride and the iodoacetic acid containing catalyst；
D. the alcoholic solution of the iodoacetic acid containing catalyst is heated and is passed through ammonia, be centrifuged or filter after reaction, respectively
The alcoholic solution of iodide to glycine and containing catalyst.
3. according to claim 1 or a kind of 2 described in any item preparation methods of glycine, it is characterised in that: the iodide
For the mixing of any one or more of ammonium iodide, sodium iodide, potassium iodide.
4. according to claim 1 or a kind of 2 described in any item preparation methods of glycine, it is characterised in that: the alcoholic solution
For the mixing of any one or more of methanol, ethyl alcohol or propyl alcohol.
5. according to claim 1 or a kind of 2 described in any item preparation methods of glycine, it is characterised in that: monoxone and iodine
The mass ratio of compound reaction is 1:0.5~5, and mass ratio of the iodide in the alcoholic solution of iodide is 10~50%.
6. according to claim 1 or a kind of 2 described in any item preparation methods of glycine, it is characterised in that: the catalyst
For methenamine, the mass ratio of iodoacetic acid and catalyst is 1:0.02~0.15.
7. according to claim 1 or a kind of 2 described in any item preparation methods of glycine, it is characterised in that: be passed through ammonia
Rate is that pH is made to be maintained at 7.0~8.5.
8. a kind of preparation method of glycine according to claim 1, it is characterised in that: first that catalyst is molten in step B
Reaction solution is formed in the alcoholic solution of the iodoacetic acid of 1/10~1/3 volume, and residual body is then slowly dropped into when being passed through ammonia
The alcoholic solution of long-pending iodoacetic acid.
9. a kind of preparation method of glycine according to claim 2, it is characterised in that: take out 1/10~1/3 in step D
The alcoholic solution of the iodoacetic acid containing catalyst of volume is slowly dropped into the iodine containing catalyst of residual volume when being passed through ammonia
The alcoholic solution of acetic acid.
10. according to claim 1 or a kind of 2 described in any item preparation methods of glycine, it is characterised in that: the temperature of heating
It is 30~65 DEG C, the reaction time is 30~180 minutes, is cooled to 20~35 DEG C after reaction and is centrifuged or filters again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710515229.2A CN109206329A (en) | 2017-06-29 | 2017-06-29 | A kind of preparation method of glycine |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710515229.2A CN109206329A (en) | 2017-06-29 | 2017-06-29 | A kind of preparation method of glycine |
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| Publication Number | Publication Date |
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| CN109206329A true CN109206329A (en) | 2019-01-15 |
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| CN201710515229.2A Withdrawn CN109206329A (en) | 2017-06-29 | 2017-06-29 | A kind of preparation method of glycine |
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2017
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Application publication date: 20190115 |