CN107903197B - The stabilizer for preparing and storing for 3- methylthiopropionaldehyde - Google Patents
The stabilizer for preparing and storing for 3- methylthiopropionaldehyde Download PDFInfo
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- CN107903197B CN107903197B CN201711404540.6A CN201711404540A CN107903197B CN 107903197 B CN107903197 B CN 107903197B CN 201711404540 A CN201711404540 A CN 201711404540A CN 107903197 B CN107903197 B CN 107903197B
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- methylthiopropionaldehyde
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/26—Separation; Purification; Stabilisation; Use of additives
- C07C319/28—Separation; Purification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/26—Separation; Purification; Stabilisation; Use of additives
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Abstract
本发明涉及用于MMP制备及储存的稳定剂，该稳定剂为单糖或者为二糖。通过本发明所公开的技术方案，能够显著地稳定MMP，特别是在高温纯化和后期的存储过程中，从而避免MMP在纯化及存储中的降解，有效节约AT88和NP99的生产成本，提高生产效率。The invention relates to a stabilizer used for MMP preparation and storage, the stabilizer is monosaccharide or disaccharide. Through the technical solution disclosed in the present invention, MMP can be significantly stabilized, especially in the process of high-temperature purification and later storage, thereby avoiding the degradation of MMP in purification and storage, effectively saving the production cost of AT88 and NP99, and improving production efficiency .
Description
Technical field
The present invention relates to the stabilizers for preparing and storing for 3- methylthiopropionaldehyde, belong to the industrialization of 3- methylthiopropionaldehyde
It produces and using 3- methylthiopropionaldehyde as the Related product field of industrialized production of intermediate.
Background technique
3- methylthiopropionaldehyde refers to that 3- methylthiopropionaldehyde, chemical structural formula are as follows:
3- methylthiopropionaldehyde is to prepare methionine powder (DL- METHIONINE) and hydroxyl similar liquids (DL-2- hydroxyl -4-
Methylmercapto butyric acid) important antecedent.Its purifying last before being DL- METHIONINE and the synthesis of DL-2- hydroxy-4-methylthiobutyric acid
Intermediary, it is therefore evident that obtaining the higher 3- methylthiopropionaldehyde of purity for subsequent DL- METHIONINE and DL-2- hydroxyl
It is very crucial for the production of base -4- methylmercapto butyric acid.
The mode generallyd use in currently available technology is made under the effect of the catalyst using methacrylaldehyde and MSH as raw material
Standby to obtain 3- methylthiopropionaldehyde, chemical equation is as follows:
For example there is such description in DE-102010064250.9, is aoxidized obtain by propylene fraction in the method
Methacrylaldehyde step is removed by quenching/by-product after, absorbed in 3- methylthiopropionaldehyde and and free methyl mercaptan or formation
For 3- methylthiopropionaldehyde/methyl mercaptan hemimercaptol (3- methylthiopropionaldehyde/MC hemimercaptol, from MC+3- first of intermediate
Sulfenyl propionic aldehyde) methyl mercaptan that is discharged reacts to obtain 3- methylthiopropionaldehyde.
In order to obtain the higher 3- methylthiopropionaldehyde of purity, we further carry out essence to 3- methylthiopropionaldehyde after the reaction
Evaporate and etc..It is in the actual production process we have found that equal carrying out 3- methylthiopropionaldehyde in purification process to 3- methylthiopropionaldehyde
There are a degree of losses.For example 3- methylthiopropionaldehyde will at least lose 3% during purification, wherein near during except tail
1.5% is lost less.Simultaneously, it should be mentioned that still have at least 0.5% loss in the memory phase of 3- methylthiopropionaldehyde.
These all cause the increase of DL- METHIONINE and DL-2- hydroxy-4-methylthiobutyric acid production cost.
It is therefore prevented that 3- methylthiopropionaldehyde is rotten, the stability of 3- methylthiopropionaldehyde is improved, including during the preparation process
Stabilization after stabilization and rectifying under the hot environment of stage of rectification in storage, for manufacturing DL-2- 2-hydroxy-4-methylthio fourth
It all has very important significance for the products such as acid, DL- METHIONINE.
Since 3- methylthiopropionaldehyde is aldehyde compound.It is therefore desirable to be able to be found from existing aldehydes stabilizer
The answer solved the problems, such as.Wherein especially cause we note that be EP0148648, US4546205 and EP0096153 this three
Part patent document,
They, which contain, makes the stabilized industry solutions of aldehyde.Although the mechanism of action of disclosed stabilizer is not
Together, but it is recommended to use phenolic antioxidant.Phenol/amine blends are preferred stabilizers in patent document US4546205, and
And furthermore present the optional type of phenol, amine.
Then, we simulate condition of storage of the 3- methylthiopropionaldehyde in stainless steel, investigate and add different phenol, the result is that enabling
People's disappointment.
Phenolic antioxidant can not stablize 3- methylthiopropionaldehyde.Here with hydroquinone (HQ) and 4- guaiacol (PMP)
Experimental data illustrate that hydroquinone (HQ) and 4- guaiacol (PMP) be added separately to pure 3- methylthiopropionaldehyde by us
It in solution, and using pure 3- methylthiopropionaldehyde as canonical reference, is put into the storage tank of stainless steel, and observes them by one
Generated aldol(s) and dimer content after the section time, as a result as shown in Figure 1, it can be seen that phenol antioxidant is not
Stabilization can be generated to 3- methylthiopropionaldehyde.
Summary of the invention
Stability in storing to improve 3- methylthiopropionaldehyde after weight-removing column and rectifying, the invention discloses a kind of use
In the stabilizer that 3- methylthiopropionaldehyde is prepared and stored, which is monosaccharide or is disaccharides.
Monosaccharide refers to the carbohydrate that cannot be hydrolyzed again, is the basic unit for constituting the molecule of various disaccharides and polysaccharide.By carbon original
Subnumber mesh, monosaccharide can be divided into triose, tetrose, pentose, hexose etc..The monosaccharide of nature is mainly pentose and hexose.According to construction,
Monosaccharide can be divided into aldose and ketose again.Polyhydroxy aldehyde is known as aldose, and polyhydroxyketone is known as ketose.For example, glucose is aldohexose,
Fructose is ketohexose.There are also galactolipin, ribose and deoxyribose etc. for common monosaccharide.
Disaccharides also known as disaccharide are formed by dimolecular monosaccharide by glycosidic bond, in the reduction group of a kind of monosaccharide and another
In the case that the alcoholic extract hydroxyl group of kind sugar combines, the common chemical property with monosaccharide is shown, for example glucose-glucose；But it is logical
Monosaccharide that reduction base junction is closed is crossed then without this property, for example sucrose, trehalose.
Further, it is monosaccharide that the present invention, which discloses preferably stabilizer, wherein particularly preferably glucose and fructose.
It there is also a kind of form of sugar is polysaccharide in nature it is worth noting that be different from monosaccharide or disaccharides.Polysaccharide
With monosaccharide and disaccharides in terms of there are gross differences.Polysaccharide be by least ten more than identical monosaccharide or
Different monosaccharide compositions.According to whether be made of identical monosaccharide, polysaccharide can be divided into homopolysaccharide (such as starch, cellulose and
Glycogen) and heteroglycan (such as Arabic gum).Not a kind of pure chemical substance of polysaccharide, the different substance of extent of polymerization
Mixture.Polysaccharide also has material difference with monosaccharide and disaccharides in nature simultaneously, therefore polysaccharide is not suitable for the present invention
The stabilization of middle 3- methylthiopropionaldehyde.
It further, is 20 DEG C -150 DEG C invention additionally discloses the stabilization temperature of the stabilizer.
Meanwhile it is 200-1000ppm that the concentration of stabilizer, which is further disclosed, in we.
Disclosed technical solution through the invention, can stablize 3- methylthiopropionaldehyde significantly, especially pure in high temperature
Change in the storing process with the later period, so that degradation of the 3- methylthiopropionaldehyde in purifying and storage is avoided, effectively save DL-2- hydroxyl
The production cost of base -4- methylmercapto butyric acid and DL- METHIONINE improves production efficiency.
Detailed description of the invention
Fig. 1 is that pure 3- methylthiopropionaldehyde aldol condensation body and the overall of dimer content in the presence of phenol stabilizer become
Change；Wherein abscissa is number of days, and ordinate is containing for the aldol condensation body formed after 3- methylthiopropionaldehyde is rotten and dimer
It measures, the cylindricality in every group of data from left to right respectively represents: pure 3- methylthiopropionaldehyde, the 3- methyl mercapto added with 979ppm HQ
Propionic aldehyde solution, the 3- methylthiopropionaldehyde solution added with 1000ppm PMP.
Fig. 2 is that pure 3- methylthiopropionaldehyde aldol condensation body and the overall of dimer content in the presence of carbohydrate stabilizer become
Change；Wherein abscissa is number of days, and ordinate is containing for the aldol condensation body formed after 3- methylthiopropionaldehyde is rotten and dimer
It measures, the cylindricality in every group of data from left to right respectively represents: pure 3- methylthiopropionaldehyde, the 3- methyl mercapto added with 556ppm sucrose
Propionic aldehyde solution, the 3- methylthiopropionaldehyde solution added with 518ppm glucose, the 3- methylthiopropionaldehyde added with 942ppm fructose
Solution.
Fig. 3 is entire change of the industrial sugared agent solution as aldol condensation body and dimer content in the presence of stabilizer,
Middle abscissa is number of days, and ordinate is the content of the aldol condensation body and dimer that are formed after 3- methylthiopropionaldehyde is rotten, by
Respectively represent up to lower curve: pure 3- methylthiopropionaldehyde, 529ppm fructose (70% fructose of 750PPM), 489ppm glucose are poly-
Close object (80.7% glucose syrup of 600ppm) ,+0.93% water of 505ppm fructose (5.5% fructose of 9200ppm), the Portugal 510ppm
+ 0.89% water of grape glycopolymers (5.7% glucose syrup of 8800ppm).
Fig. 4 is that the static stabilization of phenol antioxidant and sugared agent in the 3- methylthiopropionaldehyde for removing over-head distillate is illustrated
Figure, abscissa are hour, and ordinate is the mass fraction of heavy constituent, and from top to bottom curve respectively represents: HQ, fructose, pure 3-
Methylthiopropionaldehyde and glucose.
Fig. 5 is the changes of contents schematic diagram of heavy constituent in the 3- methylthiopropionaldehyde for add different amounts of glucose, wherein horizontal
Coordinate is hour, and ordinate is attached most importance to component percentages, and from top to bottom curve respectively represents: pure 3- methylthiopropionaldehyde, pure 3- first
Sulfenyl propionic aldehyde+223ppm glucose syrup, pure 3- methylthiopropionaldehyde+526ppm glucose syrup, pure 3- methylthiopropionaldehyde+1012ppm
Glucose syrup.
Specific embodiment
In order to better understand the present invention, we in conjunction with specific embodiments further explain the present invention below
It states.
" heavy constituent " as used in the present invention refers to the higher compound of mixture mid-boiling point；
" light component " refers to the lower compound of mixture mid-boiling point.
Embodiment 1
Sucrose, glucose and fructose is selected to carry out the stability test about pure 3- methylthiopropionaldehyde in this example.
The 3- methylthiopropionaldehyde of sucrose, glucose and fructose is added in observation respectively, and is with pure 3- methylthiopropionaldehyde
Canonical reference is put into the storage tank of stainless steel, and observe they after a period of time has passed caused by aldol(s) with
Dimer content, as a result as shown in Figure 2.
We have seen that three kinds of sugared agents produce good stabilization effect compared to pure 3- methylthiopropionaldehyde.
Embodiment 2
We carry out the stability test about pure 3- methylthiopropionaldehyde to industrial sugared agent solution in this example.
We choose respectively:
70% fructose (dry substance=70%；Ingredient=+ 5% glucose of 95% fructose)
Glucose syrup (dry substance=81%；Ingredient=+ 19% trisaccharide of+44% disaccharides of 32% glucose)
And they are dissolved in the aqueous solution of form after water.
When using pure 3- methylthiopropionaldehyde as canonical reference, being put into the storage tank of stainless steel, and observing them by one section
Between after caused by aldol(s) and dimer content, as a result as shown in Figure 3.
We have seen that industrial sugared agent solution has apparent static stabilization for 3- methylthiopropionaldehyde.Meanwhile we also anticipate
Outer discovery water and sugared agent can generate synergistic effect.It is shown according to chart, even if after 3 days, at 50 DEG C, for being added to
The 3- methylthiopropionaldehyde of 500ppm fructose or glucose polymer and 8500ppm water, alcohol aldehyde+dimer content still almost do not have
There is increase.
And we further pass through the data counted in table 1 and are illustrated to its stabilizing effect:
Table 1:
| Stabilizer | T0 days alcohol aldehyde+dimer contents | Alcohol aldehyde+dimer content at t7 days, 50 DEG C | Multiplication coefficient |
| Without stabilizer | 0.04% | 1.9% | 47.5 |
| 70% fructose soln of 750ppm | 0.04% | 1.43% | 35 |
| 81% glucose polymer solution of 600ppm | 0.04% | 1.05% | 26 |
| 5.5% fructose soln of 9200ppm | 0.04% | 0.25% | 6.2 |
| 5.7% glucose polymer solution of 8800ppm | 0.04% | 0.12% | 3 |
In t=7 angel, we measure the pH value in each solution respectively, as a result, it has been found that the 3- methyl mercapto without stabilizer
The pH value of propionic aldehyde is lower than the pH value of the 3- methylthiopropionaldehyde added with stabilizing solutions.It the results are shown in Table 2.
Table 2:
As it can be seen that the raising of pH value has the stabilization using 3- methylthiopropionaldehyde.
Embodiment 3
We consider application conditions of the sugar as stabilizer in industrialized production below.
What it is firstly the need of explanation be the 3- methylthiopropionaldehyde that is prepared by methacrylaldehyde and MSH is thick 3- methyl mercapto third
Aldehyde, wherein containing the light components such as 3- methylthiopropionaldehyde and water and methanol.And pass through (light group of water and methanol etc. of over-head distillate of removal
Point) 3- methylthiopropionaldehyde (or be referred to as it is de- light after 3- methylthiopropionaldehyde) in contain heavy constituent (3- methylthiopropionaldehyde two
Aggressiveness and tripolymer) and crucial heavy constituent impurity methyl thio hemiacetal (HTA).
We investigate phenols (HQ, HQ/OH-TEMPO), fructose, glucose, sucrose to thick 3- methylthiopropionaldehyde respectively and remove
Remove the stability action of the 3- methylthiopropionaldehyde (the 3- methylthiopropionaldehyde after taking off gently) of over-head distillate.
The results show that several stabilizers of experiment do not generate static stabilization in thick 3- methylthiopropionaldehyde.
In the 3- methylthiopropionaldehyde (the 3- methylthiopropionaldehyde after taking off gently) of removal over-head distillate, the effect of various stabilizers is such as
Shown in Fig. 4.As can be seen that in rustless steel container, glucose can generate good static stabilization under conditions of 120 DEG C.
Therefore, after we have such conclusion, stabilizer disclosed in this invention to be suitable for use in removing over-head distillate
In 3- methylthiopropionaldehyde rectification step and subsequent storing step.This is a kind of good for the 3- methylthiopropionaldehyde after taking off gently
Good stabilizer, suitable for purification of the 3- methylthiopropionaldehyde weight-removing column.
Embodiment 4
When we consider Different adding amount below, sugared stability action.
(200,500 and 1000ppm) passes through addition industrial sugared agent solution (70% fructose and 81% under various concentration respectively
Glucose syrup) the 3- methylthiopropionaldehyde damage for removing over-head distillate is compared.Result such as Fig. 5 institute that every kind of solution obtains
Show.
According to Fig. 5, we can be informed in the concentration range of 200-1000ppm, and sugared agent can play 3- methylthiopropionaldehyde
To static stabilization.
Claims (6)
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|---|---|---|---|---|
| JPS60104058A (en) * | 1983-11-10 | 1985-06-08 | Nippon Soda Co Ltd | Stabilization of sulfur-containing aldehyde |
| CN1077708A (en) * | 1991-12-26 | 1993-10-27 | 罗迪亚有限公司 | The stable composition of the aldehyde that sulphur replaces, be used for stablizing the method for aldehyde and stable aldehyde |
| JPH10152466A (en) * | 1996-11-22 | 1998-06-09 | Sumitomo Chem Co Ltd | Method for storing methylthiopropionaldehyde in metal containers |
| JPH10152467A (en) * | 1996-11-22 | 1998-06-09 | Sumitomo Chem Co Ltd | Method for stabilizing methylthiopropionaldehyde |
| CN1210849A (en) * | 1997-08-14 | 1999-03-17 | 德古萨股份公司 | Aliphatic alkane aldehyde having better storage stability and method for raising storage stability |
| CN1553776A (en) * | 2001-09-13 | 2004-12-08 | DSM IP�ʲ�����˾ | Colorants for food and pharmaceuticals |
| CN102883614A (en) * | 2010-03-26 | 2013-01-16 | Mpt芥末产品和技术公司 | Composition comprising plant material and sugar for controlling pests and method for its preparation |
| CN103476747A (en) * | 2010-12-28 | 2013-12-25 | 赢创德固赛有限公司 | Process for preparing methylmercaptopropionaldehyde |
| CN104230771A (en) * | 2013-06-11 | 2014-12-24 | 赢创德固赛有限公司 | Method for the preparation of storage-stable 3-methylmercaptopropionaldehyde |
| CN105968034A (en) * | 2016-05-13 | 2016-09-28 | 山东新和成氨基酸有限公司 | Post-treatment method and post-treatment device for 3-methylthiopropanal reaction mixture |
-
2017
- 2017-12-22 CN CN201711404540.6A patent/CN107903197B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60104058A (en) * | 1983-11-10 | 1985-06-08 | Nippon Soda Co Ltd | Stabilization of sulfur-containing aldehyde |
| CN1077708A (en) * | 1991-12-26 | 1993-10-27 | 罗迪亚有限公司 | The stable composition of the aldehyde that sulphur replaces, be used for stablizing the method for aldehyde and stable aldehyde |
| JPH10152466A (en) * | 1996-11-22 | 1998-06-09 | Sumitomo Chem Co Ltd | Method for storing methylthiopropionaldehyde in metal containers |
| JPH10152467A (en) * | 1996-11-22 | 1998-06-09 | Sumitomo Chem Co Ltd | Method for stabilizing methylthiopropionaldehyde |
| CN1210849A (en) * | 1997-08-14 | 1999-03-17 | 德古萨股份公司 | Aliphatic alkane aldehyde having better storage stability and method for raising storage stability |
| CN1553776A (en) * | 2001-09-13 | 2004-12-08 | DSM IP�ʲ�����˾ | Colorants for food and pharmaceuticals |
| CN102883614A (en) * | 2010-03-26 | 2013-01-16 | Mpt芥末产品和技术公司 | Composition comprising plant material and sugar for controlling pests and method for its preparation |
| CN103476747A (en) * | 2010-12-28 | 2013-12-25 | 赢创德固赛有限公司 | Process for preparing methylmercaptopropionaldehyde |
| CN104230771A (en) * | 2013-06-11 | 2014-12-24 | 赢创德固赛有限公司 | Method for the preparation of storage-stable 3-methylmercaptopropionaldehyde |
| CN105968034A (en) * | 2016-05-13 | 2016-09-28 | 山东新和成氨基酸有限公司 | Post-treatment method and post-treatment device for 3-methylthiopropanal reaction mixture |
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