CN112321391B - Preparation method of meso-2, 3-butanediol - Google Patents
Preparation method of meso-2, 3-butanediol Download PDFInfo
- Publication number
- CN112321391B CN112321391B CN202110010289.5A CN202110010289A CN112321391B CN 112321391 B CN112321391 B CN 112321391B CN 202110010289 A CN202110010289 A CN 202110010289A CN 112321391 B CN112321391 B CN 112321391B
- Authority
- CN
- China
- Prior art keywords
- butanediol
- meso
- tower
- rectifying tower
- rectifying
- 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.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
- C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
- C12P7/18—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic polyhydric
Abstract
The invention discloses a preparation method of meso-2, 3-butanediol, which comprises the following steps: the method comprises the following steps of taking renewable biomass as a raw material, adopting Klebsiella to ferment and produce 2, 3-butanediol to obtain 2, 3-butanediol fermentation liquor, sequentially carrying out ultrafiltration, nanofiltration, electrodialysis and multi-effect evaporation, then adopting a first rectifying tower to carry out dehydration, distillation and rectification in a second rectifying tower, separating 3-hydroxy-2-butanone from the top of the tower, and extracting 2, 3-butanediol from the lateral line; rectifying the 2, 3-butanediol collected from the side line in a third rectifying tower to obtain meso-2, 3-butanediol collected from the side line, and adsorbing the meso-2, 3-butanediol collected from the side line by using activated carbon to obtain the compound; the purity of the meso-2, 3-butanediol prepared by the method can reach more than 90 percent, the chroma is less than or equal to 10 Hazeng, no peculiar smell exists, the excellent antibacterial and antiseptic capabilities are fully utilized, no stimulation is caused to skin and the like, and the quality requirements of daily chemicals and polymer-grade products are met.
Description
Technical Field
The invention belongs to the technical field of preparation of 2, 3-butanediol and stereoisomers thereof, and particularly relates to a preparation method of meso-2, 3-butanediol.
Background
Meso-2, 3-butanediol (Meso-2, 3-butanediol) is one of the stereoisomers of 2, 3-butanediol, and studies have been carried out to date to show that Meso-2, 3-butanediol has higher antibacterial and antiseptic abilities and is less irritating to the skin than the other stereoisomers of 2, 3-butanediol (L- (+) -2, 3-butanediol), D form (D- (-) -2, 3-butanediol), such as in patent CN 2015800553290; in fact, even the currently known preservatives such as paraben, imidazolidinyl urea, phenoxyethanol, chlorphenesin and the like can suppress and destroy microorganisms in the composition and improve the preservability of the product, but all of them cause skin irritation and allergy, and in the serious cases, cause skin toxicity; therefore, compared with the known antibacterial and antiseptic products, the meso-2, 3-butanediol has excellent application value in the aspects of antibiosis, antisepsis, daily chemical products and the like. However, the efficient preparation of meso-2, 3-butanediol has not been reported yet.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a novel method for efficiently preparing meso-2, 3-butanediol, the purity of the meso-2, 3-butanediol prepared by the method can reach more than 90 percent, the chroma is less than or equal to 10 Hazeng, no peculiar smell exists, the excellent antibacterial capability and the antiseptic capability of the meso-2, 3-butanediol can be fully utilized, no stimulation is caused to skin and the like, and the quality requirements of daily chemicals and polymerization-grade products can be completely met.
In order to achieve the purpose, the invention adopts the technical scheme that:
a process for the preparation of meso-2, 3-butanediol, said process comprising the steps of:
(1) renewable biomass is used as a raw material, and Klebsiella is adopted to produce 2, 3-butanediol by fermentation to obtain 2, 3-butanediol fermentation liquor;
(2) sequentially carrying out ultrafiltration for removing bacteria and protein, nanofiltration for removing protein and partial salt, electrodialysis for desalting and multi-effect evaporation for removing partial water on the 2, 3-butanediol fermentation liquor obtained in the step (1) to obtain concentrated solution;
(3) dehydrating the concentrated solution obtained in the step (2) by adopting a first rectifying tower to obtain dehydrated solution, and then distilling the dehydrated solution to obtain distillate;
(4) rectifying the distillate obtained in the step (3) in a second rectifying tower, separating 3-hydroxy-2-butanone from the top of the tower, and extracting 2, 3-butanediol with the purity of more than or equal to 99.5% from a side line;
(5) rectifying the 2, 3-butanediol extracted from the side line in the step (4) in a third rectifying tower, extracting L- (+) -2, 3-butanediol from the top of the tower, extracting meso-2, 3-butanediol from the side line, and then adsorbing the meso-2, 3-butanediol extracted from the side line by adopting activated carbon to prepare purified meso-2, 3-butanediol.
According to some preferred aspects of the present invention, in the step (2), the ultrafiltration is performed using a ceramic membrane having a filtration pore size of 5nm to 50 nm. More preferably, in step (2), the ultrafiltration is carried out by using a ceramic membrane, and the filtration pore diameter of the ceramic membrane is 5-20 nm.
According to some preferred aspects of the present invention, in the step (2), nanofiltration membrane used for nanofiltration has a molecular weight cut-off of 300D to 1000D. More preferably, in the step (2), the nanofiltration membrane used for nanofiltration has a molecular weight cut-off of 500D-1000D.
According to some preferred aspects of the present invention, in the step (2), the ion-exchange membrane used for the electrodialysis is a heterogeneous membrane or a semi-homogeneous membrane, and the conductivity of the desalted solution after the desalination by the electrodialysis is reduced to 2000 μ s/cm. More preferably, in step (2), the process parameters of electrodialysis are as follows: the adopted ion exchange membrane is a heterogeneous membrane, and the conductivity of the desalted liquid after electrodialysis desalination is reduced to 1500 mu s/cm.
According to some preferred aspects of the present invention, in the step (2), the multiple-effect evaporation is performed using a multiple-effect evaporator, which is a three-effect evaporator, a four-effect evaporator, a five-effect evaporator, a six-effect evaporator, a seven-effect evaporator, or the like, and is reduced-pressure evaporation. More preferably, in the step (2), the multiple-effect evaporation is performed by using a multiple-effect evaporator, and the process parameters of the multiple-effect evaporator are as follows: a three-effect evaporator or a four-effect evaporator is adopted, and the operating pressure of the last-effect evaporator is-0.093 to-0.099 MPa.
According to the invention, in step (2), the water content of the concentrated solution is less than or equal to 40%.
According to some preferred aspects of the present invention, in the step (3), the process parameters of the first rectifying tower are: the theoretical plate number of the rectifying tower is 10-50, the operation pressure at the top of the tower is 80-90mmHg, and the reflux ratio at the top of the tower is 0.5-1; more preferably, in the step (3), the process parameters of the first rectifying tower are as follows: the theoretical plate number of the rectifying tower is 30-45, the operation pressure at the top of the tower is 85-90mmHg, and the reflux ratio at the top of the tower is 0.8-1.
According to some preferred aspects of the present invention, in the step (3), the distillation is performed by using a distillation column, and the process parameters of the distillation column are as follows: the operation pressure at the top of the tower is 3-20 mmHg. More preferably, in the step (3), the distillation is performed by using a distillation tower, and the process parameters of the distillation tower are as follows: the operation pressure at the top of the tower is 5-10 mmHg.
According to the present invention, in the step (3), the moisture content of the dehydrating liquid is 0.5% or less.
According to some preferred aspects of the present invention, in the step (4), the process parameters of the second rectification column are: the theoretical plate number of the rectifying tower is 10-100, the operation pressure at the top of the tower is 5-30mmHg, and the reflux ratio is 0.5-10. More preferably, in the step (4), the process parameters of the second rectifying tower are as follows: the theoretical plate number of the rectifying tower is 30-50, the operation pressure at the top of the tower is 10-20mmHg, and the reflux ratio is 2-5.
According to some preferred aspects of the present invention, in the step (5), the process parameters of the third rectifying tower are: the theoretical plate number of the rectifying tower is 25-100, the operation pressure at the top of the tower is 5-30mmHg, and the reflux ratio is 3-30. More preferably, in the step (5), the process parameters of the third rectifying tower are as follows: the theoretical plate number of the rectifying tower is 40-60, the operation pressure at the top of the tower is 5-20mmHg, and the reflux ratio is 6-25.
According to the invention, in the step (5), the preparation method further comprises the step of adsorbing the L- (+) -2, 3-butanediol extracted from the tower top by using activated carbon to obtain the purified L- (+) -2, 3-butanediol, wherein the purity is more than or equal to 51%, the chroma is less than or equal to 10 Hazeng, and no peculiar smell is generated.
According to the invention, in step (5), the purified meso-2, 3-butanediol has a purity of 90% or more, a chroma of 10% or less and no off-taste.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
the invention provides a novel high-efficiency preparation method aiming at meso-2, 3-butanediol, which is based on the factor which is discovered by the inventor and influences the fragrance and color of a 2, 3-butanediol product, namely, trace 3-hydroxy-2-butanone contained in the product, and the conventional detection method such as liquid chromatography is adopted, so that the 3-hydroxy-2-butanone is difficult to detect due to extremely low content, and the peculiar smell and the color always influence the quality of the 2, 3-butanediol; meanwhile, as the boiling points of three isomers of the 2, 3-butanediol are very close and difficult to separate, the boiling point of the 3-hydroxy-2-butanone is about 30 ℃ lower than that of 3 stereoisomers of the 2, 3-butanediol, the invention adopts the rectification operation, the 3-hydroxy-2-butanone with lower boiling point is extracted from the top of the tower by rectification, the 2, 3-butanediol with 3-hydroxy-2-butanone basically eliminated is extracted at the side line, the 2, 3-butanediol extracted at the side line can be extracted at the side line by a third rectifying tower to obtain a meso-2, 3-butanediol product as the main component, and further the active carbon is combined for adsorption, decoloration and deodorization, thereby not only eliminating the factors influencing the fragrance and the color of the 2, 3-butanediol product, but also efficiently preparing the high-purity meso-2, the 3-butanediol lays a foundation for the application of the meso-2, 3-butanediol in the fields of daily chemical products with high standard requirements on antibiosis, antisepsis, low skin irritation and the like, and has lower cost compared with other antiseptics sold in the market at present.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise.
FIG. 1 is a schematic diagram of a process flow for the preparation of meso-2, 3-butanediol according to an embodiment of the present invention;
wherein, 1, a fermentation device; 2. 2, 3-butanediol fermentation broth; 3. an ultrafiltration device; 4. ultrafiltering the filtrate; 5. a nanofiltration device; 6. nano-filtering the filtrate; 7. an electrodialysis unit; 8. electrodialysis desalination liquid; 9. a multi-effect evaporator; 10. concentrating the solution; 11. a first rectification column; 12. dehydrating liquid; 13. a distillation column; 14. distilling the liquid; 15. a second rectification column; 16. a light component comprising 3-hydroxy-2-butanone; 17. 2, 3-butanediol; 18. a third rectifying column; 19. the tower top extract of the third rectifying tower; 20. 2, 3-butanediol rich in meso-2, 3-butanediol; 21. a first activated carbon particle adsorption decolorization system; 22. meso-2, 3-butanediol; 23. a second activated carbon particle adsorption decolorization system; 24. l- (+) -2, 3-butanediol.
Detailed Description
At present, the advantages of meso-2, 3-butanediol in terms of antibacterial ability, antiseptic ability and low irritation to the skin have been found and confirmed, but the prior art has not been fully studied for the efficient preparation of meso-2, 3-butanediol, the conventional method being the direct separation from 2, 3-butanediol. The 2, 3-butanediol has 3 stereoisomers, namely L-type (L- (+) -2, 3-butanediol), D-type (D- (-) -2, 3-butanediol) and Meso-type (Meso-2, 3-butanediol), and the basic characteristics of the three isomers are shown in Table 1.
As is clear from Table 1, the boiling points of the L-form (L- (+) -2, 3-butanediol), the D-form (D- (-) -2, 3-butanediol) and the Meso-form (Meso-2, 3-butanediol) were very close to each other, and separation was difficult.
There are currently two methods for producing 2, 3-butanediol: chemical processes (traditional chemical industry) and biological fermentation processes (biorefinery). The chemical method has complex production process, harsh process conditions, complex operation, high requirements on equipment and high cost, and industrial large-scale production is difficult to realize all the time. The biological fermentation method takes microorganisms as a production tool and renewable biomass as a raw material to produce 2, 3-butanediol in a fermentation tank; common bacteria include Enterobacter (Enterobacter), Klebsiella (Klebsiella), Bacillus (Bacillus), Paenibacillus (Paenibacillus), Serratia (Serratia), etc., and various strains have differences in various factors for the fermentative synthesis of 2, 3-butanediol. The Klebsiella is considered to have the most industrial application prospect, because the culture condition is relatively simple, the fermentation substrate spectrum is wide, 2, 3-butanediol produced by fermentation is mainly in a racemic form, accounting for 65% -95%, and a small amount of L-form accounts for 5% -35%, but the biggest problem is that the product is difficult to separate and purify, the 2, 3-butanediol in the fermentation liquor is difficult to purify to the purity of more than 99.5%, and the separation of the 2, 3-butanediol mixed isomer into a higher-value single isomer (meso form or L-form) is more difficult. This limits the market for 2, 3-butanediol, particularly the use of meso-2, 3-butanediol; meanwhile, peculiar smell exists in the prepared 2, 3-butanediol product for a long time, the peculiar smell can not be completely removed by adopting activated carbon adsorption, the practical application of the product is seriously influenced, and the problem of yellowing of the product color is also accompanied in the practical storage process.
The research of the inventor of the application shows that in the process of producing 2, 3-butanediol by a fermentation method, 3-hydroxy-2-butanone is a metabolic precursor of the 2, 3-butanediol, the 3-hydroxy-2-butanone produces the 2, 3-butanediol under the catalysis of reductase, and after the fermentation is finished, a certain amount of 3-hydroxy-2-butanone remains in the fermentation broth, but the content of the 3-hydroxy-2-butanone in the fermentation broth is trace, and the detection cannot be carried out even by adopting liquid chromatography detection. The 3-hydroxy-2-butanone is an edible spice, so that even if the 2, 3-butanediol only contains a trace amount of 3-hydroxy-2-butanone, the odor of the 2, 3-butanediol product can be influenced, and diacetyl generated after the 3-hydroxy-2-butanone is oxidized is a yellow substance, and the yellowing of the color and luster of the product in the storage process is caused by the existence of the trace amount of diacetyl in the product.
Based on the above findings, the present invention provides a method for producing meso-2, 3-butanediol, comprising the steps of:
(1) renewable biomass is used as a raw material, and Klebsiella is adopted to produce 2, 3-butanediol by fermentation to obtain 2, 3-butanediol fermentation liquor;
(2) sequentially carrying out ultrafiltration for removing bacteria and protein, nanofiltration for removing protein and partial salt, electrodialysis for desalting and multi-effect evaporation for removing partial water on the 2, 3-butanediol fermentation liquor obtained in the step (1) to obtain concentrated solution;
(3) dehydrating the concentrated solution obtained in the step (2) by adopting a first rectifying tower to obtain dehydrated solution, and then distilling the dehydrated solution to obtain distillate;
(4) rectifying the distillate obtained in the step (3) in a second rectifying tower, separating 3-hydroxy-2-butanone from the top of the tower, and extracting 2, 3-butanediol with the purity of more than or equal to 99.5% from a side line;
(5) rectifying the 2, 3-butanediol extracted from the side line in the step (4) in a third rectifying tower, extracting L- (+) -2, 3-butanediol from the top of the tower, extracting meso-2, 3-butanediol from the side line, and then adsorbing the meso-2, 3-butanediol extracted from the side line by adopting activated carbon to prepare purified meso-2, 3-butanediol.
In the method for preparing meso-2, 3-butanediol, the 2, 3-butanediol is produced by fermenting the klebsiella to obtain 2, 3-butanediol raw material containing the meso-2, 3-butanediol as much as possible, and meanwhile, the rectification and the activated carbon adsorption are combined, but the rectification is not adopted when the mixture with approximate boiling point is separated; however, based on the findings of the inventor, 3-hydroxy-2-butanone needs to be separated, the boiling point of 3-hydroxy-2-butanone is about 30 ℃ lower than the boiling points of 3 stereoisomers of 2, 3-butanediol, and the invention adopts a rectification operation, the lower boiling 3-hydroxy-2-butanone is extracted from the top of the tower through rectification, 2, 3-butanediol with 3-hydroxy-2-butanone basically eliminated is extracted from the side line, and the 2, 3-butanediol extracted from the side line can be respectively prepared into a product with the main component of L- (+) -2, 3-butanediol and a product with the main component of meso-2, 3-butanediol through a third rectification tower; the two products are further adsorbed by active carbon respectively to remove trace impurities, pigments and odor.
Practice proves that the purity of 2, 3-butanediol prepared by adsorbing a side-line extract by using granular activated carbon is more than or equal to 99.5 percent, the internal-rotation-2, 3-butanediol accounts for more than or equal to 90 percent, the chroma is less than or equal to 10 Hazeng, and no peculiar smell exists, namely, the method can completely obtain an internal-rotation-2, 3-butanediol product with the purity of more than or equal to 90 percent, can completely meet the quality requirements of polymerization-grade and daily chemical-grade products, fills the gap of the prior method for efficiently preparing the internal-rotation-2, 3-butanediol, further can fully utilize the advantages of the internal-rotation-2, 3-butanediol in the aspects of antibiosis, anticorrosion, low irritation to skin and the like, and has excellent practical significance.
And the purity of the 2, 3-butanediol prepared by absorbing the extract at the top of the tower by active carbon is more than or equal to 99.5 percent, the ratio of the L- (+) -2, 3-butanediol is more than or equal to 51 percent, the chroma is less than or equal to 10 Hazeng, no peculiar smell exists, and the quality requirement of a polymerization-grade product can be completely met.
Further, in step (1), the renewable biomass is a renewable biological raw material conventional in the art, and specifically may be glycerol and the like.
Further, in the step (1), the method for producing 2, 3-butanediol by using the fermentation of the Klebsiella as the raw material is a conventional method in the field. In the present invention, preferably, the specific embodiments are as follows: after inoculation of a fermentation tank, controlling the temperature of fermentation liquor to be 30-40 ℃, the pH value to be 6-7, the ventilation volume to be 0.01-0.5vvm, the stirring speed to be 20-100rpm, measuring the substrate glycerol concentration in the fermentation liquor in the fermentation process, adding glycerol according to the glycerol consumption rate to ensure that the glycerol concentration in the fermentation liquor is 0.5-30g/L, and discharging the fermentation liquor after 30-60 hours of fermentation.
Further, in the step (2), ultrafiltration is carried out by adopting a ceramic membrane, and the filtering aperture of the ceramic membrane is 5-20 nm.
Further, in the step (2), the nanofiltration membrane adopted for nanofiltration has the molecular weight cutoff of 500-1000D.
Further, in the step (2), the process parameters of the electrodialysis are as follows: the adopted ion exchange membrane is a heterogeneous membrane, and the conductivity of the desalted liquid after electrodialysis desalination is reduced to 1500 mu s/cm.
Further, in the step (2), multiple-effect evaporation is performed by using a multiple-effect evaporator, and the process parameters of the multiple-effect evaporator are as follows: a three-effect evaporator or a four-effect evaporator is adopted, and the operating pressure of a last-effect evaporator is-0.093 to-0.099 MPa.
According to the invention, in step (2), the water content of the concentrated solution can reach less than or equal to 40%.
Further, in the step (3), the process parameters of the first rectifying tower are as follows: the theoretical plate number of the rectifying tower is 30-45, the operation pressure at the top of the tower is 85-90mmHg, and the reflux ratio at the top of the tower is 0.8-1.
Further, in the step (3), distillation is carried out by using a distillation tower, and the process parameters of the distillation tower are as follows: the operation pressure at the top of the tower is 5-10 mmHg.
According to the present invention, in the step (3), the moisture content of the dehydrating liquid may be 0.5% or less.
Further, in the step (4), the process parameters of the second rectifying tower are as follows: the theoretical plate number of the rectifying tower is 30-50, the operation pressure at the top of the tower is 10-20mmHg, and the reflux ratio is 2-5.
Further, in the step (5), the process parameters of the third rectifying tower are as follows: the theoretical plate number of the rectifying tower is 40-60, the operation pressure at the top of the tower is 10-20mmHg, and the reflux ratio is 6-25.
Preferably, the method for preparing meso-2, 3-butanediol of the present invention employs a preparation process, as shown in fig. 1, 2, 3-butanediol fermentation broth 2 produced by the fermentation apparatus 1 → ultrafiltration filtrate 4 produced by the ultrafiltration apparatus 3 → nanofiltration filtrate 6 produced by the nanofiltration apparatus 5 → electrodialysis desalination and formation of electrodialysis desalination and desalination liquid 8 in the electrodialysis apparatus 7 → multi-effect evaporation in the multi-effect evaporator 9 to form concentrated liquid 10 → distillation and dehydration to form dehydrated liquid 12 in the first distillation column 11 → distillation and purification to remove heavy components and to form distilled liquid 14 in the distillation column 13 → distillation and side-draw 2, 3-butanediol 17 in the second distillation column 15 → distillation and side-draw 2, 3-butanediol-rich 2, 3-butanediol 20 → side-draw and side-draw 2, 3-butanediol-rich 2, 3-butanediol by the first activated carbon particle adsorption and decolorization system 21 for adsorption and decolorization to prepare further purified meso- 22, 3-butanediol; the overhead extract 19 of the third rectifying tower 18 mainly comprises L- (+) -2, 3-butanediol → purified L- (+) -2, 3-butanediol 24 is obtained by adsorption and decoloration through a second activated carbon particle adsorption and decoloration system 23; wherein a light fraction 16 containing 3-hydroxy-2-butanone is refined and separated from the top of the column in a second rectification column 15.
The above-described scheme is further illustrated below with reference to specific examples; it is to be understood that these embodiments are provided to illustrate the general principles, essential features and advantages of the present invention, and the present invention is not limited in scope by the following embodiments; the implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not indicated are generally the conditions in routine experiments. In the following, all starting materials are either commercially available or prepared according to methods conventional in the art, unless otherwise indicated.
Example 1
This example provides a process for the preparation of meso-2, 3-butanediol, said process comprising the steps of:
(1) renewable biomass (specifically glycerol) is used as a raw material, and Klebsiella fermentation is adopted to produce 2, 3-butanediol so as to obtain 2, 3-butanediol fermentation liquor; the specific implementation mode is as follows:
after inoculation of a fermentation tank, controlling the temperature of the fermentation liquid at 37 ℃, the pH value at 6.5, the ventilation volume at 0.08vvm and the stirring speed at 50rpm, measuring the concentration of substrate glycerol in the fermentation liquid in the fermentation process, feeding glycerol according to the glycerol consumption rate to ensure that the concentration of the glycerol in the fermentation liquid is 0.5-30g/L, and discharging the fermentation liquid after fermentation for 48 hours;
(2) sequentially carrying out the following steps on the 2, 3-butanediol fermentation liquor obtained in the step (1):
performing ultrafiltration for removing bacteria and protein to obtain ultrafiltration filtrate, wherein the ultrafiltration is performed by adopting a ceramic membrane (the filtration pore diameter of the ceramic membrane is 5 nm);
the nano-filtration membrane is used for removing protein and part of salt to obtain nano-filtration filtrate, and the nano-filtration membrane adopted in the nano-filtration is MWCO 500-1000;
electrodialysis for desalting to obtain electrodialysis desalted liquid, wherein the process parameters of the electrodialysis are as follows: the adopted ion exchange membrane is a heterogeneous membrane, and the conductivity of the desalted liquid after electrodialysis desalination is reduced to 1500 mu s/cm;
multiple-effect evaporation for removing part of water to obtain concentrated solution; the multi-effect evaporation is carried out by adopting a multi-effect evaporator, and the technological parameters of the multi-effect evaporator are as follows: the four-effect evaporator has the operation pressure of-0.096 MPa at the end effect;
(3) dehydrating the concentrated solution obtained in the step (2) by adopting a first rectifying tower to obtain dehydrated solution, and then distilling the dehydrated solution to obtain distillate;
wherein, the technological parameters of the first rectifying tower are as follows: the operation pressure at the top of the tower is 90mmHg, and the reflux ratio at the top of the tower is 1;
the distillation is carried out by adopting a distillation tower, and the technological parameters of the distillation tower are as follows: the operating pressure at the top of the distillation column was 10 mmHg;
(4) rectifying the distillate obtained in the step (3) in a second rectifying tower, separating a light component containing 3-hydroxy-2-butanone from the top of the tower, and extracting 2, 3-butanediol with the purity of more than or equal to 99.5% from a side line;
wherein the technological parameters of the second rectifying tower are as follows: the operation pressure at the top of the tower is 19mmHg, and the reflux ratio is 3;
(5) rectifying the 2, 3-butanediol extracted from the side line in the step (4) in a third rectifying tower, extracting L- (+) -2, 3-butanediol from the top of the tower, extracting meso-2, 3-butanediol from the side line, and then adsorbing the meso-2, 3-butanediol extracted from the side line by adopting activated carbon to prepare purified meso-2, 3-butanediol;
wherein the technological parameters of the third rectifying tower are as follows: the pressure at the top of the column was 5mmHg and the reflux ratio was 10.
The experimental data for this example are shown in Table 2.
As can be seen from Table 2, in the final product meso-2, 3-butanediol produced in this example, the purity of 2, 3-butanediol was 99.5%, the content of meso-2, 3-butanediol was 90%, the color number was 5 Blues, and no odor was observed.
In the final product L- (+) -2, 3-butanediol, the purity of 2, 3-butanediol is 99.5%, the content of L- (+) -2, 3-butanediol is 55%, the chroma is 5 Blacker, and no peculiar smell is produced.
Example 2
This example provides a process for the preparation of meso-2, 3-butanediol, said process comprising the steps of:
(1) renewable biomass (specifically glycerol) is used as a raw material, and Klebsiella fermentation is adopted to produce 2, 3-butanediol so as to obtain 2, 3-butanediol fermentation liquor; the specific implementation mode is as follows:
after inoculation of a fermentation tank, controlling the temperature of the fermentation liquid at 37 ℃, the pH value at 6.5, the ventilation volume at 0.08vvm and the stirring speed at 50rpm, measuring the concentration of substrate glycerol in the fermentation liquid in the fermentation process, feeding glycerol according to the glycerol consumption rate to ensure that the concentration of the glycerol in the fermentation liquid is 0.5-30g/L, and discharging the fermentation liquid after fermentation for 48 hours;
(2) sequentially carrying out the following steps on the 2, 3-butanediol fermentation liquor obtained in the step (1):
performing ultrafiltration for removing bacteria and protein to obtain ultrafiltration filtrate, wherein the ultrafiltration is performed by adopting a ceramic membrane (the filtration pore diameter of the ceramic membrane is 5 nm);
the nano-filtration membrane is used for removing protein and part of salt to obtain nano-filtration filtrate, and the nano-filtration membrane adopted in the nano-filtration is MWCO 500-1000;
electrodialysis for desalting to obtain electrodialysis desalted liquid, wherein the process parameters of the electrodialysis are as follows: the adopted ion exchange membrane is a heterogeneous membrane, and the conductivity of the desalted liquid after electrodialysis desalination is reduced to 1500 mu s/cm;
multiple-effect evaporation for removing part of water to obtain concentrated solution; the multi-effect evaporation is carried out by adopting a multi-effect evaporator, and the technological parameters of the multi-effect evaporator are as follows: the four-effect evaporator has the operation pressure of-0.097 MPa at the end effect;
(3) dehydrating the concentrated solution obtained in the step (2) by adopting a first rectifying tower to obtain dehydrated solution, and then distilling the dehydrated solution to obtain distillate;
wherein, the technological parameters of the first rectifying tower are as follows: the operation pressure at the top of the tower is 90mmHg, and the reflux ratio at the top of the tower is 1;
the distillation is carried out by adopting a distillation tower, and the technological parameters of the distillation tower are as follows: the operating pressure at the top of the distillation column was 10 mmHg;
(4) rectifying the distillate obtained in the step (3) in a second rectifying tower, separating a light component containing 3-hydroxy-2-butanone from the top of the tower, and extracting 2, 3-butanediol with the purity of more than or equal to 99.5% from a side line;
wherein the technological parameters of the second rectifying tower are as follows: the operation pressure at the top of the tower is 19mmHg, and the reflux ratio is 3;
(5) rectifying the 2, 3-butanediol extracted from the side line in the step (4) in a third rectifying tower, extracting L- (+) -2, 3-butanediol from the top of the tower, extracting meso-2, 3-butanediol from the side line, and then adsorbing the meso-2, 3-butanediol extracted from the side line by adopting activated carbon to prepare purified meso-2, 3-butanediol;
wherein the technological parameters of the third rectifying tower are as follows: the pressure at the top of the column was 5mmHg and the reflux ratio was 24.
The experimental data for this example are shown in Table 3.
As can be seen from Table 3, in the final product meso-2, 3-butanediol produced in this example, the purity of 2, 3-butanediol was 99.7%, the content of meso-2, 3-butanediol was 95%, the chroma was 5 Blues, and no off-flavor was observed.
In the final product L- (+) -2, 3-butanediol, the purity of 2, 3-butanediol is 99.7%, the content of L- (+) -2, 3-butanediol is 50%, the chroma is 5 Blacker, and no peculiar smell is produced.
Example 3
This example provides a process for the preparation of meso-2, 3-butanediol, said process comprising the steps of:
(1) renewable biomass (specifically glycerol) is used as a raw material, and Klebsiella fermentation is adopted to produce 2, 3-butanediol so as to obtain 2, 3-butanediol fermentation liquor; the specific implementation mode is as follows:
after inoculation of a fermentation tank, controlling the temperature of the fermentation liquid at 37 ℃, the pH value at 6.5, the ventilation volume at 0.08vvm and the stirring speed at 50rpm, measuring the concentration of substrate glycerol in the fermentation liquid in the fermentation process, feeding glycerol according to the glycerol consumption rate to ensure that the concentration of the glycerol in the fermentation liquid is 0.5-30g/L, and discharging the fermentation liquid after fermentation for 48 hours;
(2) sequentially carrying out the following steps on the 2, 3-butanediol fermentation liquor obtained in the step (1):
performing ultrafiltration for removing bacteria and protein to obtain ultrafiltration filtrate, wherein the ultrafiltration is performed by adopting a ceramic membrane (the filtration pore diameter of the ceramic membrane is 5 nm);
the nano-filtration membrane is used for removing protein and part of salt to obtain nano-filtration filtrate, and the nano-filtration membrane adopted in the nano-filtration is MWCO 500-1000;
electrodialysis for desalting to obtain electrodialysis desalted liquid, wherein the process parameters of the electrodialysis are as follows: the adopted ion exchange membrane is a heterogeneous membrane, and the conductivity of the desalted liquid after electrodialysis desalination is reduced to 1500 mu s/cm;
multiple-effect evaporation for removing part of water to obtain concentrated solution; the multi-effect evaporation is carried out by adopting a multi-effect evaporator, and the technological parameters of the multi-effect evaporator are as follows: the four-effect evaporator has the operation pressure of-0.097 MPa at the end effect;
(3) dehydrating the concentrated solution obtained in the step (2) by adopting a first rectifying tower to obtain dehydrated solution, and then distilling the dehydrated solution to obtain distillate;
wherein, the technological parameters of the first rectifying tower are as follows: the operation pressure at the top of the tower is 90mmHg, and the reflux ratio at the top of the tower is 1;
the distillation is carried out by adopting a distillation tower, and the technological parameters of the distillation tower are as follows: the operating pressure at the top of the distillation column was 10 mmHg;
(4) rectifying the distillate obtained in the step (3) in a second rectifying tower, separating a light component containing 3-hydroxy-2-butanone from the top of the tower, and extracting 2, 3-butanediol with the purity of more than or equal to 99.5% from a side line;
wherein the technological parameters of the second rectifying tower are as follows: the operation pressure at the top of the tower is 19mmHg, and the reflux ratio is 3;
(5) rectifying the 2, 3-butanediol extracted from the side line in the step (4) in a third rectifying tower, extracting L- (+) -2, 3-butanediol from the top of the tower, extracting meso-2, 3-butanediol from the side line, and then adsorbing the meso-2, 3-butanediol extracted from the side line by adopting activated carbon to prepare purified meso-2, 3-butanediol;
wherein the technological parameters of the third rectifying tower are as follows: the pressure at the top of the column was 5mmHg and the reflux ratio was 20.
The experimental data for this example are shown in Table 4.
As can be seen from Table 4, in the final product meso-2, 3-butanediol produced in this example, the purity of 2, 3-butanediol was 99.6%, the content of meso-2, 3-butanediol was 92%, the chroma was 5 Blues, and no off-flavor was observed.
In the final product L- (+) -2, 3-butanediol, the purity of 2, 3-butanediol is 99.6%, the content of L- (+) -2, 3-butanediol is 52%, the chroma is 5 Blacker, and no peculiar smell is produced.
In the above examples, the experimental data of tables 2 to 4 were measured by liquid chromatography or gas chromatography, respectively.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (8)
1. A preparation method of meso-2, 3-butanediol, which is characterized by comprising the following steps:
(1) renewable biomass is used as a raw material, and Klebsiella is adopted to produce 2, 3-butanediol by fermentation to obtain 2, 3-butanediol fermentation liquor;
(2) sequentially carrying out ultrafiltration for removing bacteria and protein, nanofiltration for removing protein and partial salt, electrodialysis for desalting and multi-effect evaporation for removing partial water on the 2, 3-butanediol fermentation liquor obtained in the step (1) to obtain concentrated solution;
(3) dehydrating the concentrated solution obtained in the step (2) by adopting a first rectifying tower to obtain dehydrated solution, and then distilling the dehydrated solution to obtain distillate; the technological parameters of the first rectifying tower are as follows: the theoretical plate number of the rectifying tower is 10-50, the operation pressure at the top of the tower is 80-90mmHg, and the reflux ratio at the top of the tower is 0.5-1;
(4) rectifying the distillate obtained in the step (3) in a second rectifying tower, separating 3-hydroxy-2-butanone from the top of the tower, and extracting 2, 3-butanediol with the purity of more than or equal to 99.5% from a side line; the technological parameters of the second rectifying tower are as follows: the theoretical plate number of the rectifying tower is 10-100, the operation pressure at the top of the tower is 5-30mmHg, and the reflux ratio is 0.5-10;
(5) rectifying the 2, 3-butanediol extracted from the side line in the step (4) in a third rectifying tower, extracting L- (+) -2, 3-butanediol from the top of the tower, extracting meso-2, 3-butanediol from the side line, and then adsorbing the meso-2, 3-butanediol extracted from the side line by adopting activated carbon to prepare purified meso-2, 3-butanediol; the technological parameters of the third rectifying tower are as follows: the theoretical plate number of the rectifying tower is 25-100, the operation pressure at the top of the tower is 5-30mmHg, and the reflux ratio is 3-30.
2. The method for producing meso-2, 3-butanediol as defined in claim 1, wherein in the step (2), the ultrafiltration is carried out using a ceramic membrane having a filtration pore size of 5nm to 50 nm; and/or in the step (2), the molecular weight cut-off of the nanofiltration membrane adopted in nanofiltration is 300D-1000D.
3. The method for producing meso-2, 3-butanediol as defined in claim 1, wherein in the step (2), the ion-exchange membrane used in the electrodialysis is a heterogeneous membrane or a semi-homogeneous membrane, and the conductivity of the desalted solution after the desalting by the electrodialysis is reduced to 2000 μ s/cm; and/or in the step (2), performing multiple-effect evaporation by using a multiple-effect evaporator, wherein the multiple-effect evaporator is a three-effect evaporator, a four-effect evaporator, a five-effect evaporator, a six-effect evaporator or a seven-effect evaporator and is pressure-reducing evaporation.
4. The process for producing meso-2, 3-butanediol as claimed in claim 1, wherein the water content of the concentrate in the step (2) is 40% or less.
5. The process for producing meso-2, 3-butanediol as defined in claim 1, wherein in the step (3), the distillation is carried out using a distillation column having process parameters of: the operation pressure at the top of the tower is 3-20 mmHg.
6. The process for producing meso-2, 3-butanediol as defined in claim 1, wherein in the step (3), the moisture content of the dehydrated liquid is 0.5% or less.
7. The method of producing meso-2, 3-butanediol as defined in claim 1, wherein in the step (5), the method further comprises adsorbing L- (+) -2, 3-butanediol withdrawn from the top of the column with activated carbon to obtain purified L- (+) -2, 3-butanediol having a purity of 51% or more and a chroma of 10 or less, and having no off-flavor.
8. The process for producing meso-2, 3-butanediol as claimed in claim 1, wherein in the step (5), the purity of the purified meso-2, 3-butanediol is 90% or more, and the chroma is 10% or less, and there is no off-flavor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110010289.5A CN112321391B (en) | 2021-01-06 | 2021-01-06 | Preparation method of meso-2, 3-butanediol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110010289.5A CN112321391B (en) | 2021-01-06 | 2021-01-06 | Preparation method of meso-2, 3-butanediol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112321391A CN112321391A (en) | 2021-02-05 |
| CN112321391B true CN112321391B (en) | 2021-04-06 |
Family
ID=74302440
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110010289.5A Active CN112321391B (en) | 2021-01-06 | 2021-01-06 | Preparation method of meso-2, 3-butanediol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112321391B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113337548B (en) * | 2021-08-02 | 2022-03-22 | 苏州苏震生物工程有限公司 | Preparation method of bio-based 1, 3-propylene glycol |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102459138A (en) * | 2009-06-04 | 2012-05-16 | 基因组股份公司 | Process of separating components of a fermentation broth |
| CN103740771A (en) * | 2014-02-10 | 2014-04-23 | 中国科学院上海高等研究院 | Method for producing 2R,3R-butanediol by utilizing Klebsiella pneumoniae |
| CN105585432A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司大连石油化工研究院 | Method for separating and extracting 2,3-butanediol from fermentation broth |
| CN105622342A (en) * | 2014-11-03 | 2016-06-01 | 中国石油化工股份有限公司 | Method for separating 2,3-butanediol |
-
2021
- 2021-01-06 CN CN202110010289.5A patent/CN112321391B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102459138A (en) * | 2009-06-04 | 2012-05-16 | 基因组股份公司 | Process of separating components of a fermentation broth |
| CN103740771A (en) * | 2014-02-10 | 2014-04-23 | 中国科学院上海高等研究院 | Method for producing 2R,3R-butanediol by utilizing Klebsiella pneumoniae |
| CN105585432A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司大连石油化工研究院 | Method for separating and extracting 2,3-butanediol from fermentation broth |
| CN105622342A (en) * | 2014-11-03 | 2016-06-01 | 中国石油化工股份有限公司 | Method for separating 2,3-butanediol |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112321391A (en) | 2021-02-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102732589A (en) | Method for treating threonine mother liquor | |
| CN100339364C (en) | Method for extracting natural taurine from octopus residue using membrane separation technology | |
| CN109294893B (en) | Resource utilization system and method for white spirit brewing byproduct yellow water | |
| WO2023010982A1 (en) | Preparation method for bio-based 1,3-propanediol | |
| CN112321391B (en) | Preparation method of meso-2, 3-butanediol | |
| US20230357805A1 (en) | Methods for co-producing erythritol and arabinose by using xylose mother liquor | |
| CN112125941A (en) | Preparation method of high-purity zhongshengmycin mother medicine | |
| CN105017360A (en) | Vitamin B12 preparation method | |
| CN102557970B (en) | Preparation method of anhydrous betaine | |
| CN110759959B (en) | Vitamin B is separated and extracted from fermentation liquor 12 Method (2) | |
| KR101198746B1 (en) | Method for preparing fermented liquor containing natural GABA and the fermented liquor made thereof | |
| CN105837488B (en) | A kind of hydroxyproline fermentation manufacturing technique | |
| KR20130057540A (en) | Methods for purifying lactic acid | |
| CN107083407B (en) | Preparation, separation, impurity removal and purification method of L-malic acid | |
| CN109517858A (en) | A method of production and extraction L-Trp | |
| CN105439847A (en) | Separation purification method for natural abscisic acid | |
| JP7324478B2 (en) | Method for preparing meso-2,3-butanediol | |
| CN103695490A (en) | High-purity arginine production process | |
| CN103450295A (en) | Method for purifying gentamicin sulphate | |
| CN110885866B (en) | Novel glutamic acid fermentation and monosodium glutamate production method | |
| CN100509757C (en) | Purification method of *N-L-arginine | |
| CN111732502A (en) | Method for separating malic acid from succinic acid | |
| WO2020103937A1 (en) | Method for producing bacteriocin and propanoic acid based on xylose mother liquor raffinate | |
| EP4223380A1 (en) | System for producing industrial proteins using carbon-containing industrial gases | |
| CN219670514U (en) | Gallic acid extraction and concentration device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |