CN105254486B - A kind of D lactic acid decoloration process - Google Patents
A kind of D lactic acid decoloration process Download PDFInfo
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Abstract
A kind of D lactic acid decoloration process, temperature raising is passed through air after D lactic fermentation cultures terminate carries out after-ripening, after the completion of after-ripening, quick temperature raising is carried out under a certain pressure after D lactic fermentation liquids are adjusted into pH with aqua calcis, and maintain a period of time, then filtered, sulfuric acid solution is used afterwards, after acid hydrolysis solution is maintained to separate out coloring matter under high temperature and certain pressure, disposable active carbon decoloring is carried out, cation exchange, anion exchange are carried out after decolouring, obtain lactate buffer solution, finally lactate buffer solution is concentrated, that is, obtains finished product.The present invention realizes disposable decolouring, and the technique for greatly simplifying decolouring has saved cost, while heated the yield and colourity of lactic acid.
Description
Technical field
The present invention relates to lactic acid treatment technical field, more particularly to the technique that a kind of D-ALPHA-Hydroxypropionic acid decolourizes.
Background technology
Lactic acid (lactic acid) also known as α-hydracrylate (α-hydroxypropionic acid), because not right containing one
Claim carbon atom, be divided into D-ALPHA-Hydroxypropionic acid and Pfansteihl.There was only the LDH of metabolism Pfansteihl due to human body, Pfansteihl is used as food
Product additive etc. is widely used, and D-ALPHA-Hydroxypropionic acid has been used for various chiral materials as an important chiral intermediate
Synthesis.The D-ALPHA-Hydroxypropionic acid of high-optical-purity in the practical application of heating poly-lactic acid material aspect of performance because obtained more in recent years
Many concerns.D-ALPHA-Hydroxypropionic acid and its derivative are the precursors for synthesizing various chiral materials, in answering for the fields such as medicine, agricultural chemicals and chemical industry
With quite varied.Especially with the popularization and popularization of novel biomaterial, D-ALPHA-Hydroxypropionic acid is achieved in terms of new diseases
Greater advance.
The production method of lactic acid includes fermentation method, chemical synthesis and enzyme process.At present, the production of the lactic acid of high-optical-purity
Based on microbial fermentation, fermented bacterium is lactobacillus, Rhizopus oryzae etc..Extraction to lactic fermentation liquid is separated, and China is general at present
All over the calcium lactate crystallization-acidolysis process for using.
Sour calcium crystallization-acidolysis process flow be upstream fermentation liquid through heating up, after basification, remove thalline, protein etc.
Colloidal impurity.The calcium lactate mash that obtains is concentrated, crystallization, centrifugation remove mother liquor, obtains calcium lactate crystal.Heating is redissolved
Afterwards, acidolysis is carried out with sulfuric acid, adds proper amount of active carbon to decolourize, separate removal calcium sulfate and activated carbon residue, obtain crude lactic acid molten
Liquid.Then crude lactic acid solution is removed into foreign ion therein respectively by anion and cation exchange resin, resulting solution is passed through again
More than 80% is concentrated into, lactic acid solution is got product.The upstream position that activated carbon decolorizing step is placed on technique is that is to say, this is just
In the presence of very fatal defect：1st, substantial amounts of impurity is contained in the lactic fermentation liquid at technique initial stage so that charcoal is to foreign pigment
Absorption is not very complete, therefore, during actual lactic acid purification, often once decolourize that GB Se Du≤50 can not be reached
Requirement, it is necessary to repeatedly decolourized, and it is larger on the yield influence of lactic acid repeatedly to decolourize, and damages the yield of lactic acid and lactate
Lose up to 30%, and energy consumption is also higher；2nd, coloring matter can not be separated out fully at the technique initial stage, even if or even the multiple activated carbon of appearance
The also excessively poor situation of effect after decolouring.
Therefore, a kind of method that new D-ALPHA-Hydroxypropionic acid decolourizes is developed, not only with urgent researching value, it may have good
Economic benefit and commercial application potentiality, this where power that exactly present invention is accomplished and basis.
The content of the invention
In order to overcome the defect in prior art as indicated above, the present inventor has made intensive studies to this, is paying
After a large amount of creative works, so as to completing the present invention.
Specifically, the technical problems to be solved by the invention are：A kind of D-ALPHA-Hydroxypropionic acid decoloration process is provided, to solve now
Need D-ALPHA-Hydroxypropionic acid repeatedly decolourize and also decolouring poor quality technical problem.
In order to solve the above technical problems, the technical scheme is that：
A kind of D-ALPHA-Hydroxypropionic acid decoloration process, temperature raising is passed through air and carries out after-ripening after D-ALPHA-Hydroxypropionic acid fermented and cultured terminates, and makes lactic acid
Production bacterium is in micro- aerobic state, continues to consume the nutriment that carbohydrate, amino acids etc. are also easy to produce pigment, after the completion of after-ripening,
Quick temperature raising is carried out under a certain pressure after D-ALPHA-Hydroxypropionic acid zymotic fluid is adjusted into pH with aqua calcis, and maintains a period of time,
Then filtered, afterwards using sulfuric acid solution, after acid hydrolysis solution is maintained to separate out coloring matter under high temperature and certain pressure, entered
Row disposable active carbon decoloring, carries out cation exchange, anion exchange after decolouring, obtain lactate buffer solution, finally that lactate buffer solution is dense
Contracting, that is, obtain finished product.
A kind of D-ALPHA-Hydroxypropionic acid decoloration process, comprises the following steps：
(1) after D-ALPHA-Hydroxypropionic acid production 35-40 DEG C of anaerobic fermentation culture of bacterium terminates, zymotic fluid after-ripening improves temperature to 40-50 DEG C,
10-20h is maintained, air is intermittently passed through, lactic-acid-producing strain is in micro- aerobic state, continue to consume the nutrients for being also easy to produce pigment
Matter, is easy to follow-up desolventing technology；
(2) after D-ALPHA-Hydroxypropionic acid fermentation after-ripening terminates, the pH of zymotic fluid is adjusted to 11-13 using aqua calcis, then will
The quick temperature raising of zymotic fluid is held time 20-40 minutes to 110-130 DEG C in the case where pressure is 0.06mpa-0.15mpa, allows fermentation
Coloring matter is fully separated out in liquid, and less than 20%, (3000 leave the heart 5 minutes to control solution light transmittance, take supernatant 440nm, dilution
10 times of detections)；
(3) treat that the broth temperature of step (2) is down to less than 100 DEG C, using ceramic membrane filter, concentration rate 10-20 is obtained
To filtrate；
(4) sulfuric acid is added in the filtrate for step (3) being obtained, pH to 2.0-3.0 is adjusted, the 3-6h that holds time is stirred, to lactic acid
Calcium carries out acidolysis, obtains the mixed liquor of crude lactic acid solution and calcium sulfate, filtering, removes the calcium sulfate of precipitation, obtains acidolysis filtering
Liquid；
(5) the acidolysis filtered fluid temperature raising for step (4) being obtained is to 110-130 DEG C, pressure 0.1mpa-0.15mpa, during maintenance
Between 30-50 minutes, coloring matter is separated out completely, less than 30%, (3000rpm is centrifuged 5 minutes control solution light transmittance, takes supernatant
440nm, dilutes 10 times of detections)；
(6) step (5) is obtained into filtrate to be decolourized using seed activity charcoal post, filtrate flow volume per minute is 0.1-0.5 times
Granular activated carbon column volume, maintains 30-90min to decolourize, and more than 95%, (3000rpm is centrifuged 5 minutes control discharging light transmittance, takes
Supernatant 440nm, dilutes 10 times of detections), filtrate after being decolourized；
(7) filtrate carries out cation exchange after the decolouring for step (6) being obtained, then by anion exchange, removes anion
Impurity, obtains crude lactic acid liquid；
(8) the crude lactic acid liquid for step (7) being obtained is concentrated under the conditions of 80-95 DEG C, -0.09~-0.097mpa, to requiring
Concentration, that is, obtain finished product lactic acid.
In the present invention, as a kind of perferred technical scheme, in the step (1), D-ALPHA-Hydroxypropionic acid production bacterium anaerobic fermentation training
Support after terminating, zymotic fluid is preferably heated to 42.5 DEG C, Aging storage 15h.
In the present invention, as a kind of perferred technical scheme, in the step (2), the D-ALPHA-Hydroxypropionic acid fermented and cultured process
In with aqua calcis adjust pH, after-ripening terminate after using stream be hydrogenated with calcium oxide solution by the way of the pH of zymotic fluid is adjusted to 11-
13, the concentration of above-mentioned aqua calcis is 20-40wt%.
In the present invention, as a kind of perferred technical scheme, in the step (2), by heating zymotic fluid, at 2-3 points
Temperature is promoted to 110-130 DEG C, preferably 125 DEG C in clock.
In the present invention, as a kind of perferred technical scheme, in the step (3), treat that temperature is down to less than 100 DEG C, profit
With ceramic membrane filter, concentration rate is preferably 16.
In the present invention, as a kind of perferred technical scheme, in step (4), sulfuric acid concentration is 45-98wt%, more preferably
98wt% sulfuric acid.
In the present invention, as a kind of perferred technical scheme, in step (4), filtering preferably uses vacuum band-type filter machine
Carry out.
In the present invention, as a kind of perferred technical scheme, in step (5), by acidolysis filtered fluid temperature raising to 125 DEG C, dimension
Hold 30min.
In the present invention, as a kind of perferred technical scheme, in step (6), treat that the filtrate temperature that step (5) is obtained is down to
70-100 DEG C, the decolouring of seed activity charcoal post is entered back into, maintenance bleaching time is 30-90min, is more preferably cooled to 90 DEG C and enters again
Enter the decolouring of seed activity charcoal post, maintain bleaching time 45min, flow velocity is according to charcoal post volume and determination of holding time.
In the present invention, as a kind of perferred technical scheme, in step (8), crude lactic acid liquid in 80-90 DEG C, -0.09~-
Concentrated under the conditions of 0.097mpa.
After employing above-mentioned technical proposal, the beneficial effects of the invention are as follows：
(1) be adjusted for traditional processing step by the present invention, has carried out the treatment of early stage to D-ALPHA-Hydroxypropionic acid zymotic fluid first,
Then recycle activated carbon to be absorbed to coloring matter at a certain temperature, realize disposable decolouring.This eliminates the need for existing
There is calcium lactate crystallization-acidolysis process once to decolourize that requirement can not be reached, after lactate buffer solution temperature is raised, remained in lactate buffer solution
The materials such as sugar, protein, pigment can again lead to lactic acid and darken, it is necessary to repeatedly decolouring, finally have impact on the purity of product
With the defect of recovery rate.
(2) inventor is it should be noted that the present invention is not only that process sequence has been carried out into simple adjustment, Er Qieshi
By experiment largely repeatedly, technological parameter therein and specific steps strict restriction is carried out into, for example：D-ALPHA-Hydroxypropionic acid ferments
After-ripening 10-20h is carried out after end at 40-50 DEG C, and interval is passed through air, D-ALPHA-Hydroxypropionic acid is produced bacterium and continues under the conditions of micro- oxygen consumption
Consumption carbohydrate, amino acids etc. are also easy to produce the nutriment of pigment, recycle aqua calcis to be adjusted to the pH of zymotic fluid
11-13, then by the quick temperature raising of zymotic fluid to 110-130 DEG C, the mode of this quick temperature raising is heavier not only beneficial to the adjustment of pH
Want, coloring matter can fully be separated out, be easy to follow-up work to carry out；For another example, ceramic membrane mistake has been selected in the present invention
The techniques such as filter, anion exchange, cation exchange, can fully remove by impurity, by the decolorization of activated carbon play to
Maximize；And for example：At 110-130 DEG C, after separating out coloring matter under the conditions of pressure 0.1mpa-0.15mpa, reuse activated carbon and enter
Row decolourizes, and this high temperature decolourizes, and further separates coloring matter, strengthens the effect of decolouring.
In a word, the present invention is filtered, and lifts temperature to 120- twice by after-ripening, ceramic membrane filter, filter in zymotic fluid
130 DEG C, coloring matter is fully separated out, then foreign pigment is removed in the case where high temperature is maintained by activated carbon, then by sun
Ion exchange, anion exchange these steps obtain high-purity, the finished product of low colourity, and requirement is reached so as to reach once decolourize
Purpose.The present invention realizes disposable decolouring, and the technique for greatly simplifying decolouring has saved cost, while improve the receipts of lactic acid
Rate and colourity.
Specific embodiment
With reference to specific embodiment, the present invention is further described.But the purposes and mesh of these exemplary embodiments
Be only used for enumerate the present invention, any type of any restriction not is constituted to real protection scope of the invention, it is more non-to incite somebody to action this
The protection domain of invention is confined to this.
Embodiment 1
A kind of D-ALPHA-Hydroxypropionic acid decoloration process, comprises the following steps：
(1) D-ALPHA-Hydroxypropionic acid production bacterium carries out anaerobic fermentation culture at 35 DEG C, with 20wt% aqua calcises in incubation
After adjusting pH, culture to terminate, zymotic fluid after-ripening improves temperature to 40 DEG C, maintains 10h, is intermittently passed through air, makes at lactic-acid-producing strain
In micro- aerobic state, continue to consume the nutriment for being also easy to produce pigment, be easy to follow-up desolventing technology；
(2) after D-ALPHA-Hydroxypropionic acid fermentation after-ripening terminates, the pH of zymotic fluid is adjusted by the way of stream plus 40wt% aqua calcises
It is whole to 11, then by zymotic fluid, quick temperature raising, to 110 DEG C, and is held time 20 points in the case where pressure is 0.06mpa in 2 minutes
Clock, allows coloring matter in zymotic fluid fully to separate out, and less than 20%, (3000 leave the heart 5 minutes to control solution light transmittance, take supernatant
440nm, dilutes 10 times of detections)；
(3) treat that the broth temperature of step (2) is down to less than 100 DEG C, using ceramic membrane filter, concentration rate 10 is filtered
Liquid；
(4) 45wt% sulfuric acid is added in the filtrate for step (3) being obtained, pH to 2.0 is adjusted, the 3-6h that holds time is stirred, to breast
Sour calcium carries out acidolysis, obtains the mixed liquor of crude lactic acid solution and calcium sulfate, is filtered using vacuum band-type filter machine, and it is heavy to remove
The calcium sulfate in shallow lake, obtains acidolysis filtered fluid；
(5) to 110 DEG C, pressure 0.1mpa holds time 30 minutes for the acidolysis filtered fluid temperature raising for step (4) being obtained, and makes to have
Color substance is separated out completely, and less than 30%, (3000rpm is centrifuged 5 minutes control solution light transmittance, takes supernatant 440nm, dilutes 10 times of inspections
Survey)；
(6) step (5) is obtained into filtrate and be down to 70 DEG C, decolourized using seed activity charcoal post, filtrate flow volume per minute is
0.1 times of granular activated carbon column volume, maintains 30min to decolourize, control discharging light transmittance more than 95% (3000rpm is centrifuged 5 minutes,
Supernatant 440nm is taken, 10 times of detections are diluted), filtrate after being decolourized；
(7) filtrate carries out cation exchange after the decolouring for step (6) being obtained, then by anion exchange, removes anion
Impurity, obtains crude lactic acid liquid；
(8) the crude lactic acid liquid for step (7) being obtained is concentrated under the conditions of 80 DEG C, -0.09mpa, to concentration is required, that is, is obtained
Finished product lactic acid.
The present embodiment prepares finished product lactic acid, and purity is 98%, and colourity is 25.
Embodiment 2
A kind of D-ALPHA-Hydroxypropionic acid decoloration process, comprises the following steps：
(1) D-ALPHA-Hydroxypropionic acid production bacterium carries out anaerobic fermentation culture at 37 DEG C, with 30wt% aqua calcises in incubation
After adjusting pH, culture to terminate, zymotic fluid after-ripening improves temperature to 42.5 DEG C, maintains 15h, is intermittently passed through air, makes lactic-acid-producing strain
In micro- aerobic state, continue to consume the nutriment for being also easy to produce pigment, be easy to follow-up desolventing technology；
(2) after D-ALPHA-Hydroxypropionic acid fermentation after-ripening terminates, the pH of zymotic fluid is adjusted by the way of stream plus 30wt% aqua calcises
It is whole to 12, then by zymotic fluid, quick temperature raising, to 125 DEG C, and is held time 30 points in the case where pressure is 0.10mpa in 2 minutes
Clock, allows coloring matter in zymotic fluid fully to separate out, and less than 20%, (3000 leave the heart 5 minutes to control solution light transmittance, take supernatant
440nm, dilutes 10 times of detections)；
(3) treat that the broth temperature of step (2) is down to less than 100 DEG C, using ceramic membrane filter, concentration rate 16 is filtered
Liquid；
(4) 98wt% sulfuric acid is added in the filtrate for step (3) being obtained, pH to 2.5 is adjusted, the 5h that holds time is stirred, to lactic acid
Calcium carries out acidolysis, obtains the mixed liquor of crude lactic acid solution and calcium sulfate, is filtered using vacuum band-type filter machine, removes precipitation
Calcium sulfate, obtain acidolysis filtered fluid；
(5) to 125 DEG C, pressure 0.10mpa holds time 30 minutes, makes for the acidolysis filtered fluid temperature raising for step (4) being obtained
Coloring matter is separated out completely, and less than 30%, (3000rpm is centrifuged 5 minutes control solution light transmittance, takes supernatant 440nm, dilutes 10 times
Detection)；
By step (5) obtain filtrate be cooled to 90 DEG C reuse seed activity charcoal post decolourize, filtrate flow body per minute
Product is 0.2 times of granular activated carbon column volume, maintains 45min to decolourize, and more than 95%, (3000rpm is centrifuged 5 points to control discharging light transmittance
Clock, takes supernatant 440nm, dilutes 10 times of detections), filtrate after being decolourized；
(7) filtrate carries out cation exchange after the decolouring for step (6) being obtained, then by anion exchange, removes anion
Impurity, obtains crude lactic acid liquid；
(8) the crude lactic acid liquid for step (7) being obtained is concentrated under the conditions of 90 DEG C, -0.095mpa, to concentration is required, that is, is obtained
Finished product lactic acid.
The present embodiment prepares finished product lactic acid, and purity is 98%, and colourity is 20.
Embodiment 3
A kind of D-ALPHA-Hydroxypropionic acid decoloration process, comprises the following steps：
(1) D-ALPHA-Hydroxypropionic acid production bacterium carries out anaerobic fermentation culture at 40 DEG C, with 40wt% aqua calcises in incubation
After adjusting pH, culture to terminate, zymotic fluid after-ripening improves temperature to 50 DEG C, maintains 20h, is intermittently passed through air, makes at lactic-acid-producing strain
In micro- aerobic state, continue to consume the nutriment for being also easy to produce pigment, be easy to follow-up desolventing technology；
(2) after D-ALPHA-Hydroxypropionic acid fermentation after-ripening terminates, the pH of zymotic fluid is adjusted by the way of stream plus 40wt% aqua calcises
It is whole to 13, then by zymotic fluid, quick temperature raising, to 130 DEG C, and is held time 40 points in the case where pressure is 0.15mpa in 3 minutes
Clock, allows coloring matter in zymotic fluid fully to separate out, and less than 20%, (3000 leave the heart 5 minutes to control solution light transmittance, take supernatant
440nm, dilutes 10 times of detections)；
(3) treat that the broth temperature of step (2) is down to less than 100 DEG C, using ceramic membrane filter, concentration rate 20 is filtered
Liquid；
(4) 50wt% sulfuric acid is added in the filtrate for step (3) being obtained, pH to 3.0 is adjusted, the 3-6h that holds time is stirred, to breast
Sour calcium carries out acidolysis, obtains the mixed liquor of crude lactic acid solution and calcium sulfate, is filtered using vacuum band-type filter machine, and it is heavy to remove
The calcium sulfate in shallow lake, obtains acidolysis filtered fluid；
(5) to 130 DEG C, pressure 0.15mpa holds time 50 minutes, makes for the acidolysis filtered fluid temperature raising for step (4) being obtained
Coloring matter is separated out completely, and less than 30%, (3000rpm is centrifuged 5 minutes control solution light transmittance, takes supernatant 440nm, dilutes 10 times
Detection)；
(6) step (5) is obtained after filtrate temperature is down to 100 DEG C, being decolourized using seed activity charcoal post, filtrate stream per minute
Amount volume is 0.5 times of granular activated carbon column volume, maintains 90min to decolourize, control discharging light transmittance more than 95% (3000rpm from
The heart 5 minutes, takes supernatant 440nm, dilutes 10 times of detections), filtrate after being decolourized；
(7) filtrate carries out cation exchange after the decolouring for step (6) being obtained, then by anion exchange, removes anion
Impurity, obtains crude lactic acid liquid；
(8) the crude lactic acid liquid for step (7) being obtained is concentrated under the conditions of 95 DEG C, -0.097mpa, to concentration is required, that is, is obtained
Finished product lactic acid.
The present embodiment prepares finished product lactic acid, and purity is 98%, and colourity is 29.
Embodiment 4
A kind of D-ALPHA-Hydroxypropionic acid decoloration process, comprises the following steps：
(1) D-ALPHA-Hydroxypropionic acid production bacterium carries out anaerobic fermentation culture at 37 DEG C, with 20wt% aqua calcises in incubation
After adjusting pH, culture to terminate, zymotic fluid after-ripening improves temperature to 45 DEG C, maintains 13h, is intermittently passed through air, makes at lactic-acid-producing strain
In micro- aerobic state, continue to consume the nutriment for being also easy to produce pigment, be easy to follow-up desolventing technology；
(2) after D-ALPHA-Hydroxypropionic acid fermentation after-ripening terminates, the pH of zymotic fluid is adjusted by the way of stream plus 35wt% aqua calcises
It is whole to 13, then by zymotic fluid, quick temperature raising, to 120 DEG C, and is held time 25 points in the case where pressure is 0.08mpa in 2.5 minutes
Clock, allows coloring matter in zymotic fluid fully to separate out, and less than 20%, (3000 leave the heart 5 minutes to control solution light transmittance, take supernatant
440nm, dilutes 10 times of detections)；
(3) treat that the broth temperature of step (2) is down to less than 100 DEG C, using ceramic membrane filter, concentration rate 18 is filtered
Liquid；
(4) 90wt% sulfuric acid is added in the filtrate for step (3) being obtained, pH to 2.0 is adjusted, the 5h that holds time is stirred, to lactic acid
Calcium carries out acidolysis, obtains the mixed liquor of crude lactic acid solution and calcium sulfate, is filtered using vacuum band-type filter machine, removes precipitation
Calcium sulfate, obtain acidolysis filtered fluid；
(5) to 115 DEG C, pressure 0.15mpa holds time 45 minutes, makes for the acidolysis filtered fluid temperature raising for step (4) being obtained
Coloring matter is separated out completely, and less than 30%, (3000rpm is centrifuged 5 minutes control solution light transmittance, takes supernatant 440nm, dilutes 10 times
Detection)；
(6) step (5) is obtained into filtrate temperature and be down to 80 DEG C, decolourized using seed activity charcoal post, filtrate flow body per minute
Product is 0.3 times of granular activated carbon column volume, maintains 60min to decolourize, and more than 95%, (3000rpm is centrifuged 5 points to control discharging light transmittance
Clock, takes supernatant 440nm, dilutes 10 times of detections), filtrate after being decolourized；
(7) filtrate carries out cation exchange after the decolouring for step (6) being obtained, then by anion exchange, removes anion
Impurity, obtains crude lactic acid liquid；
(8) the crude lactic acid liquid for step (7) being obtained is concentrated under the conditions of 90 DEG C, -0.095mpa, to concentration is required, that is, is obtained
Finished product lactic acid.
The present embodiment prepares finished product lactic acid, and purity is 98%, and colourity is 25.
Embodiment 5
A kind of D-ALPHA-Hydroxypropionic acid decoloration process, comprises the following steps：
(1) D-ALPHA-Hydroxypropionic acid production bacterium carries out anaerobic fermentation culture at 35 DEG C, with 25wt% aqua calcises in incubation
After adjusting pH, culture to terminate, zymotic fluid after-ripening improves temperature to 43 DEG C, maintains 18h, is intermittently passed through air, makes at lactic-acid-producing strain
In micro- aerobic state, continue to consume the nutriment for being also easy to produce pigment, be easy to follow-up desolventing technology；
(2) after D-ALPHA-Hydroxypropionic acid fermentation after-ripening terminates, the pH of zymotic fluid is adjusted by the way of stream plus 25wt% aqua calcises
It is whole to 12, then by zymotic fluid, quick temperature raising, to 130 DEG C, and is held time 25 points in the case where pressure is 0.12mpa in 3 minutes
Clock, allows coloring matter in zymotic fluid fully to separate out, and less than 20%, (3000 leave the heart 5 minutes to control solution light transmittance, take supernatant
440nm, dilutes 10 times of detections)；
(3) treat that the broth temperature of step (2) is down to less than 100 DEG C, using ceramic membrane filter, concentration rate 16 is filtered
Liquid；
(4) 55wt% sulfuric acid is added in the filtrate for step (3) being obtained, pH to 3.0 is adjusted, the 5h that holds time is stirred, to lactic acid
Calcium carries out acidolysis, obtains the mixed liquor of crude lactic acid solution and calcium sulfate, is filtered using vacuum band-type filter machine, removes precipitation
Calcium sulfate, obtain acidolysis filtered fluid；
(5) to 125 DEG C, pressure 0.14mpa holds time 35 minutes, makes for the acidolysis filtered fluid temperature raising for step (4) being obtained
Coloring matter is separated out completely, and less than 30%, (3000rpm is centrifuged 5 minutes control solution light transmittance, takes supernatant 440nm, dilutes 10 times
Detection)；
(6) step (5) is obtained into filtrate temperature and be down to 75 DEG C, decolourized using seed activity charcoal post, filtrate flow body per minute
Product is 0.5 times of granular activated carbon column volume, maintains 60min to decolourize, and more than 95%, (3000rpm is centrifuged 5 points to control discharging light transmittance
Clock, takes supernatant 440nm, dilutes 10 times of detections), filtrate after being decolourized；
(7) filtrate carries out cation exchange after the decolouring for step (6) being obtained, then by anion exchange, removes anion
Impurity, obtains crude lactic acid liquid；
(8) the crude lactic acid liquid for step (7) being obtained is concentrated under the conditions of 95 DEG C, -0.09mpa, to concentration is required, that is, is obtained
Finished product lactic acid.
The present embodiment prepares finished product lactic acid, and purity is 98%, and colourity is 23.
Embodiment 6
A kind of D-ALPHA-Hydroxypropionic acid decoloration process, comprises the following steps：
(1) D-ALPHA-Hydroxypropionic acid production bacterium carries out anaerobic fermentation culture at 39 DEG C, with 35wt% aqua calcises in incubation
After adjusting pH, culture to terminate, zymotic fluid after-ripening improves temperature to 50 DEG C, maintains 13h, is intermittently passed through air, makes at lactic-acid-producing strain
In micro- aerobic state, continue to consume the nutriment for being also easy to produce pigment, be easy to follow-up desolventing technology；
(2) after D-ALPHA-Hydroxypropionic acid fermentation after-ripening terminates, the pH of zymotic fluid is adjusted by the way of stream plus 30wt% aqua calcises
It is whole to 12, then by zymotic fluid, quick temperature raising, to 110 DEG C, and is held time 25 points in the case where pressure is 0.15mpa in 2 minutes
Clock, allows coloring matter in zymotic fluid fully to separate out, and less than 20%, (3000 leave the heart 5 minutes to control solution light transmittance, take supernatant
440nm, dilutes 10 times of detections)；
(3) treat that the broth temperature of step (2) is down to less than 100 DEG C, using ceramic membrane filter, concentration rate 17 is filtered
Liquid；
(4) 60wt% sulfuric acid is added in the filtrate for step (3) being obtained, pH to 2.5 is adjusted, the 5h that holds time is stirred, to lactic acid
Calcium carries out acidolysis, obtains the mixed liquor of crude lactic acid solution and calcium sulfate, is filtered using vacuum band-type filter machine, removes precipitation
Calcium sulfate, obtain acidolysis filtered fluid；
(5) to 117 DEG C, pressure 0.12mpa holds time 45 minutes, makes for the acidolysis filtered fluid temperature raising for step (4) being obtained
Coloring matter is separated out completely, and less than 30%, (3000rpm is centrifuged 5 minutes control solution light transmittance, takes supernatant 440nm, dilutes 10 times
Detection)；
(6) step (5) is obtained into filtrate temperature and be down to 80 DEG C, decolourized using seed activity charcoal post, filtrate flow body per minute
Product is 0.3 times of granular activated carbon column volume, maintains 60min to decolourize, and more than 95%, (3000rpm is centrifuged 5 points to control discharging light transmittance
Clock, takes supernatant 440nm, dilutes 10 times of detections), filtrate after being decolourized；
(7) filtrate carries out cation exchange after the decolouring for step (6) being obtained, then by anion exchange, removes anion
Impurity, obtains crude lactic acid liquid；
(8) the crude lactic acid liquid for step (7) being obtained is concentrated under the conditions of 85 DEG C, -0.05mpa, to concentration is required, that is, is obtained
Finished product lactic acid.
The present embodiment prepares finished product lactic acid, and purity is 98%, and colourity is 22.
Comparative example
Traditional lactic acid extraction process is as follows：
(1) after lactic fermentation terminates, lactic fermentation liquid is heated to 80~90 DEG C, addition calcium hydroxide regulation pH to 10~
12, insulated and stirred is filtrated to get filtrate 1 after 15~60 minutes；
(2) filtrate 1 is decolourized with activated carbon, activated carbon is 0.05: 100~1: 100 with the mass ratio of lactic fermentation liquid, is taken off
Color temperature is 65~80 DEG C, and bleaching time is 30~70min, then priority sheet frame and inorganic ceramic membrane be filtrated to get filtrate 2；
(3) by filtrate 2 take successively concentration, decrease temperature crystalline, be centrifuged, wash it is brilliant, dry, calcium lactate crystal is obtained；
(4) the calcium lactate crystal plus distilled water for obtaining step (3) dissolve it, then add concentration to be 80wt% sulfuric acid, adjust
PH to 2.5, acidolysis is carried out to calcium lactate, obtains the mixed liquor of crude lactic acid solution and calcium sulfate, is filtered to remove the calcium sulfate of precipitation,
Obtain acidolysis filtered fluid；
(5) filtered fluid is decolourized again, the discoloration method of repeat step 2.
(6) foreign ion in crude lactic acid is removed with anion and cation exchange resin；
(7) finished product lactic acid is concentrated to give, its purity is 85%~90%, determines the need for taking off again according to finished product colourity
Color.
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example |
| Decolouring number of times | 1 | 1 | 1 | 1 | 1 | 1 | 2-3 |
| Purity | 98 | 98 | 98 | 98 | 98 | 98 | 86 |
| Colourity | 25 | 20 | 29 | 25 | 23 | 22 | 36 |
| Yield | 96 | 96.5 | 94.6 | 95.8 | 96.2 | 94.3 | 82.9 |
It should be appreciated that the purposes of these embodiments is merely to illustrate the present invention and is not intended to limit protection model of the invention
Enclose.Additionally, it will also be appreciated that after technology contents of the invention have been read, those skilled in the art can make each to the present invention
Plant and change, change and/or modification, all these equivalent form of value equally falls within the guarantor that the application appended claims are limited
Within the scope of shield.
Claims (10)
1. a kind of D-ALPHA-Hydroxypropionic acid decoloration process, it is characterised in that：It is passed through after air carries out in temperature raising after D-ALPHA-Hydroxypropionic acid fermented and cultured terminates
Ripe, the detailed process of after-ripening is：After D-ALPHA-Hydroxypropionic acid production 35-40 DEG C of anaerobic fermentation culture of bacterium terminates, zymotic fluid after-ripening improves temperature
To 40-50 DEG C, 10-20h is maintained, be intermittently passed through air, lactic-acid-producing strain is in micro- aerobic state, continued consumption and be also easy to produce color
The nutriment of element, is easy to follow-up desolventing technology, after the completion of after-ripening, after D-ALPHA-Hydroxypropionic acid zymotic fluid is adjusted into pH with aqua calcis
Quick temperature raising is carried out under a certain pressure, and maintains a period of time, then to be filtered, afterwards using sulfuric acid solution, by acidolysis
After liquid maintains to separate out coloring matter under high temperature and certain pressure, disposable active carbon decoloring is carried out, cation is carried out after decolouring
Exchange, anion exchange, obtain lactate buffer solution, finally concentrate lactate buffer solution, that is, obtain finished product.
2. a kind of D-ALPHA-Hydroxypropionic acid decoloration process as claimed in claim 1, it is characterised in that：Comprise the following steps：
(1) after D-ALPHA-Hydroxypropionic acid production 35-40 DEG C of anaerobic fermentation culture of bacterium terminates, zymotic fluid after-ripening improves temperature to 40-50 DEG C, maintains
10-20h, is intermittently passed through air, lactic-acid-producing strain is in micro- aerobic state, continues to consume the nutriment for being also easy to produce pigment,
It is easy to follow-up desolventing technology；
(2) after D-ALPHA-Hydroxypropionic acid fermentation after-ripening terminates, the pH of zymotic fluid is adjusted to 11-13 using aqua calcis, then will fermentation
The quick temperature raising of liquid is held time 20-40 minutes to 110-130 DEG C in the case where pressure is 0.06mpa-0.15mpa, is allowed in zymotic fluid
Coloring matter is fully separated out, and control solution light transmittance is less than 20%；
(3) treat that the broth temperature of step (2) is down to less than 100 DEG C, using ceramic membrane filter, concentration rate 10-20 is filtered
Liquid；
(4) sulfuric acid is added in the filtrate for step (3) being obtained, pH to 2.0-3.0 is adjusted, the 3-6h that holds time is stirred, calcium lactate is entered
Row acidolysis, obtains the mixed liquor of crude lactic acid solution and calcium sulfate, filtering, removes the calcium sulfate of precipitation, obtains acidolysis filtered fluid；
(5) the acidolysis filtered fluid temperature raising for step (4) being obtained to 110-130 DEG C, pressure 0.1mpa-0.15mpa, hold time 30-
50 minutes, coloring matter is set to separate out completely, control solution light transmittance is less than 30%；
(6) step (5) is obtained into filtrate to be decolourized using seed activity charcoal post, filtrate flow volume per minute is 0.1-0.5 times of particle
Activated-charcoal column volume, maintains 30-90min to decolourize, and control discharging light transmittance is more than 95%, filtrate after being decolourized；
(7) filtrate carries out cation exchange after the decolouring for step (6) being obtained, then by anion exchange, removes anion miscellaneous
Matter, obtains crude lactic acid liquid；
(8) the crude lactic acid liquid for step (7) being obtained is concentrated under the conditions of 80-95 DEG C, -0.09~-0.097mpa, to requiring concentration,
Obtain finished product lactic acid.
3. a kind of D-ALPHA-Hydroxypropionic acid decoloration process as claimed in claim 2, it is characterised in that：In the step (1), D-ALPHA-Hydroxypropionic acid production
After bacterium anaerobic fermentation culture terminates, zymotic fluid heating is improved into temperature to 42.5 DEG C, Aging storage 15h.
4. a kind of D-ALPHA-Hydroxypropionic acid decoloration process as claimed in claim 2, it is characterised in that：In the step (2), after after-ripening terminates
The pH of zymotic fluid is adjusted to 11-13 by the way of stream hydrogenation calcium oxide solution, the concentration of the aqua calcis is 20-
40wt%.
5. a kind of D-ALPHA-Hydroxypropionic acid decoloration process as claimed in claim 2, it is characterised in that：In the step (2), sent out by heating
Zymotic fluid, 110-130 DEG C was promoted in 2-3 minutes by temperature.
6. a kind of D-ALPHA-Hydroxypropionic acid decoloration process as claimed in claim 2, it is characterised in that：In the step (3), concentration rate is
16。
7. a kind of D-ALPHA-Hydroxypropionic acid decoloration process as claimed in claim 2, it is characterised in that：Sulfuric acid concentration is 45-98wt%.
8. a kind of D-ALPHA-Hydroxypropionic acid decoloration process as claimed in claim 2, it is characterised in that：In step (5), acidolysis filtered fluid is carried
Temperature maintains 30min to 125 DEG C.
9. a kind of D-ALPHA-Hydroxypropionic acid decoloration process as claimed in claim 2, it is characterised in that：In step (6), treat that step (5) is obtained
Filtrate temperature be down to 70-100 DEG C, enter back into seed activity charcoal post decolouring, maintenances bleaching time be 45min.
10. a kind of D-ALPHA-Hydroxypropionic acid decoloration process as claimed in claim 2, it is characterised in that：In step (8), crude lactic acid liquid is in 80-
90 DEG C, concentrate under the conditions of -0.09~-0.097mpa.
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