CN104327082B - A kind of method that high-efficiency environment friendly reclaims riboflavin from crystalline mother solution - Google Patents
A kind of method that high-efficiency environment friendly reclaims riboflavin from crystalline mother solution Download PDFInfo
- Publication number
- CN104327082B CN104327082B CN201410579130.5A CN201410579130A CN104327082B CN 104327082 B CN104327082 B CN 104327082B CN 201410579130 A CN201410579130 A CN 201410579130A CN 104327082 B CN104327082 B CN 104327082B
- Authority
- CN
- China
- Prior art keywords
- riboflavin
- crystalline mother
- mother solution
- stripping liquid
- acid
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D475/00—Heterocyclic compounds containing pteridine ring systems
- C07D475/12—Heterocyclic compounds containing pteridine ring systems containing pteridine ring systems condensed with carbocyclic rings or ring systems
- C07D475/14—Benz [g] pteridines, e.g. riboflavin
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
A kind of from crystalline mother solution high-efficiency environment friendly reclaim the method for riboflavin and belong to the clean preparation method field of riboflavin.The present invention provides a kind of economically feasible, high-efficiency environment friendly, is prone to the method reclaiming riboflavin from crystalline mother solution that industry is amplified.The present invention selects the riboflavin in macroporous resin adsorption crystalline mother solution, carrys out desorbing with suitable eluent, extracts riboflavin from stripping liquid, and its process includes dynamic adsorption and the dynamic desorption of resin, and reclaims mineral acid and ethanol from stripping liquid.The present invention uses macroporous adsorbent resin to reclaim the riboflavin in crystalline mother solution, improve productivity, and decrease the liquid waste processing amount in riboflavin production process, reduce the totle drilling cost of riboflavin industrialized production, the riboflavin of more than 80% in crystalline mother solution can be reclaimed, purity is higher than 98%, reaches pharmaceutical grade.It addition, use the acid of more than 80% in the recyclable stripping liquid of electrodialysis plant, use the ethanol of more than 75% in the recyclable stripping liquid of evaporation and concentration, to realize recycling of acid and alcohol.
Description
Technical field:
The present invention relates to a kind of method reclaiming riboflavin from riboflavin crystalline mother solution, specifically belong to
The clean preparation method field of riboflavin.
Background technology:
Riboflavin, i.e. vitamin B2, it is a kind of water soluble vitamins, but is slightly soluble in water, at 27.5 DEG C,
Dissolubility is 120mg/L.Dissolve in sodium chloride solution, be soluble in dilute sodium hydroxide solution, in neutrality
Or in acid solution, heating is stable, heats perishable, also easily irradiated by ultraviolet in alkaline solution
And destroy structure.Riboflavin is flavin mononucleotide (FMN) (FMN) and the coenzyme of flavin purine two thuja acid (FAD),
Participate in biooxidation reactions and the energy metabolism of living organism, be that human body is healthy and normal growth institute is required；
Substantial amounts of epidemiology and animal data show, riboflavin has anti-cancer and anticancer effect；Research
Also showing, riboflavin has the effects such as reduction blood fat, antiplatelet aggregation, anti-lipid peroxidation, these
It is all the danger relevant to hypertension complication.Vitamin B2Lack with oral cavity and the mucosal inflammation of throat,
Skin pruritus is relevant with inflammation and similar skin injury, conjunctiva inflammation, visual deterioration and the corneal opacity etc.,
Such as be deficient in vitamin in baby and child B2May result in growth to stop and body weight reduction.Riboflavin can conduct
Conventional clinical medicine, it is possible to be used in food industry as pigment and nourishing additive agent, can be used as feedstuff
Additive, meets growth of animal needs, and improves nutrient utilization.
Industrial full chemical synthesis, semi-chemical synthesis and the microorganism being mainly with glucose as raw material
Fermentative Production riboflavin.It is due to full chemical synthesis and semi-chemical synthesis complex process, relatively costly,
The riboflavin purity obtained and yield are the best, and along with the birth of microbe fermentation method, front several method is gradually
It is eliminated.Microbe fermentation method is the most cost-effective method of one that development in recent years is got up, and is given birth to
The riboflavin purity produced is high, and compared with front several method, its advantage of lower cost, and to environment
Pollution with product is few, and therefore, microbe fermentation method is increasingly favored by riboflavin manufacturer.Now
Guanji Pharmaceutical of Hubei China, (BASF) BASF AG of Germany and (Roche) Roche of Switzerland
Company all uses Production by Microorganism Fermentation riboflavin.
Owing to riboflavin is the intracellular product obtained by microbe fermentation method, therefore containing big in its fermentation liquid
Thalline, cell debris, protein, nucleic acid and other organic stickums of amount, its viscosity is relatively big,
Thus bring bigger difficulty to the isolated and purified of riboflavin.For different production methods, riboflavin
Separating and extracting process also have difference, generally speaking, the separating and extracting process of riboflavin mainly has: with much money
Belong to salt precipitation method, Morehouse method, acid pasting and alkali solution technique, current commercial production mainly use after two
The method of kind.
First acid pasting is by Lactochrome fermentation liquor dilute acid hydrolysis, discharges the core of part and protein bound
Flavin；Then add potassium ferrocyanide and zinc sulfate, remove the impurity such as protein；Add 3-hydroxyl-2-how sodium formate,
It is allowed to form double salt with riboflavin, is finally separating refined.Zhang Guosheng application the method is withered from riboflavin
Separation and Extraction riboflavin in grass bacillus fermentation liquid, riboflavin yield is 56.61%.By Gyure etc.
The United States Patent (USP) US5103005 proposition alkaline solution of application in 1989 approval in 1992 dissolves riboflavin,
Oxidizer the most in the solution, adjusts pH value by acid solution the most again, makes riboflavin Precipitation.1998
Year, the dissolubility of riboflavin is studied by Wuxi Light Industry Univ. Zhang Kechang etc., and riboflavin is dissolved by pH
The impact of degree is very big, particularly after pH value reaches 11.0, if the change that pH value is the least, will
Riboflavin dissolubility is caused to produce the biggest fluctuation, as shown in the table.Zhang Kechang with mass concentration is
The Lactochrome fermentation liquor of 6400mg/L is raw material, with alkali solution technique, crystallizes through secondary separation, final acquisition
Finished product purity reaches 92.6%, and total recovery is close to 80%.Table 1 shows that riboflavin is dissolved by different pH
The impact of degree.
Table 1 riboflavin dissolubility (25 DEG C) under different pH
The process route that acid pasting extracts riboflavin is long, and process loss is many, and yield is relatively low, and energy consumption is relatively
Greatly, it is 60% 70% through once dissolving, separate, crystallize the product purity of acquisition, high-purity to be obtained
Riboflavin, recrystallization can only be carried out, its advantage is that riboflavin is more stable in acid solution, and structure is not
Can be destroyed.And alkali solution technique extraction riboflavin yield is higher, energy consumption is relatively low, riboflavin in alkaline solution
Dissolubility the biggest.But riboflavin is susceptible to irreversible denaturation reaction in the basic conditions, and stability is relatively
Difference, if controlling bad, will result in loss, such as the temperature of solution, lucifuge condition, the pH of solution
Value, the concentration of riboflavin action time in the solution and riboflavin etc. has shadow to the stability of riboflavin
Ring.No matter it is acid pasting or alkali solution technique, the most all can cause substantial amounts of crystalline mother solution, wherein have a large amount of
Riboflavin can not be collected and as liquid waste processing, not only cause serious waste and pollution but also make raw
Producing efficiency to can not get improving, this is also the subject matter of dilution crystallization.
Li Wenzhao once used macroporous adsorbent resin AB-8 to reclaim the riboflavin in crystalline mother solution, and it uses second
Alcohol-0.1mol/LNaOH solution (v/v is 1:1) is eluent, only finally gives the riboflavin response rate
44%, due to riboflavin instability in alkaline solution, therefore use alkaline solution eluting easily to make riboflavin
Occur irreversible denaturation to destroy its structure, finally make yield relatively low.And this patent uses nonpolar greatly
Hole resin SP207, SP825, SP850, H103 or HP20 etc. adsorb the riboflavin in crystalline mother solution,
Eluent be mineral acid and ethanol solution (wherein acid concentration is 5%～15%, concentration of alcohol be 60%～
80% (volume fraction)), the final riboflavin response rate reaches more than 80%, purity more than 98%,
Comply fully with relevant national standard requirement.Owing to crystalline mother solution containing certain acid, therefore in chromatography process
Effluent can be re-used for the acidifying step during the acidization of fermentation liquid or riboflavin purifying crude
Suddenly.Secondly, use the mineral acid in the recyclable stripping liquid of electrodialysis plant, use evaporation and concentration recyclable
Ethanol in stripping liquid, to realize acid and the recycling of ethanol.
Summary of the invention:
The purpose of the present invention: provide a kind of economically feasible, high-efficiency environment friendly, be prone to industry amplification from crystallization
The method reclaiming riboflavin in mother solution, reduces production cost, and effectively alleviates the pollution produced environment.
The technical scheme is that the riboflavin selected in suitable macroporous resin adsorption crystalline mother solution,
Carrying out desorbing with suitable eluent, extract riboflavin from stripping liquid, its process includes the dynamic suction of resin
Echo dynamic desorption, and from stripping liquid, reclaim mineral acid and ethanol.The present invention uses macroporous absorption tree
Fat reclaims the riboflavin in crystalline mother solution, decreases the waste of riboflavin, improves productivity, and decrease
Liquid waste processing amount in riboflavin production process, reduces the totle drilling cost of riboflavin industrialized production, this method
Can reclaim the riboflavin of more than 80% in crystalline mother solution, purity is higher than 98%, reaches pharmaceutical grade.It addition,
Use the acid of more than 80% in the recyclable stripping liquid of electrodialysis plant, use the recyclable stripping liquid of evaporation and concentration
In more than 75% ethanol, to realize acid and the recycling of alcohol.
The concrete technical scheme of the present invention is: reclaiming riboflavin from riboflavin crystalline mother solution, it specifically walks
Rapid as follows:
(1) Lactochrome fermentation liquor is isolated and purified: Lactochrome fermentation liquor is preprocessed, acidifying, oxidation
Crystallization, solid-liquid separation obtains riboflavin crude product, and riboflavin crude product is through being recrystallized to give riboflavin fine work and knot
Brilliant mother solution, and crystalline mother solution recycles in subsequent step.Detailed process refers to riboflavin fermentation
Liquid heats 1～2 hour at 40～80 DEG C, and then using aperture is 100～500nm ceramic membrane filters
Remove the impurity such as thalline；Penetrating fluid after membrane filtration adds inorganic acid for adjusting pH to 2～3, carry out
Acidifying；Fermentation liquid after acidifying adds the hydrogen peroxide that mass fraction is 0.3%～0.5%, addition
It is the 1%～5% of fermentating liquid volume, then at 70～90 DEG C of heated and stirred 30min～1h, then exists
Being cooled to room temperature, and centrifugation in 30min, precipitum is riboflavin crude product 75～85 DEG C of drying,
And supernatant continues on for the acidifying of lower batch fermentation liquid as inorganic acid solution.Next riboflavin crude product is taken
Adding inorganic acid solution makes its pH be 2～3, dissolves and is acidified, and being subsequently added into mass fraction is
The hydrogen peroxide of 0.3%～0.5%, addition is the 1%～5% of fermentating liquid volume, then adds at 70～90 DEG C
Thermal agitation 30min～1h, is then cooled to room temperature, and centrifugation in 30min, precipitum 75～
85 DEG C of drying are riboflavin fine work, and supernatant recycles in next step as crystalline mother solution.
(2) dynamic adsorption of riboflavin crystalline mother solution: select non-pole preferable to riboflavin absorption property
Property macroporous resin adsorbs riboflavin crystalline mother solution under 5～20BV/h flow velocitys.Said herein nonpolar macroporous
Resin refers to that aperture is less than, general aperture between 40～, such as SP 207, HP20, H 103,
SP825 or SP850 resins etc., in effluent, riboflavin concentration stops when being the 10% of crystalline mother solution concentration
Absorption.Containing certain density acid in effluent in adsorption process, after mineral acid adjusts pH to be 2～3
Acidification step in step (1).
(3) dynamic desorption of riboflavin crystalline mother solution: with deionized water rinsing chromatographic column to effluent pH
When being 6～7, then to use dehydrated alcohol and mineral acid mixed solution be that eluent is at 5～20BV/h flow velocitys
Under carry out eluting, collect stripping liquid.Molten used herein of the mixing that eluent is dehydrated alcohol and mineral acid
Liquid, wherein acid concentration controls 5%～15%, and concentration of alcohol is 60%～80%, and effluent volume controls
4～6BV, mineral acid refers to hydrochloric acid, sulphuric acid or nitric acid；
(4) recovery of mineral acid in stripping liquid: use electrodialysis plant to process stripping liquid, reclaim desorbing
Mineral acid in liquid, the mineral acid of recovery is reused for preparing the eluent in (3).Electrodialysis time control
Making its electric current density is 3～9mA/cm2, flow velocity is 18～25L/h, this process recyclable more than 80%
Mineral acid；
(5) recovery of ethanol in stripping liquid: use evaporation concentration equipment to process stripping liquid, reclaim desorbing
Ethanol in liquid, the ethanol of recovery can be reused for preparing the eluent in (3).Due to stripping liquid
In containing substantial amounts of ethanol and minimal amount of mineral acid, therefore rotation can be used to steam the ethanol reclaiming in solution,
Rotation is steamed temperature and is controlled at 30～50 DEG C, and vacuum is 45～80bar, the ethanol of recyclable more than 75%；
(6) collection of riboflavin fine work: add in the riboflavin that evaporation and concentration obtains in step (5)
Water-soluble go out and sucking filtration, be placed in the baking oven of 75～85 DEG C and be dried, and survey its purity by GB 14752-2010.
The riboflavin of more than 80% in the final recyclable crystalline mother solution of above step, purity reach 98% with
On, the requirement that indices is all up to state standards.This process had both decreased the waste of riboflavin, again
Decrease the treating capacity of waste liquid, and in adsorption process effluent recycle with mineral acid in stripping liquid and
Recycling of ethanol, alleviates the pollution produced environment, thus greatly reduces the work of riboflavin
Skill total production cost.
Beneficial effect:
(1) can reclaim the product of more than 80% from crystalline mother solution, its effective ingredient is higher than 98%,
Reach the requirement of relevant national standard.
(2) effluent in chromatography process can be re-used for the crystallization of fermentation liquid, on the one hand decreases
Mineral acid and the consumption of water, on the other hand decrease the treating capacity of waste liquid, thus reduce total production cost.
(3) refer to the riboflavin in non-polar macroporous resin absorption crystalline mother solution, and set with electrodialysis
The standby mineral acid reclaimed in stripping liquid, makes whole technique realize high efficiency, and the cleaning of low energy consumption produces.
(4) open a method reclaiming riboflavin from crystalline mother solution, and make experimental technique route
Optimized, beneficially industrialized production.
Accompanying drawing illustrates:
Fig. 1 is the separation purifying technique flow chart of Lactochrome fermentation liquor.
Fig. 2 is the process chart reclaiming riboflavin from crystalline mother solution.
Detailed description of the invention:
Below in conjunction with example, the invention will be further described.
Embodiment 1
(1) Lactochrome fermentation liquor is isolated and purified, takes Lactochrome fermentation liquor 1200ml and heats at 40 DEG C
2h, the ceramic membrane filter using aperture to be 100nm removes the impurity such as thalline；Penetrating fluid after membrane filtration
The salt acid for adjusting pH of middle addition 36%～38%, to 2, is acidified；Again the fermentation liquid after acidifying adds
Enter the hydrogen peroxide 60ml that mass fraction is 0.3%, 70 DEG C of heated and stirred 1h, then cold in 30min
But to room temperature, 6000r/min centrifugation 15min, precipitum is riboflavin crude product 75 DEG C of drying,
Supernatant adds hydrochloric acid and continues regulation its pH to 2, for the acidifying of lower batch fermentation liquid.Next take
Riboflavin crude product adds the hydrochloric acid of 36%～38% and adjusts its pH to be 2, dissolves and is acidified, being subsequently added into
Mass fraction is the hydrogen peroxide 60ml of 0.3%, 70 DEG C of heated and stirred 1h, finally cools down in 30min
To room temperature, and at 6000r/min centrifugation 15min, precipitum is riboflavin essence 75 DEG C of drying
Product, and supernatant recycles in next step as crystalline mother solution.
(2) dynamic adsorption of riboflavin crystalline mother solution, uses wet method dress post nonpolar macroporous for 15ml tree
Fat SP207 is filled in the chromatographic column of 20cm × 1cm, then with peristaltic pump under the flow velocity of 5BV/h
Adsorb above-mentioned crystalline mother solution, when in effluent, riboflavin concentration stops inhaling when being the 10% of crystalline mother solution concentration
Attached.
(3) dynamic desorption of riboflavin crystalline mother solution: with deionized water rinsing chromatographic column to effluent pH
When being 6, then with hydrochloric acid (mass fraction 36%～38%) and ethanol solution (volume ratio 2:8)
90ml desorbing under the desorbing flow velocity of 20BV/h altogether, collects stripping liquid.
(4) recovery of sour water in stripping liquid: stripping liquid through electrodialysis process, wherein electric current density
For 3mA/cm2, flow velocity is 18L/h, the hydrochloric acid of 82% in recyclable solution.
(5) recovery of ethanol in stripping liquid: use Rotary Evaporators to enter the stripping liquid of electrodialysis process
Row rotation is steamed, and it is 30 DEG C that temperature is steamed in rotation, and vacuum is 45bar, the ethanol of recyclable 78%.
(6) collection of riboflavin fine work: the riboflavin in bottle is steamed in previous step rotation, adds 20ml water-soluble
Out and sucking filtration, it is placed in the baking oven of 75 DEG C and is dried, and survey its purity by GB 14752-2010.
During this, using the riboflavin of 84.3% in the recyclable crystalline mother solution of SP207 resin, purity is
98.6%, use electrodialysis plant to reclaim the hydrochloric acid of 82% in stripping liquid, rotation steaming has been reclaimed in stripping liquid
The ethanol of 78%, and be acidization or the purge process saving of riboflavin crude product of Lactochrome fermentation liquor
The acid of more than 90% and water.
Embodiment 2
(1) Lactochrome fermentation liquor is isolated and purified, takes Lactochrome fermentation liquor 1200ml and heats at 60 DEG C
80min, the ceramic membrane filter then using aperture to be 300nm removes the impurity such as thalline；After membrane filtration
Penetrating fluid in add mass fraction 98% concentrated sulphuric acid regulation pH to 2.5, be acidified；Again to acidifying
After fermentation liquid in add mass fraction be 0.4% hydrogen peroxide 30ml, then 80 DEG C of heated and stirred
45min, is then cooled to room temperature in 30min, at 8000r/min centrifugation 10min, precipitum
It is riboflavin crude product 80 DEG C of drying, and supernatant adds concentrated sulphuric acid and continues regulation its pH to 2.5,
Acidifying for lower batch fermentation liquid.Next take riboflavin crude product and add the concentrated sulphuric acid tune of mass fraction 98%
Its pH is 2.5, dissolves and is acidified, and is subsequently added into the hydrogen peroxide 30ml that mass fraction is 0.4%,
80 DEG C of heated and stirred 45min, in 30min, finally it is cooled to room temperature, and is centrifuged at 8000r/min
Separating 10min, precipitum is riboflavin fine work 80 DEG C of drying, and supernatant exists as crystalline mother solution
Next step recycles.
(2) dynamic adsorption of riboflavin crystalline mother solution, uses wet method dress post nonpolar macroporous for 15ml tree
Fat SP825 is filled in the chromatographic column of 20cm × 1cm, then with peristaltic pump under the flow velocity of 5BV/h
Adsorb above-mentioned crystalline mother solution, when in effluent, riboflavin concentration stops inhaling when being the 10% of crystalline mother solution concentration
Attached.
(3) dynamic desorption of riboflavin crystalline mother solution: with deionized water rinsing chromatographic column to effluent pH
When being 7, then with concentrated sulphuric acid (mass fraction 98%) and ethanol solution (volume ratio 6:94)
90ml desorbing under the desorbing flow velocity of 20BV/h altogether, collects stripping liquid.
(4) recovery of sour water in stripping liquid: stripping liquid through electrodialysis process, wherein electric current density
For 6mA/cm2, flow velocity is 21L/h, the sulphuric acid of 83% in recyclable solution.
(5) recovery of ethanol in stripping liquid: use Rotary Evaporators to enter the stripping liquid of electrodialysis process
Row rotation is steamed, and it is 40 DEG C that temperature is steamed in rotation, and vacuum is 50bar, the ethanol of recyclable 82%.
(6) collection of riboflavin fine work: the riboflavin in bottle is steamed in previous step rotation, adds 20ml water-soluble
Out and sucking filtration, it is placed in the baking oven of 80 DEG C and is dried, and survey its purity by GB 14752-2010.
During this, using the riboflavin of 79.4% in the recyclable crystalline mother solution of SP825 resin, purity is
98.2%, use electrodialysis plant to reclaim the sulphuric acid of 83% in stripping liquid, rotation steaming has been reclaimed in stripping liquid
The ethanol of 82%, and be acidization or the purge process saving of riboflavin crude product of Lactochrome fermentation liquor
The acid of more than 90% and water.
Embodiment 3
(1) Lactochrome fermentation liquor is isolated and purified, takes Lactochrome fermentation liquor 1200ml and heats at 60 DEG C
80min, the ceramic membrane filter then using aperture to be 300nm removes the impurity such as thalline；After membrane filtration
Penetrating fluid in add mass fraction be 65% concentrated nitric acid regulation pH to 2.5, be acidified；Again to acid
Fermentation liquid after change adds the hydrogen peroxide 30ml that mass fraction is 0.4%, then 80 DEG C of heated and stirred
45min, is then cooled to room temperature in 30min, at 8000r/min centrifugation 10min, precipitum
It is riboflavin crude product 80 DEG C of drying, and supernatant adds concentrated nitric acid and continues regulation its pH to 2.5,
Acidifying for lower batch fermentation liquid.Next take riboflavin crude product adding mass fraction is the concentrated nitric acid of 65%
Adjusting its pH is 2.5, dissolves and is acidified, and is subsequently added into the hydrogen peroxide 30ml that mass fraction is 0.4%,
80 DEG C of heated and stirred 45min, in 30min, finally it is cooled to room temperature, and is centrifuged at 8000r/min
Separating 10min, precipitum is riboflavin fine work 80 DEG C of drying, and supernatant exists as crystalline mother solution
Next step recycles.
(2) dynamic adsorption of riboflavin crystalline mother solution, uses wet method dress post nonpolar macroporous for 15ml tree
Fat SP850 is filled in the chromatographic column of 20cm × 1cm, then with peristaltic pump under the flow velocity of 5BV/h
Adsorb above-mentioned crystalline mother solution, when in effluent, riboflavin concentration stops inhaling when being the 10% of crystalline mother solution concentration
Attached.
(3) dynamic desorption of riboflavin crystalline mother solution: with deionized water rinsing chromatographic column to effluent pH
When being 7, then with the concentrated nitric acid that mass fraction is 65% and ethanol solution (volume ratio 15:85)
90ml desorbing under the desorbing flow velocity of 20BV/h altogether, collects stripping liquid.
(4) recovery of sour water in stripping liquid: stripping liquid through electrodialysis process, wherein electric current density
For 9mA/cm2, flow velocity is 25L/h, the nitric acid of 86% in recyclable solution.
(5) recovery of ethanol in stripping liquid: use Rotary Evaporators to enter the stripping liquid of electrodialysis process
Row rotation is steamed, and it is 40 DEG C that temperature is steamed in rotation, and vacuum is 50bar, the ethanol of recyclable 83%.
(6) collection of riboflavin fine work: the riboflavin in bottle is steamed in previous step rotation, adds 20ml water-soluble
Out and sucking filtration, it is placed in the baking oven of 80 DEG C and is dried, and survey its purity by GB 14752-2010.
During this, using the riboflavin of 81.2% in the recyclable crystalline mother solution of SP850 resin, purity is
97.1%, use electrodialysis plant to reclaim the nitric acid of 86% in stripping liquid, rotation steaming has been reclaimed in stripping liquid
The ethanol of 83%, and be acidization or the purge process saving of riboflavin crude product of Lactochrome fermentation liquor
The acid of more than 90% and water.
Embodiment 4
(1) Lactochrome fermentation liquor is isolated and purified, takes Lactochrome fermentation liquor 1200ml and heats at 60 DEG C
80min, the ceramic membrane filter then using aperture to be 300nm removes the impurity such as thalline；After membrane filtration
Penetrating fluid in add 36%～38% salt acid for adjusting pH to 2.5, be acidified；Again after acidifying
Fermentation liquid adds the hydrogen peroxide 30ml that mass fraction is 0.4%, then 80 DEG C of heated and stirred 45min,
Then being cooled to room temperature in 30min, at 8000r/min centrifugation 10min, precipitum is at 80 DEG C
Drying is riboflavin crude product, and adds hydrochloric acid in supernatant and continue regulation its pH to 2.5, for lower batch
The acidifying of fermentation liquid.Next the hydrochloric acid taking riboflavin crude product addition 36%～38% adjusts its pH to be 2.5,
Dissolve and be acidified, being subsequently added into the hydrogen peroxide 30ml that mass fraction is 0.4%, stir 80 DEG C of heating
Mix 45min, in 30min, be finally cooled to room temperature, and at 8000r/min centrifugation 10min, heavy
Fall thing is riboflavin fine work 80 DEG C of drying, and supernatant is carried out back in next step as crystalline mother solution
Receive and utilize.
(2) dynamic adsorption of riboflavin crystalline mother solution, uses wet method dress post nonpolar macroporous for 15ml tree
Fat HP20 is filled in the chromatographic column of 20cm × 1cm, then with peristaltic pump under the flow velocity of 10BV/h
Adsorb above-mentioned crystalline mother solution, when in effluent, riboflavin concentration stops inhaling when being the 15% of crystalline mother solution concentration
Attached.
(3) dynamic desorption of riboflavin crystalline mother solution: with deionized water rinsing chromatographic column to effluent pH
When being 6, then with hydrochloric acid (mass fraction 36%～38%) and ethanol solution (volume ratio 3:7)
75ml desorbing under the desorbing flow velocity of 15BV/h altogether, collects stripping liquid.
(4) recovery of sour water in stripping liquid: stripping liquid through electrodialysis process, wherein electric current density
For 6mA/cm2, flow velocity is 21L/h, the hydrochloric acid of 84% in recyclable solution.
(5) recovery of ethanol in stripping liquid: use Rotary Evaporators to enter the stripping liquid of electrodialysis process
Row rotation is steamed, and it is 50 DEG C that temperature is steamed in rotation, and vacuum is 45bar, the ethanol of recyclable 84%.
(6) collection of riboflavin fine work: the riboflavin in bottle is steamed in previous step rotation, adds 20ml water-soluble
Out and sucking filtration, it is placed in the baking oven of 75 DEG C and is dried, and survey its purity by GB 14752-2010.
During this, using the riboflavin of 82.7% in the HP 20 recyclable crystalline mother solution of resin, purity is
98.3%, use electrodialysis plant to reclaim the hydrochloric acid of 84% in stripping liquid, rotation steaming has been reclaimed in stripping liquid
The ethanol of 84%, and be acidization or the purge process saving of riboflavin crude product of Lactochrome fermentation liquor
The acid of more than 90% and water.
Embodiment 5
(1) Lactochrome fermentation liquor is isolated and purified, takes Lactochrome fermentation liquor 1200ml and heats at 80 DEG C
1h, the ceramic membrane filter then using aperture to be 500nm removes the impurity such as thalline；Oozing after membrane filtration
In transparent liquid, the salt acid for adjusting pH of addition 36%～38% is to 3, is acidified；Fermentation liquid after acidifying again
Middle addition mass fraction is the hydrogen peroxide 10ml of 0.5%, then 90 DEG C of heated and stirred 30min, then
Being cooled to room temperature in 30min, at 10000r/min centrifugation 5min, precipitum is 85 DEG C of drying
It is riboflavin crude product, and supernatant adds hydrochloric acid and continues regulation its pH to 3, for lower batch fermentation
The acidifying of liquid.Next the hydrochloric acid taking riboflavin crude product addition 36%～38% adjusts its pH to be 3, carries out molten
Solve and be acidified, be subsequently added into the hydrogen peroxide 10ml that mass fraction is 0.5%, 90 DEG C of heated and stirred 30min,
Finally in 30min, it is cooled to room temperature, and at 10000r/min centrifugation 5min, precipitum is 85
DEG C drying is riboflavin fine work, and supernatant recycles in next step as crystalline mother solution.
(2) dynamic adsorption of riboflavin crystalline mother solution, uses wet method dress post nonpolar macroporous for 15ml tree
Fat H103 is filled in the chromatographic column of 20cm × 1cm, then with peristaltic pump under the flow velocity of 15BV/h
Adsorb above-mentioned crystalline mother solution, when in effluent, riboflavin concentration stops inhaling when being the 15% of crystalline mother solution concentration
Attached.
(3) dynamic desorption of riboflavin crystalline mother solution: with deionized water rinsing chromatographic column to effluent pH
When being 6, then with hydrochloric acid (mass fraction 36%～38%) and ethanol solution (volume ratio 4:6)
60ml desorbing under the desorbing flow velocity of 10BV/h altogether, collects stripping liquid.
(4) recovery of sour water in stripping liquid: stripping liquid through electrodialysis process, wherein electric current density
For 9mA/cm2, flow velocity is 25L/h, the hydrochloric acid of 86% in recyclable solution.
(5) recovery of ethanol in stripping liquid: use Rotary Evaporators to enter the stripping liquid of electrodialysis process
Row rotation is steamed, and it is 30 DEG C that temperature is steamed in rotation, and vacuum is 80bar, the ethanol of recyclable 72%.
(6) collection of riboflavin fine work: the riboflavin in bottle is steamed in previous step rotation, adds 20ml water-soluble
Out and sucking filtration, it is placed in the baking oven of 85 DEG C and is dried, and survey its purity by GB 14752-2010.
During this, using the riboflavin of 72.3% in the recyclable crystalline mother solution of H103 resin, purity is
97.7%, use electrodialysis plant to reclaim the hydrochloric acid of 86% in stripping liquid, rotation steaming has been reclaimed in stripping liquid
The ethanol of 72%, and be acidization or the purge process saving of riboflavin crude product of Lactochrome fermentation liquor
The acid of more than 90% and water.
Claims (8)
1. the method that high-efficiency environment friendly reclaims riboflavin from crystalline mother solution, it is characterised in that step
As follows:
(1) Lactochrome fermentation liquor is isolated and purified: Lactochrome fermentation liquor is preprocessed, acidifying, oxygen
Changing crystallization, solid-liquid separation obtains riboflavin crude product, and riboflavin crude product is through being recrystallized to give riboflavin essence
Product and crystalline mother solution, and crystalline mother solution recycles in subsequent step；
(2) dynamic adsorption of riboflavin crystalline mother solution: select aperture between 40～300Non-pole
Property macroporous resin, 5～20BV/h flow velocitys adsorb riboflavin crystalline mother solutions；
(3) dynamic desorption of riboflavin crystalline mother solution: with deionized water rinsing chromatographic column to effluent
When pH is 6～7, then to use dehydrated alcohol and mineral acid mixed solution be that eluent is 5～20BV/h
Carry out eluting under flow velocity, collect stripping liquid；
(4) recovery of mineral acid in stripping liquid: use electrodialysis plant to process stripping liquid, reclaim and solve
Mineral acid in imbibition, the mineral acid of recovery is reused for preparing the eluent in (3)；
(5) recovery of ethanol in stripping liquid: use evaporation concentration equipment to process stripping liquid, reclaim and solve
Ethanol in imbibition, the ethanol of recovery is reused for preparing the eluent in (3)；
(6) collection of riboflavin fine work: in step (5) in the riboflavin that evaporation and concentration obtains
Add water-soluble go out and sucking filtration, be placed in the baking oven of 75～85 DEG C be dried.
Method the most according to claim 1, it is characterised in that: described non-polar macroporous resin
Selected from SP207, HP20, H103, SP825 or SP850.
Method the most according to claim 1, it is characterised in that: the absorption in step (2)
Flow velocity is 5～10BV/h.
Method the most according to claim 1, it is characterised in that: the outflow in step (2)
Liquid is the acidification step in step (1) after mineral acid tune pH is 2～3.
Method the most according to claim 1, it is characterised in that: the eluting in step (3)
Liquid is dehydrated alcohol and mineral acid mixed solution, and wherein mineral acid mass concentration is 5%～15%, second
Alcohol mass concentration is 60%～80%；Described mineral acid is selected from hydrochloric acid, sulphuric acid or nitric acid；Eluent
Fixing fabric structure is 4～6BV.
Method the most according to claim 1, it is characterised in that: the flow velocity in step (3)
Control 10～20BV/h.
Method the most according to claim 1, it is characterised in that: the electric osmose in step (4)
Analysis process, electric current density controls 3～9mA/cm2, flow speed control is 18～25L/h.
Method the most according to claim 1, it is characterised in that: the evaporation in step (5)
In concentration process, temperature controls at 30～50 DEG C, and vacuum degree control is 45～80bar.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410579130.5A CN104327082B (en) | 2014-10-26 | 2014-10-26 | A kind of method that high-efficiency environment friendly reclaims riboflavin from crystalline mother solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410579130.5A CN104327082B (en) | 2014-10-26 | 2014-10-26 | A kind of method that high-efficiency environment friendly reclaims riboflavin from crystalline mother solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104327082A CN104327082A (en) | 2015-02-04 |
| CN104327082B true CN104327082B (en) | 2016-11-16 |
Family
ID=52401901
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410579130.5A Active CN104327082B (en) | 2014-10-26 | 2014-10-26 | A kind of method that high-efficiency environment friendly reclaims riboflavin from crystalline mother solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104327082B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113943291B (en) * | 2021-11-30 | 2023-09-08 | 湖北广济药业股份有限公司 | Method for removing residual DNA in riboflavin by nuclease |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4945100A (en) * | 1972-09-08 | 1974-04-27 | ||
| CN1765897A (en) * | 2004-10-27 | 2006-05-03 | 上海凯赛生物技术研发中心有限公司 | Lactochrome fermentation liquor extraction process |
-
2014
- 2014-10-26 CN CN201410579130.5A patent/CN104327082B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4945100A (en) * | 1972-09-08 | 1974-04-27 | ||
| CN1765897A (en) * | 2004-10-27 | 2006-05-03 | 上海凯赛生物技术研发中心有限公司 | Lactochrome fermentation liquor extraction process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104327082A (en) | 2015-02-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101691349B (en) | Process for extracting tryptophan from fermentation liquid | |
| CN102295983A (en) | Production method for comprehensive utilization of microalgae | |
| CN109956856B (en) | Method for extracting coenzyme Q10 and phospholipid from coenzyme Q10 fermentation strain powder | |
| CN101870668A (en) | Method for preparing beta-carotin from Blakeslea trispora fermentation broth | |
| CN105294790A (en) | Method for extracting high-purity steviol glycosides from stevia rebaudiana | |
| CN104530173A (en) | Process for extracting tea saponin from oil tea cake | |
| CN1830996A (en) | Method for preparing chenodeoxycholic acid | |
| CN111995880B (en) | Method for extracting biologically fermented carotenoid | |
| CN104876824A (en) | Technology for separation and purification of chlorogenic acid from coffee beans | |
| CN111333600A (en) | Method for extracting vitamin C from kiwi fruits | |
| CN111484539A (en) | Novel process method for extracting hesperidin by alkaline alcohol | |
| CN105273014A (en) | Preparation method of high-content geniposide crystals | |
| CN106188181B (en) | A method of extracting aurantiin from pomelo peel | |
| CN102320953B (en) | Method for preparing natural alpha-linolenic acid from crude oil of idesia polycarpa var.vestita diels | |
| CN106632547A (en) | Method for extracting naringin, synephrine and pectin from young shaddock fruits | |
| CN102643315A (en) | Method for purifying phlorizin from apple velamen | |
| CN104327082B (en) | A kind of method that high-efficiency environment friendly reclaims riboflavin from crystalline mother solution | |
| CN109942657A (en) | A method of extracting dehydrobenzene from sweet potato | |
| CN103333213B (en) | The method of oleuropein is extracted from leaf of Fructus oleae europaeae | |
| CN105534897A (en) | Preparation method of highly water-soluble quercetin microemulsion | |
| CN101375863A (en) | Method for extracting polysaccharide and other multiple active components in boiling juice of trepang | |
| CN104357527B (en) | A kind of method that microbe fermentation method extracts Tea Saponin from leached tea oil slag | |
| CN103694280B (en) | From containing the method extracting glucosamine hydrochloride glucosamine hydrochloride mother liquid | |
| CN111018929B (en) | Process for extracting and separating isocoryzanol | |
| CN102321143A (en) | Method for preparing high-purity betulin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |