CN101475972B - Method for producing L-arabinose from corncob - Google Patents
Method for producing L-arabinose from corncob Download PDFInfo
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- CN101475972B CN101475972B CN2009100779433A CN200910077943A CN101475972B CN 101475972 B CN101475972 B CN 101475972B CN 2009100779433 A CN2009100779433 A CN 2009100779433A CN 200910077943 A CN200910077943 A CN 200910077943A CN 101475972 B CN101475972 B CN 101475972B
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Abstract
The present invention provides a method of using corn core to produce L-arabinose, including the following steps: processing the corn cob to get the raw materials containing L-arabinose, inoculating microorganism to improve the purity of the L-arabinose component and simultaneously produce other byproducts, and then isolating the byproducts and L-arabinose, respectively extracting, refining, to get the high-purity L-arabinose and byproducts. The method has advantages of low production cost, high productivity, a wide array of raw material sources, and capability of adjusting the byproduct kinds at any time in accordance with market conditions, etc.
Description
Technical field
The present invention relates to a kind of working method of L-arabinose, specifically, relate to a kind of method of utilizing corn cob to produce L-arabinose, belong to medicine, food chemical field.
Background technology
L-arabinose is a kind of function sugar of using industries such as food and medicine, has special physiological properties.Physiologist and nutritionist with regard to L-arabinose in enteron aisle to being used as of sugar metabolism the series of studies discovery: L-arabinose has remarkable blocking effect to the metabolic conversion of sucrose, makes its good in fat-reducing, application prospect aspect the control of diabetes.It is reported that the L-arabinose that needs only interpolation 2% in common sucrose just can suppress the absorption of sucrose, has suppressed blood glucose value simultaneously and has raise about 50% less.If the L-arabinose addition reaches 4%, blood glucose value is not raise fully, Regular Insulin is secreted hardly.
According to estimates, China has 4,000 ten thousand above diabeticss at least, has become the third-largest state of world diabetics, and other has 6,000 ten thousand pre-diabetes crowds.Therefore, L-arabinose for ordinary people influence bigly may add iodine with salt, soy sauce adds iron and mentions in the same breath.
CN1299420A has proposed a kind of method of producing L-arabinose through acid hydrolysis; This method weak point is the simple degrade plant material such as hydrochloric acid or sulfuric acid of using in the whole process; The product of preparation is the mixed sugar liquid that contains L-arabinose, wood sugar, semi-lactosi and glucose etc.; Its raw material treatment capacity is 500 grams to the maximum, how not to show in the technological process to obtain L-arabinose xln product by purifying.
CN1373135A proposes to use the acid hydrolysis gum arabic, separates the method for L-arabinose then through column chromatography, and weak point is that production cost is high, efficient is low.
CN1966665A, CN101100685A propose to produce L-arabinose with sulfuric acid and glycase degrading maize wheat bran, and its weak point is the corn bran feedstock quantity not sufficient to satisfy the demands, and output is restricted, and the corn bran price is higher than corn cob far away.
Existing in a word L-arabinose production technology is sayed from large-scale production, all exists certain problem on its economy and the production efficiency.
Summary of the invention
The purpose of this invention is to provide that a kind of production cost is low, production efficiency is high, raw material sources L-arabinose working method widely.
In order to realize the object of the invention, a kind of method of utilizing corn cob to produce L-arabinose of the present invention comprises the steps:
1) earlier corn cob is carried out s.t., obtain corn cob liquid glucose and corn cob slag, again corn cob liquid glucose purifying treatment is obtained containing the raw material of L-arabinose;
The raw material that 2) will contain L-arabinose then ferments through microbe inoculation, fermented liquid;
3) again to fermented liquid handle sub product and L-arabinose;
4) respectively sub product and L-arabinose are made with extra care at last, obtained sub product and crystallization L-arabinose.
Wherein, the acid that the said corn cob s.t. of step 1) is used is sulfuric acid, hydrochloric acid, phosphoric acid etc. or their mixture, and acid concentration is 0.01N-0.5N, and temperature is 80-150 ℃, and the treatment time is 10-300 minute.
Corn cob can obtain corn cob liquid glucose and corn cob slag through peracid treatment.
Said corn cob liquid glucose can further be handled and obtain L-arabinose, can mainly contain the fermention medium or the fuel of glucose as preparation for the corn cob slag.
Steps such as said corn cob liquid glucose purifying treatment comprises decolouring, desalination, concentrate, specifically, the general gac that adopts of decolouring carries out, and desalination adopts ion exchange resin to carry out, and concentrates to adopt reverse osmosis membrane to carry out.
Step 2) said mikrobe is a yeast, specifically comprises candiyeast, bread yeast, cereuisiae fermentum or pichia spp etc.
The present invention inoculates different types of yeast will utilize wood sugar or the different product of glucose generation in the corn cob liquid glucose, just can produce alcohol like the inoculation pichia spp, and the inoculation candida tropicalis just can produce Xylitol, but L-arabinose can not be utilized.
Microbial fermentation according to the invention can adopt this area strain inclined plane commonly used to cultivate and the seed enlarged culturing.
The gained fermented liquid need carry out degerming, removal of impurities, decolouring, desalination step process behind the microbial fermentation.Can obtain sub product and the material that is rich in L-arabinose respectively.
The material that is rich in L-arabinose through concentrating, crystallization, centrifugal highly purified crystallization L-arabinose.
Said concentrating adopts reverse osmosis membrane-systems and/or vaporizers to carry out more.
Through the processing of the present invention, except obtaining also can to obtain different sub products the L-arabinose, such as changing into Xylitol or ethanol by glucose, wood sugar to corn cob.
The working method of L-arabinose of the present invention; Use the corn cob raw material of wide material sources,, obtain containing the raw material of L-arabinose through the s.t. method and the liquid glucose purifying method of routine; Through microbe inoculation, produce other products when having improved in the material purity of L-arabinose.Its advantage is:
1. use the corn cob raw material, production cost is low;
2. L-arabinose content is higher in the corn cob, and production efficiency is high, and the yield of L-arabinose generally can reach about 85%, and the L-arabinose product purity can reach 99.5%;
3. raw material sources is extensive;
4. through microbe inoculation, make that glucose, wood sugar are converted into easily and the L-arabinose components separated in the corn cob liquid glucose, and the kind of the sub product that is changed into by glucose, wood sugar can adjust also, such as changing into Xylitol or ethanol.
Embodiment
Following examples are used to explain the present invention, but are not used for limiting scope of the present invention.
Embodiment 1
The method of corn cob pre-treatment and corn cob liquid glucose purifying treatment comprises the steps:
1. the weight of will giving money as a gift earlier is 1000 kilograms, and putting into volume through the corn cob of washing after the removal of impurities is in the 5 cubical acidolysis pots, after adding water and being settled to 4.5 cubes temperature is heated to 110 ℃ and add 40 kilograms of vitriol oils, is incubated 60 minutes.
2. above-mentioned material is separated through sheet frame, and the washing solid phase, 4.5 cubes of corn cob liquid glucoses and corncob acid hydrolysis slag obtained.
In the corn cob liquid glucose by volume 1 ‰ add Powdered Activated Carbons, insulation is 30 minutes under 55 ℃ of conditions, removes gac with candle filter then, obtains the liquid glucose that decolours.
4. the decolouring liquid glucose gets into cationic exchange coloum that loads 001 * 7 Zeo-karb and the anion-exchange column that loads 201 * 7 anionite-exchange resin, removes foreign ion in the liquid glucose, obtains from handing over liquid glucose;
5. after handing over liquid glucose to get into the reverse osmosis membrane concentrating unit to concentrate, obtain total sugar concentration and be 15% corn cob liquid glucose (for containing the raw material of L-arabinose).
Following table 1 is a corn cob liquid glucose staple.
The staple of table 1 corn cob liquid glucose
Project | Content (%) |
The DNS total reducing sugar | 15 |
Glucose | 0.57 |
Wood sugar | 12.65 |
L-arabinose | 1.80 |
Embodiment 2
Produce L-arabinose, the working method of by-product Xylitol, the Xylitol preparation comprises the steps:
1. Xylitol seed preparation: from the strain inclined plane to the shake-flask culture, insert seeding tank then, the seed tank culture base consist of embodiment 1 preparation corn cob concentrate liquid glucose, yeast powder, steeping water, feed sterile air and cultivate.
Bacterial classification: candida tropicalis (G.tropicalis)
Slant medium: glucose 1%, wood sugar 1%, yeast powder 0.3%, peptone 0.5%, corn cob liquid glucose 3%, agar 2%.
Shake-flask culture base: glucose 1%, wood sugar 2%, yeast powder 0.5%, peptone 0.8%.Seed tank culture base: corn cob liquid glucose 3%, yeast powder 0.5%, steeping water 0.8%, glucose 1%.
Seed tank culture condition: ventilating ratio: 1: 0.5;
Culture temperature: 29~31 ℃
Cultivate pH:6.0~6.5
2. fermentative prepn Xylitol
The corn cob of embodiment 1 preparation is concentrated liquid glucose, add in the fermentor tank, add the steeping water of 0.1% ammonium sulfate and 0.3%; Steam heating to 121 ℃ was kept 30 minutes, was cooled to 32 ℃; Insert the seed liquor that step 1 is cultivated, inoculum size is 10% of a fermention medium volume.
Technological condition for fermentation: initial pH6.0; Ventilating ratio adopts two sections control methods: preceding 10 hours 1: 0.4, reduce to 1: 0.15 then, up to fermentation ends.30~32 ℃ of leavening temperatures, fermentation period was less than 72 hours.
The fermenting-ripening mash is seen: brown liquid, proportion 1.06, wet amount of yeast 5%; Xylitol concentration 9.5%; Xylitol is to wood sugar transformation efficiency 75%.
3. xylitol fermentation liquor is handled
Fermented liquid degerming, removal of impurities
Fermented liquid is the board-like membrane filtration of 50KD through molecular weight cut-off, obtains clarifying fermentation clear liquid and yeast, and yeast oven dry back is as feed.
The decolouring of powder carbon
Under 75~80 ℃ of conditions, add Powdered Activated Carbon, dosage is 3 ‰ of a volume of material, is incubated after 30 minutes to filter with plate-and-frame filter press, obtains the Xylitol destainer.
The IX desalination
Destainer gets into the cationic exchange coloum of filling 001 * 7 strongly acidic cation-exchange, the anion-exchange column of filling 201 * 7 strong basic type anion-exchange resins, and input speed is controlled at 5BVS/h, obtains Xylitol from handing over liquid.
Concentrate: the material solid content is brought up to 90% with plate-type evaporator.
Crystallization: the material after will concentrating is put into horizontal crystallizer, is cooled to 50~60 ℃, presses 10% of Xylitol amount and adds xylitol seed crystals, and growing the grain by the cooling of 1 ℃/h cooling rate, cooled to below 25 ℃ after 10 hours.
Separate:, obtain xylitol crystal and Xylitol mother liquor with whizzer fractional crystallization material.
Embodiment 3
Produce L-arabinose, the working method of by-product Xylitol, the L-arabinose preparation comprises the steps:
1. L-arabinose separates in the Xylitol mother liquor
The Xylitol mother liquor that embodiment 2 is produced pumps into the simulated moving bed system of loading PCR642,60 ℃ of system operation temperature, and washing water quantity is 8 times of inlet amount, collects wood sugar phase, L-arabinose phase, Xylitol phase respectively.
2.L-pectinose concentrates
The L-arabinose that simulated moving bed system is collected gets into RO system (reverse osmosis system) mutually, and material is concentrated into solid content 15%, with plate-type evaporator the material solid content is brought up to 75% then.
3.L-pectinose crystallization
L-arabinose after concentrating is put into horizontal crystallizer, is cooled to the crystal seed that adds L-arabinose amount 2% after 45 ℃, and growing the grain by the cooling of 1 ℃/h cooling rate, cooled to below 25 ℃ after 10 hours.
4.L-pectinose is centrifugal
With whizzer fractional crystallization material, and, obtain L-arabinose crystal and L-arabinose mother liquor with 10 ℃ of cold water washing crystal.
Embodiment 4
Produce L-arabinose, by-product alcoholic acid working method, ethanol preparation comprises the steps:
1. ethanol fermentation seed preparation
Substratum consists of corn cob and concentrates liquid glucose 5 ± 1%, yeast extract paste 0.2%, steeping water 1%, potassium hydrogenphosphate 0.15%, ammonium sulfate 0.05%, Secondary ammonium phosphate 0.2%.
With substratum through 110 ℃ of sterilizations 20 minutes, be cooled to 31 ℃ after, by 10% inoculum size inoculation yeast CGMCC No.1859 (preservation date: on November 08th, 2006, and open in CN101186943), culture condition: 31 ℃, cultivated 36 hours.
2. fermentation culture
Substratum consists of corn cob and concentrates liquid glucose 14 ± 1%, yeast extract paste 0.2%, steeping water 1%, potassium hydrogenphosphate 0.05%, ammonium sulfate 0.05%, Secondary ammonium phosphate 0.15%.
Substratum is through 121 ℃ of sterilizations 30 minutes, be cooled to 36 ℃ after, insert to cultivate sophisticated seed liquor by 10% inoculum size; Fermentation condition: 36 ℃ of leavening temperatures, fermentation pH4.8 ± 0.2, ventilating ratio was 1: 0.2 in preceding 4 hours; Stop after 4 hours ventilating fermentation period 58 hours.
3. the degerming of ethanol fermentation liquid, removal of impurities
Fermentation liquid is obtained yeast and fermentation clear liquid after through the disk plate centrifuge separated yeast, and yeast oven dry back is as feed.
4. ethanol distillation
Through distillation tower, cat head is gathered ethanol with the fermentation clear liquid after degerming, the removal of impurities, and tower bottoms is the component that is rich in L-arabinose.
Embodiment 5
Produce L-arabinose, by-product alcoholic acid working method, the L-arabinose preparation comprises the steps:
1. tower bottoms decolouring
Under 75 ℃ of conditions, add Powdered Activated Carbon, dosage is 2 ‰ of a volume of material, is incubated after 30 minutes to filter with plate-and-frame filter press, obtains the tower bottoms destainer.
2. IX desalination
Destainer gets into the cationic exchange coloum of filling 001 * 7 strongly acidic cation-exchange, the anion-exchange column of filling 201 * 7 strong basic type anion-exchange resins, and input speed is controlled at 5BVS/h, obtains tower bottoms from handing over liquid.
3. concentrate: the material solid content is brought up to 15% with the RO film.
4.L-pectinose separates
RO membrane-concentrated liquid gets into the simulated moving bed system of filling PCR642,60 ℃ of system operation temperature, and washing water quantity is 4 times of inlet amount, collects wood sugar phase, L-arabinose phase, fusel phase respectively.
5.L-pectinose concentrates
The L-arabinose that simulated moving bed system is collected gets into the RO system mutually, and material is concentrated into solid content 15%, with plate-type evaporator the material solid content is brought up to 75% then.
6.L-pectinose crystallization
L-arabinose after concentrating is put into horizontal crystallizer, is cooled to the crystal seed that adds L-arabinose amount 2% after 45 ℃, and growing the grain by the cooling of 1 ℃/h cooling rate, cooled to below 25 ℃ after 10 hours.
7.L-pectinose is centrifugal
With whizzer fractional crystallization material, and, obtain the L-arabinose crystal with 10 ℃ of cold water washing crystal.Product purity reaches 99.5%.
Though, the present invention has been done detailed description in the preceding text with general explanation and specific embodiments, on basis of the present invention, can to some modifications of do or improvement, this will be apparent to those skilled in the art.Therefore, these modifications or the improvement on the basis of not departing from spirit of the present invention, made all belong to the scope that requirement of the present invention is protected.
Claims (2)
1. a method of utilizing corn cob to produce L-arabinose is characterized in that, comprises the steps:
1) earlier corn cob is carried out s.t.; The acid that s.t. is used is sulfuric acid, and acid concentration is 0.01N-0.5N, and temperature is 80-150 ℃; Treatment time is 10-300 minute; Obtain corn cob liquid glucose and corn cob slag, again with the corn cob liquid glucose through gac, ion exchange resin, reverse osmosis membrane processing, obtain containing the raw material of L-arabinose;
The raw material that 2) will contain L-arabinose then ferments through inoculation yeast CGMCC No.1859, fermented liquid;
3) again fermented liquid is carried out degerming, removal of impurities, decolouring, desalting treatment and get sub product ethanol and L-arabinose;
4) respectively sub product ethanol and L-arabinose are made with extra care at last, obtained sub product ethanol and crystallization L-arabinose.
2. according to the said L-arabinose working method of claim 1, it is characterized in that refining concentrated, crystallization, the centrifugation step of comprising described in the step 4).
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CN101665523B (en) * | 2009-09-30 | 2015-09-30 | 济南圣泉唐和唐生物科技有限公司 | The production method of L-arabinose and D-xylose pref |
CN101824055B (en) * | 2009-12-30 | 2012-07-25 | 山东福田药业有限公司 | Method for preparing L-arabinose by taking corn bran as material |
CN101818216B (en) * | 2010-04-26 | 2012-07-04 | 安徽丰原发酵技术工程研究有限公司 | Method for refining corncob acid hydrolysis solution |
CN102659854B (en) * | 2012-03-15 | 2014-08-13 | 济南圣泉唐和唐生物科技有限公司 | Purification method for L-arabinose |
CN103274404B (en) * | 2013-06-19 | 2016-03-30 | 济南圣泉集团股份有限公司 | The method of active carbon adsorption material is prepared by plant acidolysis slag |
CN114032256A (en) * | 2021-10-15 | 2022-02-11 | 山东寿光巨能金玉米开发有限公司 | Method for co-producing ethanol and L-arabinose by using corn bran |
CN117069776A (en) * | 2023-08-01 | 2023-11-17 | 北京澳特舒尔保健品开发有限公司 | Method for preparing L-arabinose from liquid xylitol |
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CN1299420A (en) * | 1998-05-01 | 2001-06-13 | 三和兴产株式会社 | Process for producing L-arabinose by acid hydrolysis method |
CN101100685A (en) * | 2007-08-01 | 2008-01-09 | 李萍 | Method for preparing L-arabinose |
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CN1299420A (en) * | 1998-05-01 | 2001-06-13 | 三和兴产株式会社 | Process for producing L-arabinose by acid hydrolysis method |
CN101100685A (en) * | 2007-08-01 | 2008-01-09 | 李萍 | Method for preparing L-arabinose |
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