CN101665524B - Method for producing L-arabinose - Google Patents
Method for producing L-arabinose Download PDFInfo
- Publication number
- CN101665524B CN101665524B CN2009100187996A CN200910018799A CN101665524B CN 101665524 B CN101665524 B CN 101665524B CN 2009100187996 A CN2009100187996 A CN 2009100187996A CN 200910018799 A CN200910018799 A CN 200910018799A CN 101665524 B CN101665524 B CN 101665524B
- Authority
- CN
- China
- Prior art keywords
- membrane
- time
- glucose
- acid
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The invention relates to a method for producing L-arabinose, which can simultaneously produce ethanol, D-ribose and citric acid as byproducts. The method utilizes a hydrolyzate of agricultural waste, a xylose mother liquor and/or a production waste liquor containing pentose as the raw materials and comprises the following steps: (a) pretreating the raw materials; (b) carrying out the chromatographic resolution to separate the raw materials into an arabinose-stage liquor and a xylose-stage liquor; (c) removing impurities and unwanted bacteria, which have an inhibiting effect on fermentation, as well as unwanted saccharides at least comprising glucose and galactose; (d) and carrying out the post treatment on the arabinose-stage liquor to obtain the L-arabinose. Steps (c1) and (c2) are arranged before the chromatographic resolution in step (b) or after step (b). The invention has the advantages of low production cost and high efficiency, and is suitable for large-scale industrial production.
Description
Technical field
The present invention relates to the production technology of L-arabinose, especially take hemicellulose hydrolysate, xylose mother liquid and the production waste liquid that contains five-carbon sugar as raw material production L-arabinose goods, the method for the glucose fermentation products such as by-product ethanol, D-ribose, citric acid simultaneously.
Technical background
L-arabinose belongs to five-carbon ring aldehydo sugar, exists with arabinan, aralino xylan, aralino galactan and the form that is similar to higher plant half fiber.L-arabinose is a kind of sweeting agent that does not have heat, can also be used as medicine intermediate, to be used for the preparation of biochemical field bacteria culture medium and spices synthetic etc.Xylose pref such as wood sugar, Xylitol more and more are subject to people's favor as sweetening agent.A lot of medical health care functions of wood sugar, Xylitol are confirmed by scientific research, such as lowering blood glucose, prevent the functions such as carious tooth.
Plant tissue is comprised of Mierocrystalline cellulose, hemicellulose, xylogen and similar material mostly, and wherein hemicellulose mainly is to be made of L-arabinose and D-wood sugar.The L-arabinose content of different plant tissues is different.
Chinese patent 200910077943.3 discloses a kind of method of utilizing corn cob to produce L-arabinose, disclosed a kind of pectinose, the technique of by-product Xylitol simultaneously of producing of embodiment 1～3 wherein, the step that specifically comprises has: acidolysis corn cob, biological fermentation prepare Xylitol, fermented liquid aftertreatment, Xylitol crystallization, Xylitol mother liquor chromatographic separation and get pectinose.Limitation and deficiency that this patent exists are: 1) can only produce pectinose and Xylitol with corn cob, raw material sources are single.2) the materials such as the polymer substance such as the fermentation inhibitor of feed liquid such as phenyl ring class, heterocyclic and metal ion are not removed before the fermentation, cause fermentation not carry out smoothly; 3) this patent not except the step of glucose and semi-lactosi, can not be purified after causing chromatographic separation pectinose and Xylitol before chromatographic separation pectinose and Xylitol.What 4) feed liquid fermentation is adopted is candida tropicalis, and pectinose generates arabitol when removing xylose and glucose, thereby consumes in a large number pectinose even exhaust and can not obtain the pectinose product.5) this patented technology can only be produced Xylitol, and can not the direct production wood sugar, and range of application is greatly limited.
Chinese patent CN101100685A discloses a kind of method for preparing L-arabinose, its method is: the raw material corn bran is processed with amylase first, then use the dilute acid hydrolysis corn bran, spent ion exchange resin carries out the desalination removal of impurities to hydrolyzed solution, the inoculation yeast bacterium is fermented and removes assorted monose, and the fermented liquid crystallization obtains the L-arabinose product.All assorted sugar that comprise wood sugar, xylan in this patent all remove with yeast fermentation, and so just bring several problems: at first, xylan can't ferment with yeast, could ferment after must being hydrolyzed into monose; In addition, what account for main component in the hydrolyzed solution is wood sugar, must with the bacterial classification that can utilize five-carbon sugar, certainly will cause like this fermentation loss of pectinose if most of wood sugars are removed in fermentation.And if because Xylose Content is more is removed as impurity, slattern on the one hand a large amount of wood sugars, economic not environmental protection; Can all not change into carbonic acid gas and water after the wood-sugar fermentation on the other hand, but generate other metabolic intermediate, as: glycerine, pyruvic acid, Glycerose, xylulose etc.These impurity are difficult for removing by the way of crystallization, thereby cause the pectinose product purity inadequate.
In sum, also there is not the production method that a kind of cost is low, efficient is high, can realize large-scale industrial production high purity L-arabinose in the prior art.
Summary of the invention
In order to overcome the defective of above-mentioned prior art, the purpose of this invention is to provide a kind of from hemicellulose hydrolysate, xylose mother liquid and contain the agriculture and forestry organic waste material of five-carbon sugar and waste liquid, waste material the production high purity L-arabinose method of the glucose fermentation products such as by-product ethanol, D-ribose, citric acid simultaneously.Method production cost of the present invention is low, efficient is high, is suitable for large-scale industrial production.
In order to realize the foregoing invention purpose, the present invention has adopted following technical scheme:
1, a kind of production method of L-arabinose take hydrolyzed solution, the xylose mother liquid of agriculture and forestry organic waste material and/or the production waste liquid that contains five-carbon sugar as raw material, may further comprise the steps at least:
(a) feed liquid pre-treatment is treated to described raw material the mixed liquor that comprises at least wood sugar, xylan, L-arabinose, glucose and semi-lactosi;
(b) chromatographic separation is separated into pectinose fraction feed liquid and wood sugar fraction feed liquid with described mixed liquor, obtains pectinose fraction feed liquid;
(c) may further comprise the steps (c1) and (c1), this two step or place before the chromatographic separation of step (b) described mixed liquor processed or place the chromatographic separation of step (b) after described pectinose fraction feed liquid is carried out the processing of following two steps:
(c1) except fermentation inhibitor, described fermentation inhibitor is impurity and the miscellaneous bacteria that fermentation is had inhibition;
(c2) fermentation removal of impurities sugar, described assorted sugar comprises glucose and semi-lactosi at least;
(d) at last described pectinose fraction feed liquid is carried out aftertreatment and obtain L-arabinose.
2, the feed liquid pre-treatment of the hydrolyzed solution of the wherein said agriculture and forestry organic waste material of technique scheme comprises the following steps:
1. clean: silt and the chip of removing described agriculture and forestry organic waste material surface;
2. dilute acid pretreatment: soak described agriculture and forestry organic waste material to remove impurity with diluted acid, described dilute acid concentration is at 0.05～0.15%wt, and temperature is 110～130 ℃, and the treatment time is 1～3 hour; Described diluted acid comprises the mixed solution of in sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, nitric acid or these acid certain two kinds and two or more acid;
3. hydrolysis: add the dense acid solution at 0.5～1%wt of acid, 128～132 ℃ of insulations of temperature 2.5 hours; Described acid solution comprises the mixed solution of in sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, nitric acid or these acid certain two kinds and two or more acid;
4. neutralization: at first liquid glucose is heated to 80～82 ℃, then adds calcium carbonate powders, until pH rises to 3.3～3.6, when mineral acid during at 0.09～0.12%wt, add again gac;
5. for the first time decolouring: at first liquid glucose is cooled to 50～52 ℃, then add the gac stirring until sampling detects printing opacity and reach 60～76%;
6. desalination for the first time: adopt ash content, salt, organic acid and the mineral acid that ion-exchange, electrodialysis or EDI electricity desalination method contain in the destainer for the first time to be removed;
7. for the first time evaporation: adopt triple effect or quadruple effect falling-film evaporator that sugar concentration is brought up to 26.0～28.0%;
8. for the second time decolouring: add gac and stir;
9. desalination for the second time: adopt ash content, salt, organic acid and the mineral acid that ion-exchange, electrodialysis or EDI electricity desalination method contain in the destainer for the second time to be removed.
The ion-exchange of the wherein said step of the technique scheme desalination employing first time 6. is continuously through resin cation exchange, resin anion(R.A) exchange and resin cation exchange; The exchange second time that the described step desalination second time 9. adopts be selected from following methods one of them: a kind of is first through anionresin, again through cationic exchange; Another kind is first through cationic exchange, again through anionresin; Also having a kind of is the use that is together in series of positive post and cloudy post, comes into operation simultaneously, regenerates simultaneously.
5. the wherein said step of technique scheme decolours the described first time and 8. step decolours the described second time adopts respectively reverse-flow decoloration process: minute N adding gac, wherein N is the natural number more than or equal to 2, new charcoal is used in last i.e. the N time decolouring, use the old carbon of using after the N time decolouring for the N-1 time, use the old carbon of using after the N-1 time decolouring for the N-2 time, by that analogy, all filter after each decolouring, the gac behind the decolorization filtering reclaims as solid waste for the first time.
The wherein said agriculture and forestry organic waste material of technique scheme is the agriculture and forestry organic waste material that contains five-carbon sugar, comprises at least cauline leaf root, the kind skin of corn cob, wheat straw, beet pulp, bagasse, agricultural crop straw, plant.
The wherein said xylose mother liquid of technique scheme and/or the described pre-treatment that contains the waste liquid of five-carbon sugar comprise:
1. filter: adopt first mechanical filter equipment, adopt membrane filter plant to filter again; Described mechanical filter equipment comprises plate-and-frame filter press, bag type filtering machine, horizontal filtering machine, microfroc filter and filtering centrifuge; Described membrane filter plant comprises ceramic membrane, metallic membrane, organic rolled film and tubular membrane, holds back and is of a size of 100～5000g/mol;
2. desalination: adopt the mode of ion-exchange or adopt electrodialysis, EDI electricity desalination method.
The wherein said membrane filter plant of technique scheme is organic rolled film, holds back and is of a size of 100～3000g/mol.
The wherein said organic rolled film of technique scheme is held back and is of a size of 200～2500g/mol.
The wherein said waste liquid that contains five-carbon sugar of technique scheme comprises at least: the waste liquid that produces in the paper-making pulping process, the spentsulfiteliquor that contains five-carbon sugar, acid accumulator sulfite pulping waste liquor or the solution that biomass digestion or hydrolysis is made with acid.
Also comprise enrichment step before the chromatographic separation of the wherein said step of technique scheme (b), the sugared concentration of feed liquid is concentrated into 50～60%.
Wherein in described chromatrographic separation step, all enter described mixed liquor and the process water of chromatographic separation equipment and remove solia particle by the strainer of aperture at least 20 μ m technique scheme; Described mixed liquor and process water keep temperature to be not less than 60 ℃; Eluent is 55～75 ℃ deionized water.
The technique scheme wherein described fermentation inhibitor in the step (c1) comprises impurity and miscellaneous bacteria, impurity wherein comprises the coloring matter with phenyl ring, macromolecular pigment, macromolecular compound, heavy metal ion, muriate, colloid and polymkeric substance, and miscellaneous bacteria wherein comprises natural airborne yeast and bacterium; The fermentation inhibitor that removes of described step (c1) further may further comprise the steps:
1. for the charged ion heavy metal ion in the described impurity, muriate, and colloid, adopt the method for electrodeionization or ion-exchange to be removed;
2. for the coloring matter in the described impurity, macromolecular compound, polymkeric substance, and miscellaneous bacteria, adopt membrane filtration, ultrafiltration or the real method that disappears to be removed.
1. and 2. the wherein said step of technique scheme order or arbitrary arrangement, perhaps first step 1., rear step 2..
1. the wherein said step of technique scheme adopts the electrodeionization system, and described electrodeionization system comprises EDI electrodeionization and electrodialysis;
The hyperfiltration process of described step in 2. selects mineral membrane or polymer organic membrane to adopt the mode of cross flow filter to filter, and described mineral membrane is held back size in 30～500 nanometers; Described polymer organic membrane is held back size at 1000～10000g/mol;
The membrane filtration of described step in 2. adopts ceramic membrane, metal pipe type film, organic rolled film, organic tubular membrane or flat sheet membrane, holds back and is of a size of 500～6000g/mol;
The reality of described step in the 2. method that disappears is that described feed liquid is heated to 60～120 ℃ of capable sterilising treatment.
The hyperfiltration process of the wherein said step of technique scheme in 2. selects mineral membrane to hold back size in 50～200 nanometers, and the polymer organic membrane is held back size at 1000～6000g/mol;
The membrane filtration of described step in 2. adopts organic rolled film or tubular membrane, holds back and is of a size of 500g/mol～2000g/mol;
The described reality method that disappears is heated to 80～115 ℃ with feed liquid and carries out sterilising treatment.
The wherein said polymer organic membrane of technique scheme comprises: poly (ether sulfone) film, sulfonated polyether sulfone film, polyester film, polysulfone membrane, polyaramide film, polyvinyl alcohol film and poly-piperazine film and combination thereof; Described mineral membrane comprises: ZrO
2-and Al
2O
3-film; The configuration of described film comprises: tubular type, rolling, and tubular fibre.
The step byproduct of the fermentation removal of impurities sugar of the wherein said step of technique scheme (c2) comprising: ethanol, D-ribose and/or citric acid, and described step (c2) comprises one of them of following methods:
1. under anaerobic glucose fermentation, semi-lactosi generate ethanol to use bacterial classification;
2. use bacterial classification to remove glucose, semi-lactosi generation ethanol, carbonic acid gas and water at the aerobic condition bottom fermentation;
3. use shikimic acid defective type subtilis to remove glucose, semi-lactosi generation D-ribose at the aerobic condition bottom fermentation;
4. use fermentation of Aspergillus niger to remove glucose, semi-lactosi generation citric acid;
Wherein said method 1. and the bacterial classification 2. be selected from one of following: yeast saccharomyces cerevisiae, bread yeast, saccharomyces uvarum, Xue's watt yeast, Hansenula anomala, Lip river lattice yeast or Ka Er Persian yeast.
Four kinds of methods of the wherein said step of technique scheme (c2) further may further comprise the steps respectively, and per-cent number wherein is mass percent:
Method is 1.:
(a) at first the sugared concentration of feed liquid is adjusted to 10～40%;
(b) consisting of of bacterium culture medium nutritive salt: urea or ammonium sulfate: 0.01～0.5%, potassium primary phosphate: 0.01～0.5%, sal epsom: 0.01～0.4%;
(c) fermentation parameter is: pH:2.5～5, and 33～45 ℃ of temperature, in blowing air or when beginning fermentation, do not pass into the air of 0.1～0.3vvm, when cell concentration reaches 10
8Individual/as during ml, to stop blowing air, carry out anaerobically fermenting; Fermentation time 8～22 hours;
(d) obtain at last inversion rate of glucose 97.15～98.5%, alcohol getting rate 98～99%, pectinose yield 96～100%, semi-lactosi clearance 35～55%;
Method is 2.:
(a) at first the sugared concentration of feed liquid is adjusted to 8～30%;
(b) consisting of of bacterium culture medium nutritive salt: ammonium sulfate: 0.1～3.5%, potassium primary phosphate: 0.1～5%, sal epsom: 0.05～4%, the corn steep liquor material meter of giving money as a gift: 0.5～20%;
(c) fermentation parameter is: 25～45 ℃ of temperature, pH:3.5-5.5, air flow 0.2～0.5vvm, fermentation time 10～28 hours;
(d) obtaining at last the glucose clearance is 95%～98%, and the semi-lactosi clearance is 50%～70%, alcohol getting rate 90～95%, pectinose yield 96～100%;
Method is 3.:
(a) substratum and culture condition:
Slant medium: glucose 0.5～2%, peptone 0.4～2%, yeast extract paste 0.1～1%, sodium-chlor 0.1～1.2%, agar 0.8～3%, pH6.0～8.0,30～40 ℃ of culture temperature, incubation time 12～36 hours;
Seed culture medium: glucose 1～3%, the corn steep liquor material meter 1～3.5% of giving money as a gift, yeast extract paste 0.1～1%, dipotassium hydrogen phosphate 0.1～1%, potassium primary phosphate 0.1～0.8%, pH 6.0～8.0,30～40 ℃ of culture temperature, incubation time 10～32 hours;
Fermention medium: glucose 5-15%, the corn steep liquor material meter 1～5% of giving money as a gift, ammonium sulfate 0.2～1.5%, manganous sulfate 0.001～0.1%, calcium carbonate 1～6%, whole refractive power concentration 5～10% in the culture system of feed liquid, pH6.0～8.0,30～40 ℃ of culture temperature, incubation time 30～90 hours;
(b) processing parameter: feed liquid when beginning fermentation add or the concentration that proceeds to glucose when fermentation 0.5% the time, the mode that employing stream adds adds;
(c) obtain at last glucose clearance 96～98.5%, pectinose yield 94～98%, semi-lactosi clearance 80～90%; D-ribose yield 35～45%;
Method is 4.:
(a) at first glucose concn is adjusted to 5～10%, feed liquid refractive power concentration is controlled at 20%～30%;
(b) substratum: ammonium sulfate 0.05～1%, sal epsom 0.01～0.5%, the corn steep liquor material meter 0.01～1 of giving money as a gift;
(c) fermentation parameter: pH 5～8,30～42 ℃ of culture temperature, air flow 0.2～0.5vvm, fermentation time 35～52 hours, with glucose aspergillus niger is cultured to logarithm latter stage first, then, adds concentration in the fermentor tank and be 20～30% pectinose fraction, producing citric acid concentration is 5～6%, and transformation efficiency is 92～95%;
(d) obtain at last glucose clearance 95.6～98.7%, pectinose yield 94.6～98.3%, citric acid yield are 90～95%, semi-lactosi clearance 82～89%.
Also comprise after the wherein said step of technique scheme (c2) except thalline: by filtration or method for sieving or for the first time membrane filtering method or adopt first filter or screening is removed thalline in the fermented liquid by membrane filtering method for the first time again; Described filtration or screening plant comprise: plate-and-frame filter press, cardboard filter, filter, horizontal filtering machine and vibratory screening apparatus
Described first time, membrane filter plant comprised: ceramic membrane, metal pipe type film, organic rolled film, organic tubular membrane and flat sheet membrane, and hold back and be of a size of 2500g/mol～1 μ m.
Technique scheme is wherein said adopt to filter first or screening again by the first time membrane filtering method also comprise for the second time membrane filtration step, described second time, membrane filter plant comprised organic rolled film, tubular membrane.
The technique scheme wherein said first time of membrane filter plant adopts ceramic membrane, metal pipe type film, organic rolled film or flat sheet membrane, holds back and is of a size of 50nm～1 μ m; Described second time, membrane filter plant adopted organic rolled film, held back and was of a size of 50～2500g/mol.
The technique scheme wherein said first time of membrane filter plant and described second time membrane filter plant adopt polymer organic membrane or mineral membrane; Described polymer organic membrane comprises: poly (ether sulfone) film, sulfonated polyether sulfone film, polyester film, polysulfone membrane, polyaramide film, polyvinyl alcohol film and poly-piperazine film and combination thereof; Described mineral membrane comprises: ZrO
2-and Al
2O
3-film; The configuration of described film comprises: tubular type, rolling, and tubular fibre.
The post-processing step of the wherein said pectinose fraction of technique scheme feed liquid, to carrying out the following step except the described pectinose fraction feed liquid behind the thalline:
1. decolouring: adopt gac, add-on is 2 ‰～2%wt, and churning time is 0.5～2 hour;
2. desalination: adopt ion-exchange, electrodialysis and/or EDI electricity desalination mode;
3. concentrated: that described pectinose fraction feed liquid is concentrated into i.e. 50～85% the sugared concentration of hypersaturated state;
4. crystallization: comprise at least one times crystallization;
5. dry: as to obtain respectively the L-arabinose finished product.
1. the wherein said step of technique scheme one of decolours specifically in the following ways: a kind of is that the gac of disposable adding capacity stirs decolouring, then filters; Another kind is reverse-flow decoloration process: minute N adding gac, wherein N is the natural number more than or equal to 2, new charcoal is used in last i.e. the N time decolouring, use the old carbon of using after the N time decolouring for the N-1 time, use the old carbon of using after the N-1 time decolouring for the N-2 time, all filter after each decolouring, by that analogy, the gac behind the decolorization filtering reclaims as solid waste for the first time.
The wherein said step of technique scheme 2. desalination comprises: adopt first electrodialysis or EDI electricity desalination and then ion-exchange to carry out desalination.
The wherein said step of technique scheme is 3. concentrated specifically to be comprised: the sugared concentration of described feed liquid is using triple effect vacuum falling film vaporizer concentrated below 60%; The sugared concentration of described feed liquid is higher than 60% and uses the vacuum single-action concentrated.
The wherein said step of technique scheme 4. crystallization comprises the crystallization that twice or twice are above, and the sugar that each crystallization obtains after will the massecuite centrifuging with last crystallization dissolves again crystallization after the evaporation concentration again; Wherein each crystallization comprises: the feed liquid after will concentrating is squeezed into horizontal crystallizer tank with whipping appts and cooling device, adopts the mode of decrease temperature crystalline, and the control cooling rate is per hour lowered the temperature 0.1～3 ℃; Or when temperature is more than 55 ℃, per hour fall 0.5 ℃, treat then per hour to fall 1 ℃ when temperature is down to below 55 ℃; Described crystallizer tank mixing speed is controlled at 0.5～20rpm; The crystal seed add-on accounts for 0.5 of liquid glucose quality～10 ‰.
The invention has the beneficial effects as follows:
Method of the present invention is except producing L-arabinose, can also the by-product ethyl alcohol, the tunning of the glucose such as D-ribose, citric acid.
Method of the present invention removes in advance to materials such as the fermentation inhibitor of feed liquid such as impurity miscellaneous bacterias, and fermentation can be carried out smoothly; And removed the assorted sugar that comprises at least glucose and semi-lactosi by fermentation process, so that the inventive method can obtain highly purified product behind chromatographic separation pectinose and Xylitol, the L-arabinose crystal purity that the present invention finally obtains can be up to 98～99.8%.
Method raw material sources of the present invention are extensive; can comprise any kind agriculture and forestry organic waste material, can also be xylose mother liquid and/or the production waste liquid that contains five-carbon sugar; especially the production waste liquid that contains five-carbon sugar; it mainly is the waste liquid that produces in the paper-making pulping process; these discharging of waste liquid will cause very big pollution in environment; the present invention has carried out effective utilization with these waste liquids, not only for social creativity new wealth but also protected environment.
Method of the present invention is through the check of actual production, and its production cost is low, efficient is high, is suitable for large-scale industrial production.
Description of drawings
Fig. 1 is the process blocks synoptic diagram of the present invention's the first technical scheme;
Fig. 2 is the process blocks synoptic diagram of the present invention's the second technical scheme;
Fig. 3 is the process blocks synoptic diagram of the present invention's the 3rd technical scheme;
Fig. 4 is spectrogram before the present invention's the first technical scheme chromatographic separation;
Fig. 5 is spectrogram before the present invention's the second technical scheme chromatographic separation;
Fig. 6 is spectrogram before the present invention's the 3rd technical scheme chromatographic separation.
Embodiment
Below by specific embodiment the present invention is further set forth; it should be explicitly made clear at this point that these embodiment just are used for explaining, rather than limit of the present invention; so long as meet any technical scheme of spirit of the present invention, all should be in the scope of protection of present invention.
Raw material of the present invention can be hemicellulose hydrolysate, the xylose mother liquid of agriculture and forestry organic waste material and the waste liquid that contains five-carbon sugar, described agriculture and forestry organic waste material includes but not limited to: the cauline leaf root of corn cob, wheat straw, beet pulp, bagasse, agricultural crop straw, plant, wheat bran, maize peel, etc., all can be used as raw material of the present invention so long as contain the agriculture and forestry organic waste material of five-carbon sugar.In technical scheme of the present invention, carry out again subsequent step after at first will becoming hemicellulose hydrolysate and/or xylose mother liquid to the agriculture and forestry organic waste material pre-treatment.
Hemicellulose hydrolysate and xylose mother liquid and containing in the waste liquid of five-carbon sugar mainly contain: wood sugar, xylan, L-arabinose, glucose, semi-lactosi, other also have such as assorted sugar such as seminose, rhamnosyls.Purpose of the present invention is exactly L-arabinose wherein will to be extracted, and this just need to get rid of other compositions.In these compositions that will remove, wood sugar is to separate by the method for chromatographic separation; Glucose, and semi-lactosi can remove by conventional fermentation means, the wherein the easiest fermentation of glucose, can utilize common bread yeast or yeast saccharomyces cerevisiae as the nutritious carbon sourc of bacterial classification by change condition generation carbonic acid gas and water or ethanol; The many of difficulty are wanted in the fermentation of semi-lactosi comparatively speaking, need can utilize by screening the bacterial classification of semi-lactosi, and optimization of fermentation conditions is fermented.The assorted sugared content such as seminose, rhamnosyl is lower, has generated carbonic acid gas and water when carrying out the fermentation of glucose, semi-lactosi, even nonfermented also can not affect the crystallization of pectinose, so do not need extra step to remove.Xylan belongs to a kind of crystallization inhibitor in the inventive method, can together remove by filter method and other crystallization inhibitors before the finished product crystallization.
The below adopts three kinds of technical schemes to be described in detail with regard to the difference of Production Flow Chart of the present invention respectively:
The first technical scheme (process flow diagram is seen Fig. 1):
Step 110, the feed liquid pre-treatment
Feed liquid of the present invention has three kinds of sources: the hydrolyzed solution of agriculture and forestry organic waste material, xylose mother liquid and contain the waste liquid of five-carbon sugar.The purpose of feed liquid pre-treatment step is the various raw materials that are suitable for extracting the L-arabinose goods to be treated as contain wood sugar, xylan, L-arabinose, glucose, semi-lactosi, and feed liquids of other assorted sugar, so that subsequent step is processed.
First talk about the pre-treatment of feed liquid in the hydrolyzed solution source of agriculture and forestry organic waste material:
Agriculture and forestry organic waste material is treated as hemicellulose hydrolysate, only describes as an example of corn cob example, the processing of other agriculture and forestry organic waste materials is identical; Specifically may further comprise the steps:
1, the material loading of raw material and pre-treatment:
Corn cob is sent in the receiving hopper of workshop charging belt, delivered to by belt afterwards and enter washing machine after screening out a part of silt and chip on the vibrosieve transfer roller.The corn cob washing machine should regularly be removed the silt in its sand deposition hopper.Corn cob enters chapelet or high spud angle band rib rotary conveyor after dewatering by vibrating-dewatering screen after the washing, then be raised on the horizontal belt transfer roller that is transported to the hydrolyzer top, again by distributing plate control to send in the hydrolyzer that needs charging through chute.
2, hydrolysis:
Hydrolyzer begins to be hydrolyzed after filling material.
The first step of hydrolysis is dilute acid pretreatment.Enter the corn cob of hydrolyzer, its cellular skin still unavoidably is attached with firmly earth, and corn cob also contains the carbohydrate, pigment, pectin, nitrogenous thing of non-hemicellulose and fat etc., and these materials enter in the hydrolyzed solution will increase the weight of the burden of postorder refining step greatly.So corn cob needs to adopt dilute acid pretreatment to remove in advance these impurity before hydrolysis, treatment condition are that 110～130 ℃ in 0.05～0.15%wt sulfuric acid was processed 1～3 hour.This condition substantially can not cause hydrolysis of hemicellulose and lose wood sugar, but by after the dilute acid pretreatment, thereby impurity is removed the hydrolyzed solution quality is greatly improved.
Corn cob is after dilute acid pretreatment, and the acid solution of draining adds the dense acid solution at 0.5～1%wt of acid.Logical steam is warmed up to 128～132 ℃ of specified temperature, and the insulation kept specific time 2.5 hours, finish hydrolysis.
In other embodiments, the acid solution of above-mentioned pre-treatment step and hydrolysing step also can adopt the mixed solution of in hydrochloric acid, phosphoric acid, acetic acid, nitric acid or these acid certain two kinds and two or more acid except sulfuric acid, its acid strength is slightly different according to Acidity.
Hydrolysis is finished hydrolyzed solution is discharged collection, and waste residue is washed, and it is emptying with residue then to open residual cake valve.The hydrolyzed solution chief component of collecting is as follows: wood sugar: 3～5%wt, and pectinose: 0.4～0.65%wt, glucose: 0.4～0.65%wt, semi-lactosi: 0.1～0.2%wt, sugared concentration is generally at 5～8%wt.
3, neutralization:
Owing to contain the sulfuric acid of 0.5～1%wt in the hydrolyzed solution, if be directly used in next process meeting severe corrosion equipment and the difficult removal of sulfuric acid, therefore need sulfuric acid is neutralized.With pump said hydrolyzed liquid is sent into neutralization tank, add light calcium carbonate powder toward neutralization tank gradually while stirring, constantly detect with accurate pH test paper, until pH rises to 3.3～3.6, sample examination, mineral acid add gac again when 0.09～0.12%wt, the present invention is the old gac of the used secondary of postorder bleaching process for what add for the purpose of saving in a preferred embodiment, sends to plate-and-frame filter press after fully stirring and filters.
Neutral temperature in and effect also influential, calcium sulfate solubleness is larger under the lesser temps, can cause the residual quantity of calcium in the neutralizer to increase.Liquid glucose should be heated to 80～82 ℃ before the neutralization.
Feed liquid was processed to be neutralizer when this step was finished.
4, for the first time decolouring:
Decolouring is a certain amount of gac and neutralizer to be put in the container stir, and utilizes the decoloring ability of gac that color is taken off.Can adopt the mode of disposable adding gac, but for the decoloring ability that takes full advantage of gac is saved gac, the reverse-flow decoloration process of preferred employing, namely divide N time and add gac, wherein N is the natural number more than or equal to 2, new charcoal is used in last i.e. the N time decolouring, use the old carbon of using after the N time decolouring for the N-1 time, use the old carbon of using after the N-1 time decolouring for the N-2 time, by that analogy, all filter after each decolouring, because of the neutralizer color darker, for the first time the gac consumption of decolouring is larger, accounts for the about 3/4ths of total consumption charcoal amount, and the gac behind the decolorization filtering reclaims as solid waste for the first time.Technical process and equipment about decolouring are known public technology, no longer are described in detail at this.
The add-on of fresh gac is controlled according to the transmittance index of destainer in the bleacher, and is inadequate if the bleacher sampling detects printing opacity behind filter paper filtering, need add fresh gac until sampling detects printing opacity and reach 60～76%.
Because the many pigments in the Xylose are easier of charcoal absorption under relative low temperature, so liquid glucose should cool to 50～52 ℃ before entering bleacher, it is that destainer no longer needs cooling when entering front cationic exchange that this temperature also has a benefit.
Feed liquid was processed to be for the first time destainer when this step was finished.
5, desalination for the first time:
Contain ash content, salt, organic acid and mineral acid in the destainer for the first time, generally need to remove by ion-exchange.For the first time ion-exchange is general continuous in resin cation exchange, resin anion(R.A) exchange, resin cation exchange.Ion-exchange unit of the present invention uses ion exchange column, from handing over one regeneration of post one usefulness, realizes the operate continuously of ion-exchange.In a specific embodiment, it is that 001 * 7 resin cation (R.C.) and model are the resin anion(R.A) of D305 that the present invention adopts model.
The removal of above salt and acid can also be used the techniques such as electrodialysis, EDI electricity desalination except the method for using ion-exchange.The technique such as electrodialysis, electric desalination is traditional desalination process, no longer is described in detail at this.
6, for the first time evaporation:
The purpose of this step is that sugar concentration is brought up to 26.0～28.0%, reduce the liquid glucose volume, reduce the refining burden of postorder operation, the concentration of impurity also improves much in the liquid glucose simultaneously, for the postorder cleaning section provides convenience, it is more guaranteed also to make postorder purify rear liquid glucose quality.
General triple effect or the quadruple effect falling-film evaporator of adopting of evaporation out sent to for the second time decolouring afterwards from vaporizer.Liquid glucose is flowed through when respectively imitating film evaporator, and every effect film evaporator all evaporates removes a part of water, and sugared concentration raises by effect.Can enter the sugared concentration that a heating live steam amount of imitating film evaporator is controlled the evaporation discharging by adjusting.
To be processed to be sugared concentration be 26～28% liquid glucose to feed liquid when this step was finished.
7, for the second time decolouring:
Liquid glucose is by after evaporating for the first time, concentration improves, wherein contain the also simultaneously raising of coloring matter concentration of the compounds such as phenyl ring class, add that some organic substances produce new coloring matter under the evaporation high temperature action, liquid glucose drops to about 20% at the rear transmittance of for the first time evaporation.To make darkening of liquid glucose like this, foreign matter content raises, and therefore, in a preferred embodiment, the present invention also needs liquid glucose is carried out the decolouring second time.
For the second time decolouring also can adopt the adverse current decoloration process to reduce gac consumption as for the first time decolouring.For the first time the liquid glucose temperature is between 60～65 ℃ after the evaporation, and for the second time decolouring is to need not liquid glucose is lowered the temperature with decolouring the first time different.Decolouring should be so that printing opacity reaches 90～98% for the second time.
8, desalination for the second time:
Desalination also is a preferred embodiment of the present invention for the second time, and liquid glucose is delivered to for the second time ion-exchange process continuation and removed foreign ion after the above-mentioned decolouring second time.The duty ratio of exchange once exchanges and is much smaller for the second time, and for the second time exchange has multiple way: a kind of is first through anionresin, again through cationic exchange; Another kind is first through cationic exchange, again through anionresin; Also having a kind of is the use that is together in series of positive post and cloudy post, comes into operation simultaneously, regenerates simultaneously.The first method acid and alkali consumption is minimum, and second method is better to the negative resin protection, and the third operation is the most convenient.The general first method that adopts.
The for the second time removal of foreign ion can also be used the techniques such as electrodialysis, EDI electricity desalination except the method for using ion-exchange.The technique such as electrodialysis, electric desalination is traditional desalination process, no longer is described in detail at this.
The feed liquid in the other two kinds of sources of the present invention---xylose mother liquid and to contain the pre-treatment step of waste liquid of five-carbon sugar as follows:
Xylose mother liquid refers in traditional wood sugar production process, solid (wood sugar crystal) is separated the liquid that obtains after the removal with whizzer behind the xylose crystalline.The waste liquid that contains five-carbon sugar is mainly the waste liquid that produces in the paper-making pulping process, mainly is the spentsulfiteliquor that contains five-carbon sugar, especially the acid accumulator sulfite pulping waste liquor.Waste liquid also can be with acid biomass digestion or hydrolysis to be made any other solution.These discharging of waste liquid will cause very big pollution in environment, the present invention has carried out effective utilization with these waste liquids, not only for social creativity new wealth but also protected environment.
Xylose mother liquid and the feed liquid that contains five-carbon sugar have been the solution that contains wood sugar, pectinose, glucose, semi-lactosi than the agriculture and forestry organic waste material raw material, and its pretreatment technology is relatively simple.Generally through purifying step such as filtration, desalinations, specific as follows according to the impurity situation:
1, filter:
Liquid glucose passes through first filter type from coarse to fine, removes first oarse-grained mechanical impurity, then removes suspended particle and dust etc. with secondary filter again.At last, use membrane filter plant to remove the polymer substances such as colloid, albumen.
Filter filter plants such as adopting plate-and-frame filter press, bag type filtering machine, horizontal filtering machine, microfroc filter, filtering centrifuge.Select filter screen and the filter core of different pore size filters according to the granular size of mechanical impurity.
Membrane filter plant adopts ceramic membrane, metallic membrane, organic rolled film, tubular membrane etc., preferably adopts organic rolled film, holds back and is of a size of 100～5000g/mol, preferred 100～3000g/mol, most preferably 200～2500g/mol.
2, desalination:
All more or less contain the impurity such as ion that an operation is brought in the general waste liquid, the existence one side of foreign ion can affect next step concentratedly darkens liquid glucose and destroys sugar; Contain on the other hand foreign ion especially heavy metal ion can affect the fermentation of subsequent processing.Therefore the foreign ion in the waste liquid need to be removed.Desalination generally adopts the mode of ion-exchange or adopts the techniques such as electrodialysis, EDI electricity desalination.The techniques such as ion-exchange, electrodialysis, electric desalination are traditional desalination process, no longer are described in detail at this.The specific conductivity of feed liquid is less than 1000us behind the process desalination, and preferred specific conductivity is less than 200us, and most preferably specific conductivity is less than 50us.
More than be exactly that the present invention is for the pre-treatment of feed liquid, after pre-treatment is finished, feed liquid becomes and contains: wood sugar, xylan, L-arabinose, glucose, semi-lactosi, and liquid glucoses of other assorted sugar, and this liquid glucose also mixes the impurity such as salt is arranged, and then feed liquid is carried out following flow process:
Step 120, concentrated
Because the dense too low meeting of sugar affect separating effect and the working efficiency of chromatographic equipment, and can make the fraction sugar concentration after the separation excessively low, reduce the utilization ratio of subsequent handling equipment.Therefore, advance liquid glucose should be concentrated into before the chromatographic separation equipment 50～60% sugared dense.
Reached the xylose mother liquid more than 50% then need not concentrate and directly advance subsequent processing if feed liquid is concentration.High temperature destroys and saves the steam that evaporation consumes when avoiding the liquid glucose evaporation concentration, liquid glucose concentrated general adopt vacuum-evaporation, especially triple effect or the evaporation of quadruple effect vacuum falling film.
Certainly, in some other embodiment of the present invention, also can omit this step.
Step 130, chromatographic separation
Carry out chromatographic separation, principal security separates the wood sugar in the liquid glucose with pectinose, obtain the wood sugar fraction, reach the pectinose fraction, wood sugar could be separated like this, comprise that the assorted sugared philosophy of glucose and semi-lactosi enters wood sugar fraction, pectinose fraction.
When the feed liquid that contains salt, assorted sugar, wood sugar and pectinose is injected into chromatographic fractionation system and water flushing, because the avidity between salt, assorted sugar, wood sugar and each composition of pectinose and stationary phase strengthens successively in the feed liquid; Speed when each composition moves forward in the stationary phase layer is also corresponding to slow down successively; Produce velocity contrast, make and realize between " slowly " component and " soon " component separating.
What the present invention used is traditional separation system of simulated moving bed chromatography, and its composition and structure no longer are described in detail.
The operation process condition of separation system:
(1) pre-treatment: for the protection stationary phase, prolong working life, guarantee simultaneously the safe operation of chromatographic column, all materials (comprising process water) that advance post can not contain any solia particle, all need the security filter by aperture at least 20 μ m; For the feed liquid that makes high density crystallization not, charging must keep temperature to be not less than 60 ℃, and temperature remains unchanged substantially.
(2) enter system: the wood sugar feed liquid is sent into chromatographic fractionation system by fresh feed pump, deionized water is pumped into chromatographic fractionation system by eluent, start simultaneously the discharging pump of chromatogram xylose product fluid, pectinose product fluid and salt and glucose, system produces under automatization control continuously.
Eluent is 55～75 ℃ of deionized waters.
(3) system moves under the control of programmable logic controller (PLC) automatically by control valve and instrument.Realize the automatic switchover of the every downward root pillar of pillar, all states of pillar and turnover material all switch during switching.Thereby the simulation that realizes stationary phase is moved.
(4) go out system: sugar is dense about 50～60%, and wherein the pending liquid of the wood sugar of wood sugar purity 〉=50% enters chromatogram arrangement, and the product that goes out chromatographic fractionation system has two kinds of following described (1)+(4), (2)+(3); Perhaps (1), (2), (3)+(4) are three kinds; Perhaps (1)+(4), (2), (3) three kinds; Perhaps (1), (2)+(3), (4) three kinds; Perhaps (1), (2), (3), (4) four kinds:
(1) Xylose fraction: wood sugar purity＞80%, refractive power concentration is about 15～30%;
(2) Arabic liquid glucose fraction: pectinose purity＞50%, refractive power concentration is 5～15%;
(3) impurity fractions such as glycerine, glycitols (namely using calcium type chromatographic column or plumbous type chromatographic column, the impurity peaks part of back, pectinose peak on the HPLC spectrogram that detects): refractive power concentration is 1～8%;
(4) impurity fractions such as organic acid, part glucose (namely using calcium type chromatographic column or plumbous type chromatographic column, the impurity peaks part of front, wood sugar peak on the HPLC spectrogram that detects): refractive power concentration is 1～8%;
Please be simultaneously referring to Fig. 4, Fig. 4 is spectrogram before the present invention's the first technical scheme chromatographic separation, among the figure: A-organic acid etc., B-glucose, C-wood sugar, D-R, E-ethanol glycerine etc., F-fusel.
Like this, just the wood sugar in the liquid glucose and pectinose are separated, obtained the wood sugar fraction, reached the pectinose fraction.
The below describes with regard to the further treatment scheme of pectinose fraction:
Step 1311 removes fermentation inhibitor
Contain the fermentation inhibitor that suppresses strain fermentation in the pectinose fraction, must before the liquid glucose fermentation, be removed, these fermentation inhibitors mainly comprise impurity and miscellaneous bacteria, and impurity wherein comprises the coloring matter with phenyl ring, macromolecular pigment, macromolecular compound, heavy metal ion, muriate, colloid, polymkeric substance etc.; Miscellaneous bacteria wherein mainly is the airborne miscellaneous bacteria of occurring in nature such as yeast, bacterium etc., contains the nutritive substances such as glucose in the pectinose fraction, and liquid glucose needs only ingress of air, and airborne miscellaneous bacteria will be grown in liquid glucose, be bred.The removal method of these fermentation inhibitors comprises:
1. for charged ions such as heavy metal ion, muriate, colloids, the present invention adopts the method for electrodeionization or ion-exchange to be removed.The preferred electrodeionization system that adopts.Be used for electrodeionization of the present invention system and include but not limited to such as EDI electrodeionization, electrodialysis etc.
2. for coloring matter, macromolecular compound, polymkeric substance, and miscellaneous bacteria, the present invention adopts membrane filtration, ultrafiltration or the real method that disappears to be removed.
Above-mentioned steps 1. and 2. order can arbitrary arrangement, wherein preferred first step 1., rear step 2..
Hyperfiltration process in some embodiments of the invention selects mineral membrane or polymer organic membrane to adopt the mode of cross flow filter to filter.Be used for ultra-filtration membrane of the present invention: mineral membrane is held back size in 30～500 nanometers, and the polymer organic membrane is held back size at 1000～10000g/mol.Preferred mineral membrane is held back size in 50～200 nanometers, and the polymer organic membrane is held back size at 1000～6000g/mol.
In other embodiment of the present invention, the use membrane filtration removes the fermentation inhibitor in the pectinose fraction, film can adopt ceramic membrane, metal pipe type film, organic rolled film, organic tubular membrane, flat sheet membrane etc., preferred organic rolled film or the tubular membrane of adopting, hold back and be of a size of 500～6000g/mol, preferred 500g/mol～2000g/mol.
In other embodiment of the present invention, do not use membrane filtration, but adopt real method imurity-removal and the miscellaneous bacteria that disappears: feed liquid is heated to 60～120 ℃, and preferred 80～115 ℃ are carried out sterilising treatment.Heating installation is general-purpose equipment, repeats no more.
Be generally used for polymer organic membrane of the present invention and include but not limited to for example poly (ether sulfone) film, sulfonated polyether sulfone film, polyester film, polysulfone membrane, polyaramide film, polyvinyl alcohol film and poly-piperazine film and combination thereof.Mineral membrane commonly used includes but not limited to for example ZrO
2-and Al
2O
3-film.The configuration of film is selected from such as tubular type, rolling, tubular fibre etc.
Step 1312, fermentation removal of impurities sugar
The pectinose fraction contains the assorted sugar such as glucose, semi-lactosi.These sugar can crystallize out along with the crystallization of wood sugar and pectinose, have a strong impact on product purity.Because glucose and semi-lactosi are fermentable sugars, therefore, the present invention adopts the mode of fermentation to convert it into carbonic acid gas and water and removes; Perhaps fermentation changes into other other products low-boiling or that easily separate with pectinose, the glucose fermentation products such as by-product ethanol, D-ribose, citric acid when separating assorted sugar in chromatographic fractionation system.
For most of bacterial classification, glucose can be used as the nutritive substance of growth or carbon source and is utilized.Semi-lactosi utilizes difficulty comparatively speaking, needs by strain screening or changes fermentation parameter and culture medium prescription utilizes.
Under anaerobism and good oxygen condition, use following bacterial classification all can make the fermentation of glucose and semi-lactosi, wherein the anaerobically fermenting major part obtains ethanol, aerobic fermentation obtains ethanol and carbonic acid gas and water, and these bacterial classifications include but not limited to yeast saccharomyces cerevisiae, bread yeast, saccharomyces uvarum, Xue's watt yeast, Hansenula anomala, Lip river lattice yeast, Ka Er Persian yeast etc.Preferred yeast saccharomyces cerevisiae, bread yeast, the saccharomyces uvarum of adopting.Preferred employing yeast saccharomyces cerevisiae, saccharomyces uvarum.Ethanol is wherein removed as his usefulness by the distillation mode, and the present invention repeats no more.And semi-lactosi needs could to be utilized by yeast saccharomyces cerevisiae under good oxygen condition, and nutritive substance also has different from glucose when utilizing semi-lactosi.
The method of removing glucose, semi-lactosi generation other products under the prerequisite of pectinose by fermenting is a lot of containing, below enumerated several example of the present invention, wherein example 1 and example 2 all only describe as an example of yeast saccharomyces cerevisiae example, but can adopt in further embodiments bacterial classification above-mentioned to carry out the fermentation of glucose and semi-lactosi.But the present invention is not limited to following embodiment, as long as modification and the improvement made without departing from theon the basis of the spirit of the present invention all belong to the scope of protection of present invention.
Example 1, the pectinose fraction use yeast saccharomyces cerevisiae under anaerobic glucose fermentation, semi-lactosi to generate the concrete technology parameter of ethanol as follows: per-cent number wherein is mass percent.
(1) at first the sugared concentration of Arabic liquid glucose is adjusted to 10～40%, preferred 20～35%;
(2) consisting of of bacterium culture medium nutritive salt: urea or ammonium sulfate: 0.01～0.5%, preferred 0.05～0.2%; Potassium primary phosphate: 0.01～0.5%, preferred 0.01～0.2%; Sal epsom: 0.01～0.4%, preferred 0.01～0.2%;
(3) fermentation parameter is: pH:2.5～5,33～45 ℃ of temperature, not blowing air or when beginning fermentation pass into micro-air (0.1～0.3vvm), when cell concentration reaches 10
8Individual/as during ml, to stop blowing air, carry out anaerobically fermenting.
(4) technical indicator: glucose clearance 97.15～98.5%, alcohol getting rate 98～99%, pectinose yield 96～100%, semi-lactosi clearance 35～55%; Fermentation time 8～22h.
Example 2,The concrete technology parameter that the pectinose fraction uses yeast saccharomyces cerevisiae to remove glucose, semi-lactosi generation ethanol, carbonic acid gas and water at the aerobic condition bottom fermentation is as follows: per-cent number wherein is mass percent.
(1) at first the sugared concentration of Arabic liquid glucose is adjusted to 8～30%, preferred 10～25%;
(2) consisting of of bacterium culture medium nutritive salt: ammonium sulfate: 0.1～3.5%, preferred 0.5～2.5%; Potassium primary phosphate: 0.1～5%, preferred 0.5-3%; Sal epsom: 0.05～4%, preferred 0.2-2%; Corn steep liquor (the material meter of giving money as a gift): 0.5～20%, preferred 1～10%.
(3) fermentation parameter is: 25～45 ℃ of temperature, preferred 30～40; PH:3.5-5.5, blowing air amount 0.2～0.5vvm.
Through the fermentation of 10～28h, the glucose clearance is 95%～98%, and the semi-lactosi clearance is 50%～70%, alcohol getting rate 90～95%, pectinose yield 96～100%.
Example 3,The concrete technology parameter that the pectinose fraction uses shikimic acid defective type subtilis to remove glucose, semi-lactosi generation D-ribose at the aerobic condition bottom fermentation is as follows: per-cent number wherein is mass percent.
(1) substratum and culture condition:
A, slant medium: glucose 0.5～2%, preferred 0.8～1.6%; Peptone 0.4～2%, preferred 0.8～1.5%; Yeast extract paste 0.1～1%, preferred 0.2～0.6%; Sodium-chlor 0.1～1.2%, preferred 0.2～0.8%; Agar 0.8～3%, preferred 1.5～2.5%; PH6.0～8.0, preferred 6.8～7.5; 30～40 ℃ of culture temperature, preferred 32～38 ℃; Incubation time 12～36 hours, preferred 18～24h.
B, seed culture medium: glucose 1～3%, preferred 1.5～2.2%; Corn steep liquor (the material meter of giving money as a gift) 1～3.5%, preferred 1.5～2.5%; Yeast extract paste 0.1～1%, preferred 0.2～0.6%; Dipotassium hydrogen phosphate 0.1～1%, preferred 0.2～0.7%; Potassium primary phosphate 0.1～0.8%, preferred 0.1～0.5%; PH 6.0～8.0, and preferred 6.8～7.5; 30～40 ℃ of culture temperature, preferred 32～38 ℃; Incubation time 10～32 hours, preferred 12～20h.
C, fermention medium: glucose 5-15%, preferred 8～12%; Corn steep liquor (the material meter of giving money as a gift) 1～5%, preferred 2～4%; Ammonium sulfate 0.2～1.5%, preferred 0.5～1.0%; Manganous sulfate 0.001～0.1%, preferred 0.002～0.008%; Calcium carbonate 1～6%, preferred 2～4%; Pectinose fraction (whole refractive power concentration 5～10% in the culture system), pH 6.0～8.0, and preferred 6.8～7.5; 30～40 ℃ of culture temperature, preferred 32～38 ℃; Incubation time 30～90 hours, preferred 40～85 hours.
(2) processing parameter: pectinose joins fermentor tank in when beginning fermentation, and the concentration that perhaps proceeds to glucose when the fermentation mode that employing stream adds 0.5% time joins fermentor tank.
(3) technical indicator: glucose clearance 96～98.5%, pectinose yield 94～98%, semi-lactosi clearance 80～90%, D-ribose yield 35～45%.
Example 4,The pectinose fraction uses the concrete technology parameter of fermentation of Aspergillus niger removal glucose, semi-lactosi generation citric acid as follows: per-cent number wherein is mass percent.
(1) at first the concentration of glucose is adjusted to 5～10%, pectinose fraction refractive power concentration is controlled at 20%～30%.
(2) substratum: ammonium sulfate 0.05～1%, preferred 0.1%-0.3%; Sal epsom 0.01～0.5%, preferred 0.05～0.08%, the corn steep liquor material meter 0.01～1 of giving money as a gift, preferred 0.05～0.3%.
(3) fermentation parameter: pH 5～8, preferred 5.5～6.5; 30～42 ℃ of culture temperature, preferred 35～38 ℃; Air flow 0.2～0.5vvm, fermentation time 35～52h.
Its main points of processes control is with glucose aspergillus niger to be cultured to logarithm latter stage first, then, adds concentration in the fermentor tank and be 20～30% pectinose fraction.
(4) technical indicator: glucose clearance 95.6～98.7%, pectinose yield 94.6～98.3%, semi-lactosi clearance 82～89%.The citric acid yield is 90～95%.
After this step was finished, liquid glucose became the fermented liquid that main component is pectinose, also contained the impurity components such as thalline, salt in certain this fermented liquid.
Step 1313, remove thalline:
Because also contain the solid impurity compositions such as thalline in the fermented liquid, and thalline belongs to protein, if do not remove, protein will react in follow-up heating schedule so that liquid glucose darkens, and affect quality product, therefore preferred these thalline of removing.
Adopt in one embodiment and filter or screening plant, these equipment comprise: the equipment that plate-and-frame filter press, cardboard filter, filter, horizontal filtering machine, vibratory screening apparatus etc. can be tackled the thalline in the fermented liquid; Adopt in another embodiment the method for membrane filtration, membrane filter plant can adopt ceramic membrane, metal pipe type film, organic rolled film, organic tubular membrane, flat sheet membrane etc., preferred ceramic membrane, metal pipe type film, organic rolled film, the flat sheet membrane of adopting, hold back and be of a size of 2500g/mol～1 μ m, preferred 50nm～1 μ m; Feed liquid is introduced into plate-and-frame filter press and removes thalline and most of albumen through membrane filter plant more In yet another embodiment, filter and most of thalline and mechanical impurity in the fermented liquid can be removed with plate-and-frame filter press first, like this after film, the flux of film is strengthened, prevent from stopping up film, prolong the work-ing life of film.
Further, in a preferred embodiment, removed fermented liquid behind thalline and the most of albumen and added again a membrane filter plant and remove the impurity such as albumen, pigment, crystallization inhibitor.Described membrane filter plant adopts organic rolled film, tubular membrane etc., preferably adopts organic rolled film, holds back and is of a size of 50～2500g/mol, preferred 50～400g/mol, most preferably 100～300g/mol.The purpose that adds this mantle mainly is in order to remove albumen, pigment and crystallization inhibitor.Removing albumen is the difficulty that causes liquid glucose to darken and cause to follow-up decolouring because of Maillard reaction in order to alleviate subsequent handling; Removing pigment also is the difficulty of bringing in order to alleviate follow-up decolouring; Crystallization inhibitor mainly is the macromolecular substance such as oligose, colloid, albumen, the oligose here mainly refers to xylan, these materials can make the follow-up crystallization difficulty of sugar, make crystal childlike, these crystallization inhibitors can be removed the crystallization that is more conducive to sugar by membrane filtration.The use of this mantle will improve constant product quality of the present invention, cut down the consumption of raw materials, improves Crystal type.
Membrane filter plant of the present invention can adopt polymer organic membrane or mineral membrane.Be generally used for polymer organic membrane of the present invention and include but not limited to for example poly (ether sulfone) film, sulfonated polyether sulfone film, polyester film, polysulfone membrane, polyaramide film, polyvinyl alcohol film and poly-piperazine film and combination thereof.Mineral membrane commonly used includes but not limited to for example ZrO
2-and Al
2O
3-film.The configuration of film is selected from such as tubular type, rolling, tubular fibre etc.
Step 1314, the aftertreatment of L-arabinose
Pectinose has 8 kinds of steric isomers, and common is β-L-arabinose and β-D-R.Natural L-arabinose is likely by the D-wood sugar by the result of uridine diphosphate (UDP) derivative through the enzymatic isomerization reaction.The nature D-R is rarely found, only exists in some bacterial polysaccharides.What will extract in the following steps of the present invention is exactly L-arabinose.
Post-processing step to fermented liquid specifically comprises:
1. decolouring
Carry out activated carbon decolorizing through the fermented liquid behind the membrane filtration.Decolouring is to carry out in the bleacher of agitator, and bleaching temperature does not need strict control, generally carries out according to the temperature of coming feed liquid.The gac add-on is 2 ‰～2%wt.Churning time is 0.5～2 hour.The decoloration process mode has two kinds: a kind of is charcoal stirring decolouring, the filtration of disposable adding capacity; Another kind is reverse-flow decoloration process, it is the preferred method of the present invention, namely divide N time and add gac, wherein N is the natural number more than or equal to 2, and namely new charcoal is used in the N time decolouring for the last time, the old carbon of using after the N time decolouring of the N-1 time use, use the old carbon of using after the N-1 time decolouring for the N-2 time, all filter after each decolouring, by that analogy, the gac behind the decolorization filtering reclaims as solid waste for the first time.Preferred the second technique that adopts, this technique can greatly reduce cost.The decolouring of this step should be so that printing opacity reaches 90～98%.
2. desalination
The effect of desalination mainly is to purify liquid glucose, the salt that the nutritive salt that adds in the removal fermenting process and gac are brought into.Desalination generally adopts the mode of ion-exchange or adopts the techniques such as electrodialysis, EDI electricity desalination.The techniques such as ion-exchange, electrodialysis, electric desalination are traditional desalination process, no longer are described in detail at this.In other embodiment of the present invention, before ion-exchange, can add electrodialysis or EDI electricity desalination and carry out desalination, to alleviate the load of ion-exchange.
3. concentrated
Liquid glucose behind the desalination concentrates, and comes feed liquid sugar concentration to be generally 10～20%, needs during crystallization liquid glucose is concentrated into the sugared dense of hypersaturated state 50～85%.When liquid glucose concentrated, sugared concentration was using triple effect vacuum falling film vaporizer concentrated below 60%; Sugar concentration is higher than 60% and uses the vacuum single-action concentrated.
4. crystallization
Liquid glucose after concentrated is squeezed into crystallizer tank.Crystallizer tank is horizontal container with whipping appts and cooling device, stirs to be generally two helical-ribbon types stirrings, and crystallizer tank can pass into heat-eliminating medium and heating medium with chuck and coil pipe.The mode of decrease temperature crystalline is adopted in the crystallization of pectinose.The temperature of massecuite begins cooling after concentrated from single-action, and the control cooling rate is per hour lowered the temperature 0.1～3 ℃; Preferred 0.5～2 ℃; More preferably per hour fall 0.5 ℃ more than 55 ℃, be down to below 55 ℃, per hour fall 1 ℃.The crystallizer tank mixing speed is controlled at 0.5～20rpm, preferred 0.5～5rpm.The crystal seed add-on accounts for 0.5 of liquid glucose quality～10 ‰, and preferred 1～5 ‰.Control concentration and the temperature fall time of liquid glucose before the crystallization well, so that the solids content in the massecuite 〉=20% after the crystallization, preferred 〉=40%.
Because crystallization processes itself is the process of purifying, so the crystallization number of times of pectinose is at least once, is preferably 2 times.If when needing repeatedly crystallization, the sugar that obtains after the massecuite centrifuging with last crystallization dissolves again crystallization after the evaporation concentration again.
Crystallization obtains crystalliferous massecuite after finishing, and then uses filtering centrifuge that crystalline sugar is separated with mother liquor.The pectinose crystal purity that the present invention obtains is 98～99.8%.
5. drying obtains the L-arabinose finished product
Crystalline sugar after the filtration is moisture≤0.2% after super-dry.What drying adopted is general-purpose equipment and common processes, repeats no more.
The second technical scheme (process flow diagram is seen accompanying drawing 2):
Can obviously find out by comparison chart 1 and Fig. 2, the technical scheme of Fig. 2 is very similar to the scheme of Fig. 1, main difference be in, that the separation of advanced circumstances in which people get things ready for a trip spectrum obtains pectinose fraction and wood sugar fraction in the technical scheme of Fig. 1, to " remove fermentation inhibitor " again, " fermentation removal of impurities sugar ", and " except thalline " these three steps place the treatment scheme of pectinose fraction, the technical scheme of Fig. 2 is then carried out first " except fermentation inhibitor ", " fermentation removal of impurities sugar ", and " except thalline " these three steps, and then obtain the pectinose fraction and carry out subsequent disposal by chromatographic separation.The second technical scheme specifically may further comprise the steps:
Step 210, the feed liquid pre-treatment
Identical with the step 110 of the first technical scheme, hemicellulose hydrolysate, xylose mother liquid and the agriculture and forestry organic waste material waste liquid that contains five-carbon sugar are through concentrated behind the purification filtering or to be diluted to total reducing sugar sugar dense about 10～30%.
Step 220 removes fermentation inhibitor
Identical with step 1311.
Step 230, fermentation removal of impurities sugar
Identical with step 1312.Become fermented liquid through feed liquid after this step process.
Step 240 is except thalline
Identical with step 1313.Become the liquid glucose of total sugar concentration about 10～20% through feed liquid after this step process.
Step 250, concentrated
Through carrying out evaporation concentration to sugar dense 50～60% except the fermented liquid behind the thalline.Thickening equipment adopts the equipment identical with step 120.In preferred an enforcement, can carry out desalination with desalination modes such as ion-exchange, electrodialysis, electric desalinations before this enrichment step, thereby cause liquid glucose to darken to alleviate because ion with sugar Maillard reaction occurs when heating.
Step 260, chromatographic separation
In the second technical scheme, the chromatographic separation of the step 130 of this step chromatographic separation and the first technical scheme is basic identical.Different is, because liquid glucose has passed through step 220,230 fermentations and removed most glucose, semi-lactosi, remain slightly difference of content that a small amount of glucose, semi-lactosi assigns to each fraction.So the chromatographic separation of step 260 only needs separating xylose and pectinose to get final product, separating technology is easier to comparatively speaking.The tunning of glucose, semi-lactosi is assigned in the corresponding fraction according to the degree of absorption in chromatogram.
The feed liquid that goes out system after the concrete process chromatographic separation is:
Total reducing sugar is dense about 50～60%, and wherein the pending liquid of the wood sugar of wood sugar purity 〉=60% enters chromatogram arrangement, and the product that goes out chromatographic fractionation system has following described (1), (2), (3), (1), (2), (4) three kinds; The perhaps impurity fractions of (1), (2), (3), front, wood sugar peak, four kinds of the impurity fractions of (1), (2), (4), back, pectinose peak:
(1) Xylose fraction: wood sugar purity＞80%, refractive power concentration is about 15～30%;
(2) Arabic liquid glucose fraction: pectinose purity＞50%, refractive power concentration is 5～15%;
(3) the D-ribose fraction (namely using calcium type chromatographic column or plumbous type chromatographic column, see also shown in Figure 5, the product peak part of back, pectinose peak on the HPLC spectrogram that detects): refractive power concentration is 1～8%;
(4) citric acid fraction (namely using calcium type chromatographic column or plumbous type chromatographic column, the product peak part of front, wood sugar peak on the HPLC spectrogram that detects): refractive power concentration is 1～8%;
Shown in spectrogram before Fig. 5 the present invention the second technical scheme chromatographic separation, among the figure: G-citric acid, B-glucose, C-wood sugar, D-R, H-D-ribose.Among Fig. 5 just for above four kinds of positions that fraction is cut apart are described, in equipment substantial sepn process, can be in strict accordance with the position sharp separation of cutting apart among Fig. 5, but " you are among us and we are among you " is mixed in the inside, but main component is above four kinds of fractions.
The below is respectively the treatment scheme of pectinose fraction:
Step 261, the aftertreatment of L-arabinose
Identical with step 1314.The feed liquid of just processing is pectinose fraction feed liquid, no longer repeat specification.
After this step finished, obtaining the pectinose crystal purity was 98～99.8%.Pectinose crystal moisture after dry≤0.2%.
The 3rd technical scheme (process flow diagram is seen accompanying drawing 3):
The technical scheme of Fig. 3 is compared with Fig. 2's, the 3rd technical scheme is to carry out before the step that biological fermentation is produced Xylitol is advanceed to chromatographic separation, the fermentation removal of impurities sugar of the 3rd technical scheme only removes glucose, and keeps certain glucose concn to be beneficial to next step biological fermentation.The direct inoculation bacterial classification carries out biological fermentation generation Xylitol after removing glucose and removing thalline, uses at last chromatographic separation to separate the leavened prod of Xylitol, pectinose and other glucose.
The principle that biological fermentation is produced Xylitol is: the wood sugar feed liquid can at first generate Xylitol under the effect of bacterial classification, then be accompanied by the growth of bacterial classification, further metabolism occurs will generate other meta-bolitess such as xylulose, therefore in order to improve the output of Xylitol, the present invention has adopted the density of control oxygen supply amount and control bacterial classification, reduce wood sugar to the pathways metabolism of xylulose, wherein the present invention is to realize by the glucose content in the control wood sugar feed liquid for the control of the density of bacterial classification.
The 3rd technical scheme specifically may further comprise the steps:
Step 310, the feed liquid pre-treatment
Identical with the step 110 of the first technical scheme, hemicellulose hydrolysate, xylose mother liquid and the agriculture and forestry organic waste material waste liquid that contains five-carbon sugar are through concentrated behind the purification filtering or to be diluted to sugar dense about 10～30%.
Step 320 removes fermentation inhibitor
Identical with step 1311, be that handled feed liquid is different.
Step 330, fermentation removes glucose
Basic identical with step 1312, be that handled feed liquid is different, and only remove glucose, do not need to remove semi-lactosi.Specifically comprise:
In the technical program, the removing impurities sugar of feed liquid before fermentation that has removed fermentation inhibitor mainly is that glucose is removed in fermentation, makes the scope of glucose concn control 0.1～5%, within preferred 0.1～2%.The means of control glucose concn have a lot, include but not limited to all to be well known to those skilled in the art, so repeat no more by controlled fermentation time and/or change air flow etc.If also have semi-lactosi, the fermentation that then enters Xylitol as carbon source, semi-lactosi can be utilized by candida tropicalis in the fermenting process, so this step does not need to remove semi-lactosi.
In one embodiment, this step is used yeast saccharomyces cerevisiae except the bacterial classification of glucose, and the concrete technology parameter is as follows:
(1) at first sugared concentration is adjusted to 8～40%, preferred 10～35%;
(2) consisting of of bacterium culture medium nutritive salt: ammonium sulfate: 0.1～3.5%, preferred 0.5～2.5%; Potassium primary phosphate: 0.1～5%, preferred 0.5-3%; Sal epsom: 0.05～4%, preferred 0.2～2%; Corn steep liquor (the material meter of giving money as a gift): 0.5～20%, preferred 1～10%.
(3) fermentation parameter is: 25～45 ℃ of temperature, preferred 30～40; PH:3.5～5.5, air flow 0.2～0.8vvm.Through the fermentation of 10～28h, glucose content is down to 0.1～2%.
Step 340 is except thalline
Identical with step 1313, be that handled feed liquid is different.
Step 350, biological fermentation is produced Xylitol
The bacterial classification that biological fermentation wood sugar of the present invention generates Xylitol includes but not limited to such as candida tropicalis, Archon like yeast, not lattice candiyeast, monilia guilliermondii, Hansenula anomala, saccharomycopsis fibuligera, Candida parapsilosis and plan candida tropicalis etc.Preferred candida tropicalis, not lattice candiyeast, the Hansenula anomala of adopting.Preferred employing candida tropicalis, Hansenula anomala.Following examples only describe as an example of the Candida tropicalis kind example.
Remove fermented liquid behind the thalline through previous step and access a strain Candida tropicalis kind to the wood sugar generation Xylitol that ferments, the concrete technology condition is as follows, and per-cent number wherein is mass percent:
(1) the Candida tropicalis kind is cultivated in first class seed pot according to prescription and the condition of following seed culture medium, first order seed according to 5～20% inoculum size access secondary seed tank, is cultivated according to following seed culture based formulas and culture condition.Secondary seed is required to ferment according to following first fermention medium and technology controlling and process according to 5～20% inoculum size access fermentor tank.Remove thalline after the fermentation ends, the thalline of removal is back to next batch and ferments as bacterial classification, and the reuse fermentation is carried out according to following reuse fermention medium and technology controlling and process.
(2) substratum and technology controlling and process:
A, seed culture medium and technology controlling and process:
Fructus Hordei Germinatus soaks powder 0.5～2%, and preferred 0.8～1.5%; Yeast powder 0.1～1%, preferred 0.2～0.6%; Peptone 0.1～1, preferred 0.3～0.8%; Glucose 0.5～2.5%, preferred 1～1.5%; Wood sugar 0.5～2.5, preferred 1～1.5%, pH 5.0～7.5, and preferred 5.5～7.0; 30～40 ℃ of temperature, preferred 33-36 ℃; Incubation time 15～20h.
B, first fermention medium and technology controlling and process:
In the present embodiment, glucose content is below 2% in the pretreated liquid glucose, preferably 0.1～2%, and refractive power concentration 20～30%, primary ammonium phosphate 0.1～1%, preferred 0.2～0.6%; Potassium primary phosphate 0.05～0.5, preferred 0.1～0.3%; Sal epsom 0.005～0.02%, preferred 0.008～0.01%; The corn steep liquor material meter 0.5～2% of giving money as a gift, preferred 0.8～1.5%.
Technology controlling and process: pH 5～6; 33～42 ℃ of temperature; Air flow 0.1～2vvm, preferred 0.3～1vvm.When the concentration of glucose 0.3% when above, by the control air flow, keep dissolved oxygen more than 20%; When the concentration of glucose 0.3% when following, by the control air flow, keep dissolved oxygen below 1%.
C, candida tropicalis reuse fermention medium and technology controlling and process:
Thalline is that first fermented liquid is through whole thalline of membrane filtration or centrifugal collection, (glucose content is below 0.5% for pre-treatment wood sugar fraction, preferred 0.1～0.5%) refractive power concentration 20～30%, primary ammonium phosphate 0.05～0.3%, preferred 0.08～0.15%; Potassium primary phosphate 0.1～0.3%, preferred 0.12～0.2%; Sal epsom 0～0.1%, preferred 0～0.01%; The corn steep liquor material meter 0.01～0.3% of giving money as a gift, preferred 0.02～0.2%;
Technology controlling and process: pH 5～6,33～42 ℃ of temperature, air flow 0.1～2vvm, preferred 0.3～0.5vvm; By the control air flow, keep dissolved oxygen below 1%.
(3) technical indicator: 6～12 batches of thalline reuse lot numbers, sugar alcohol transformation efficiency 65～75%, fermentation time 22～38h.
Step 360 is except tropical candidiasis body
Fermented liquid adopts in one embodiment and filters or screening plant except tropical candidiasis body, and these equipment comprise: the equipment that plate-and-frame filter press, cardboard filter, filter, horizontal filtering machine, vibratory screening apparatus etc. can be tackled the thalline in the fermented liquid; Adopt in another embodiment the method for membrane filtration, membrane filter plant can adopt ceramic membrane, metal pipe type film, organic rolled film, organic tubular membrane, flat sheet membrane etc., preferred ceramic membrane, metal pipe type film, organic rolled film, the flat sheet membrane of adopting, hold back and be of a size of 2500g/mol～1 μ m, preferred 50nm～1 μ m; Feed liquid is introduced into plate-and-frame filter press and removes thalline and most of albumen through membrane filter plant more In yet another embodiment.
Further, in a preferred embodiment, the fermented liquid of having removed behind thalline and the most of albumen is removed the impurity such as albumen, pigment, crystallization inhibitor again with membrane filter plant.Described membrane filter plant adopts organic rolled film, tubular membrane etc., preferably adopts organic rolled film, holds back and is of a size of 50～2500g/mol, preferred 50～400g/mol, most preferably 100～300g/mol.The purpose that adds this mantle mainly is in order to remove albumen, pigment and crystallization inhibitor.Removing albumen is the difficulty that causes liquid glucose to darken and cause to follow-up decolouring because of Maillard reaction in order to alleviate subsequent handling; Removing pigment also is the difficulty of bringing in order to alleviate follow-up decolouring; Crystallization inhibitor mainly is the macromolecular substance such as oligose, colloid, albumen, and these materials can make the follow-up crystallization difficulty of sugar, make crystal childlike, these crystallization inhibitors can be removed the crystallization that is more conducive to sugar by membrane filtration.The use of this mantle will improve constant product quality of the present invention, cut down the consumption of raw materials, improves Crystal type.
Above-mentioned membrane filter plant adopts polymer organic membrane or mineral membrane; Be generally used for polymer organic membrane of the present invention and include but not limited to for example poly (ether sulfone) film, sulfonated polyether sulfone film, polyester film, polysulfone membrane, polyaramide film, polyvinyl alcohol film and poly-piperazine film and combination thereof.Mineral membrane commonly used includes but not limited to for example ZrO
2-and Al
2O
3-film.The configuration of film is selected from such as tubular type, rolling, tubular fibre etc.
Thalline after the filtration can be used as bacterial classification and receives in the wood sugar liquid glucose that next batch prepares substratum, carries out the fermentation of next batch.Xylitol liquid after the degerming then carries out further chromatography purity or directly decolours.
Step 370, concentrated
Carry out evaporation concentration to sugar dense 50～60% through the fermented liquid behind the membrane filtration.The equipment that adopts is identical with the equipment of aforementioned enrichment step, repeats no more.In preferred an enforcement, can carry out desalination with desalination modes such as ion-exchange, electrodialysis, electric desalinations before this enrichment step, thereby cause liquid glucose to darken to alleviate because ion with sugar Maillard reaction occurs when heating.
Step 380, chromatographic separation
This step and step 130 are basic identical.Difference is owing to removed most glucose and semi-lactosi before the chromatographic separation, remain slightly difference of content that a small amount of glucose, semi-lactosi assigns to each fraction.And the tunning of glucose, semi-lactosi is assigned in the corresponding fraction according to the degree of absorption in chromatogram.
The feed liquid that goes out system after the concrete process chromatographic separation is:
Sugar is dense about 50～60%, wherein the pending liquid of the Xylitol of xylitol purity 〉=50% enters chromatogram arrangement, the product that goes out chromatographic fractionation system has following described (1), (2), (3), (1), (2), (4) three kinds; The perhaps impurity fractions of (1), (2), (3), front, pectinose peak, four kinds of the impurity fractions of (1), (2), (4), back, Xylitol peak:
(1) Xylitol fraction: xylitol purity＞90%, refractive power concentration is about 15～30%;
(2) Arabic liquid glucose fraction: pectinose purity＞50%, refractive power concentration is 5～15%;
(3) D-ribose fraction (namely using calcium type chromatographic column or plumbous type chromatographic column, the product peak part of back, pectinose peak on the HPLC spectrogram that detects): refractive power concentration is 1～8%;
(4) citric acid fraction (namely using calcium type chromatographic column or plumbous type chromatographic column, the product peak part of front, wood sugar peak on the HPLC spectrogram that detects): refractive power concentration is 1～8%;
Shown in Fig. 6 color atlas, among the figure: G-citric acid, C-wood sugar, D-R, I-Xylitol, H-D-ribose.Among Fig. 6 just for above four kinds of positions that fraction is cut apart are described, in equipment substantial sepn process, can be in strict accordance with the position sharp separation of cutting apart among Fig. 6, but main component is above four kinds of fractions.
Step 381, the aftertreatment of L-arabinose
Identical with step 1314.The feed liquid of just processing is pectinose fraction feed liquid, no longer repeat specification.
After this step finished, obtaining the pectinose crystal purity was 98～99.8%.Pectinose crystal moisture after dry≤0.2%.
In the 3rd technical scheme of the invention described above, the byproduct that produces for the fermentation that removes glucose, semi-lactosi is such as the tunning of the glucose such as ethanol, D-ribose, citric acid, semi-lactosi, and the present invention separates removal in the following manner: the volatile product such as ethanol was introduced into the ethanol distillation device before fermented liquid purifies complete rear decolorizing with activated carbon carries out rectifying and reclaims.
The material of distillation can separate in the following manner if D-ribose, citric acid etc. can not volatilize.This programme is owing to directly carry out chromatographic separation after the fermentation ends, so the materials such as D-ribose, citric acid are assigned in other fraction except Xylitol, pectinose fraction.And in other fraction, account for main content, therefore can do to purify by the mode of crystallization; Perhaps, carry out separating-purifying with the mode of chromatographic separation.Preferably carry out separating-purifying with the mode of chromatographic separation.
More than by specific embodiment principle of the present invention and method are set forth, the explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof; Simultaneously, for one of ordinary skill in the art, according to thought of the present invention, all will change in specific embodiments and applications, in sum, the present disclosure content should not be construed as limitation of the present invention.
Claims (26)
1. the production method of a L-arabinose take hydrolyzed solution, the xylose mother liquid of agriculture and forestry organic waste material and/or the production waste liquid that contains five-carbon sugar as raw material, may further comprise the steps at least:
(a) feed liquid pre-treatment is treated to described raw material the mixed liquor that comprises at least wood sugar, xylan, L-pectinose, glucose and semi-lactosi;
(b) chromatographic separation is separated into pectinose fraction feed liquid and wood sugar fraction feed liquid with described mixed liquor, obtains pectinose fraction feed liquid;
Then may further comprise the steps (c1) and (c2), this two step or place before the chromatographic separation of step (b) described mixed liquor processed or place the chromatographic separation of step (b) after described pectinose fraction feed liquid is carried out the processing of following two steps:
(c1) except fermentation inhibitor, described fermentation inhibitor is impurity and the miscellaneous bacteria that fermentation is had inhibition;
(c2) fermentation removal of impurities sugar, described assorted sugar comprises glucose and semi-lactosi at least;
The step byproduct of the fermentation removal of impurities sugar of described step (c2) comprising: ethanol, D-ribose and/or citric acid, and described step (c2) comprises one of them of following methods:
1. under anaerobic glucose fermentation, semi-lactosi generate ethanol to use bacterial classification;
2. use bacterial classification to remove glucose, semi-lactosi generation ethanol, carbonic acid gas and water at the aerobic condition bottom fermentation;
3. use shikimic acid defective type subtilis to remove glucose, semi-lactosi generation D-ribose at the aerobic condition bottom fermentation;
4. use fermentation of Aspergillus niger to remove glucose, semi-lactosi generation citric acid;
Wherein said method 1. and the bacterial classification 2. be selected from one of following: yeast saccharomyces cerevisiae, bread yeast, saccharomyces uvarum, Xue's watt yeast, Hansenula anomala, Lip river lattice yeast or Ka Er Persian yeast;
(d) at last described pectinose fraction feed liquid is carried out aftertreatment and obtain L-pectinose.
2. the method for claim 1, it is characterized in that: described method comprises the hydrolysis treatment of described agriculture and forestry organic waste material being carried out following steps:
1. clean: silt and the chip of removing described agriculture and forestry organic waste material surface;
2. dilute acid pretreatment: soak described agriculture and forestry organic waste material to remove impurity with diluted acid, described dilute acid concentration is at 0.05 ~ 0.15%wt, and temperature is 110 ~ 130 ℃, and the treatment time is 1 ~ 3 hour; Described diluted acid is the mixed solution of in sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, nitric acid or these acid certain two kinds and two or more acid;
3. hydrolysis: add acid concentration in the acid solution of 0.5 ~ 1%wt, 128～132 ℃ of insulations of temperature 2.5 hours; Described acid solution is the mixed solution of in sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, nitric acid or these acid certain two kinds and two or more acid;
4. neutralization: at first liquid glucose is heated to 80～82 ℃, then adds calcium carbonate powders, until pH rises to 3.3 ~ 3.6, when mineral acid during at 0.09 ~ 0.12%wt, add again gac;
5. for the first time decolouring: at first liquid glucose is cooled to 50～52 ℃, then add the gac stirring until sampling detects transmittance and reach 60 ~ 76%;
6. desalination for the first time: adopt ash content, salt, organic acid and the mineral acid that ion-exchange, electrodialysis or EDI electricity desalination method contain in the destainer for the first time to be removed;
7. for the first time evaporation: adopt triple effect or quadruple effect falling-film evaporator that sugar concentration is brought up to 26.0～28.0%;
8. for the second time decolouring: add gac and stir;
9. desalination for the second time: adopt ash content, salt, organic acid and the mineral acid that ion-exchange, electrodialysis or EDI electricity desalination method contain in the destainer for the second time to be removed.
3. method as claimed in claim 2 is characterized in that: the ion-exchange that desalination adopts the first time 6. of described step is continuously through resin cation exchange, resin anion(R.A) exchange and resin cation exchange;
The exchange second time that the described step desalination second time 9. adopts be selected from following methods one of them: a kind of is first through anionresin, again through cationic exchange; Another kind is first through cationic exchange, again through anionresin; Also having a kind of is the use that is together in series of positive post and cloudy post, comes into operation simultaneously, regenerates simultaneously.
4. method as claimed in claim 2 or claim 3, it is characterized in that: 5. described step decolours the described first time and 8. step decolours the described second time adopts respectively reverse-flow decoloration process: minute N adding gac, wherein N is the natural number more than or equal to 2, new charcoal is used in last i.e. the N time decolouring, use the old charcoal of using after the N time decolouring for the N-1 time, use the old charcoal of using after the N-1 time decolouring for the N-2 time, by that analogy, all filter after each decolouring, the gac behind the decolorization filtering reclaims as solid waste for the first time.
5. method as claimed in claim 4, it is characterized in that: described agriculture and forestry organic waste material is the agriculture and forestry organic waste material that contains five-carbon sugar, is selected from corn cob, wheat straw, beet pulp, bagasse, kind skin.
6. the method for claim 1, it is characterized in that: described xylose mother liquid and/or the described pre-treatment that contains the waste liquid of five-carbon sugar comprise:
1. filter: adopt first mechanical filter equipment, adopt membrane filter plant to filter again; Described mechanical filter equipment is plate-and-frame filter press, bag type filtering machine, horizontal filtering machine, microfroc filter and filtering centrifuge; Described membrane filter plant is ceramic membrane, metallic membrane, organic rolled film and tubular membrane, holds back and is of a size of 100 ~ 5000g/mol;
2. desalination: adopt the mode of ion-exchange or adopt electrodialysis, EDI electricity desalination method.
7. method as claimed in claim 6, it is characterized in that: described membrane filter plant is organic rolled film, holds back and is of a size of 100 ~ 3000g/mol.
8. method as claimed in claim 7, it is characterized in that: described organic rolled film is held back and is of a size of 200 ~ 2500g/mol.
9. such as the described method of claim 6-8 any one, it is characterized in that: the described waste liquid that contains five-carbon sugar is selected from: the waste liquid that produces in the paper-making pulping process, contain the spentsulfiteliquor of five-carbon sugar or the solution that biomass digestion or hydrolysis is made with acid.
10. the method for claim 1 is characterized in that: also comprise enrichment step before the chromatographic separation of described step (b), the sugared concentration of feed liquid is concentrated into 50 ~ 60%.
11. such as claim 1 or 10 described methods, it is characterized in that: in described chromatrographic separation step, all described mixed liquor and process waters that enter chromatographic separation equipment pass through at least strainer removal solia particle of 20um of aperture; Described mixed liquor and process water keep temperature to be not less than 60 ℃; Eluent is 55 ~ 75 ℃ deionized water.
12. the method for claim 1, it is characterized in that: the described fermentation inhibitor in the step (c1) comprises impurity and miscellaneous bacteria, impurity wherein is coloring matter, macromolecular compound, heavy metal ion, muriate and the colloid with phenyl ring, and miscellaneous bacteria wherein is natural airborne yeast and bacterium; The fermentation inhibitor that removes of described step (c1) further may further comprise the steps:
1. for the heavy metal ion in the described impurity, muriate, and colloid, adopt the method for electrodeionization or ion-exchange to be removed;
2. for the coloring matter with phenyl ring in the described impurity, macromolecular compound and miscellaneous bacteria, adopt membrane filtration, ultrafiltration or the real method that disappears to be removed;
Described reality disappears and carries out sterilising treatment for feed liquid being heated to 60 ~ 120 ℃.
13. method as claimed in claim 12 is characterized in that: but 1. and 2. sequencing arbitrary arrangement of described step.
14. such as claim 12 or 13 described methods, it is characterized in that: 1. described step adopts the electrodeionization system, described electrodeionization system is EDI electrodeionization or electrodialysis;
The hyperfiltration process of described step in 2. selects mineral membrane or polymer organic membrane to adopt the mode of cross flow filter to filter, and described mineral membrane is held back size in 30 ~ 500 nanometers; Described polymer organic membrane is held back size at 1000 ~ 10000g/mol;
The membrane filtration of described step in 2. adopts ceramic membrane, metal pipe type film, organic rolled film, organic tubular membrane or flat sheet membrane, holds back and is of a size of 500 ~ 6000g/mol;
The reality of described step in the 2. method that disappears is described feed liquid to be heated to 60 ~ 120 ℃ carry out sterilising treatment.
15. method as claimed in claim 14 is characterized in that: the hyperfiltration process of described step in 2. selects mineral membrane to hold back size in 50 ~ 200 nanometers, and the polymer organic membrane is held back size at 1000 ~ 6000g/mol;
The membrane filtration of described step in 2. adopts organic rolled film or tubular membrane, holds back and is of a size of 500g/mol ~ 2000 g/mol;
The described reality method that disappears is heated to 80 ~ 115 ℃ with feed liquid and carries out sterilising treatment.
16. method as claimed in claim 15 is characterized in that: described polymer organic membrane is: poly (ether sulfone) film, sulfonated polyether sulfone film, polyester film, polysulfone membrane, polyaramide film, polyvinyl alcohol film and poly-piperazine film and combination thereof; Described mineral membrane is: ZrO
2-and Al
2O
3-film; Being configured as of described film: tubular type, rolling or tubular fibre.
17. the method for claim 1 is characterized in that: four kinds of methods of described step (c2) further may further comprise the steps respectively, and per-cent number wherein is mass percent:
Method is 1.:
(a) at first the sugared concentration of feed liquid is adjusted to 10 ~ 40%;
(b) consisting of of bacterium culture medium nutritive salt: urea or ammonium sulfate: 0.01 ~ 0.5%, potassium primary phosphate: 0.01 ~ 0.5%, sal epsom: 0.01 ~ 0.4%;
(c) fermentation parameter is: pH:2.5 ~ 5, and 33 ~ 45 ℃ of temperature, in blowing air or when beginning fermentation, do not pass into the air of 0.1 ~ 0.3vvm, when cell concentration reaches 10
8Individual/as during ml, to stop blowing air, carry out anaerobically fermenting; Fermentation time 8 ~ 22 hours;
(d) obtain at last inversion rate of glucose 97.15 ~ 98.5%, alcohol getting rate 98 ~ 99%, pectinose yield 96 ~ 100%, semi-lactosi clearance 35 ~ 55%;
Method is 2.:
(a) at first the sugared concentration of feed liquid is adjusted to 8 ~ 30%;
(b) consisting of of bacterium culture medium nutritive salt: ammonium sulfate: 0.1 ~ 3.5%, potassium primary phosphate: 0.1 ~ 5%, sal epsom: 0.05 ~ 4%, the corn steep liquor material meter of giving money as a gift: 0.5 ~ 20 %;
(c) fermentation parameter is: 25 ~ 45 ℃ of temperature, pH:3.5-5.5, air flow 0.2 ~ 0.5vvm, fermentation time 10 ~ 28 hours;
(d) obtaining at last the glucose clearance is 95% ~ 98%, and the semi-lactosi clearance is 50% ~ 70%, alcohol getting rate 90 ~ 95%, pectinose yield 96 ~ 100%;
Method is 3.:
(a) substratum and culture condition:
Slant medium: glucose 0.5 ~ 2%, peptone 0.4 ~ 2%, yeast extract paste 0.1 ~ 1%, sodium-chlor 0.1 ~ 1.2%, agar 0.8 ~ 3%, pH6.0 ~ 8.0,30 ~ 40 ℃ of culture temperature, incubation time 12 ~ 36 hours;
Seed culture medium: glucose 1 ~ 3%, the corn steep liquor material meter 1 ~ 3.5% of giving money as a gift, yeast extract paste 0.1 ~ 1%, dipotassium hydrogen phosphate 0.1 ~ 1%, potassium primary phosphate 0.1 ~ 0.8%, pH 6.0 ~ 8.0,30 ~ 40 ℃ of culture temperature, incubation time 10 ~ 32 hours;
Fermention medium: glucose 5-15%, the corn steep liquor material meter 1 ~ 5% of giving money as a gift, ammonium sulfate 0.2 ~ 1.5%, manganous sulfate 0.001 ~ 0.1%, calcium carbonate 1 ~ 6%, whole refractive power concentration 5 ~ 10% in the culture system of feed liquid, pH 6.0 ~ 8.0,30 ~ 40 ℃ of culture temperature, incubation time 30 ~ 90 hours;
(b) processing parameter: feed liquid when beginning fermentation add or the concentration that proceeds to glucose when fermentation 0.5% the time, the mode that employing stream adds adds;
(c) obtain at last glucose clearance 96 ~ 98.5%, pectinose yield 94 ~ 98%, semi-lactosi clearance 80 ~ 90%; D-ribose yield 35 ~ 45%;
Method is 4.:
(a) at first glucose concn is adjusted to 5 ~ 10%, feed liquid refractive power concentration is controlled at 20% ~ 30%;
(b) substratum: ammonium sulfate 0.05 ~ 1%, sal epsom 0.01 ~ 0.5%, the corn steep liquor material meter 0.01 ~ 1 of giving money as a gift;
(c) fermentation parameter: pH 5 ~ 8,30 ~ 42 ℃ of culture temperature, air flow 0.2 ~ 0.5vvm, fermentation time 35 ~ 52 hours, with glucose aspergillus niger is cultured to logarithm latter stage first, then, adds concentration in the fermentor tank and be 20 ~ 30% pectinose fraction, producing citric acid concentration is 5 ~ 6%, and transformation efficiency is 92 ~ 95%;
(d) obtain at last glucose clearance 95.6 ~ 98.7%, pectinose yield 94.6 ~ 98.3%, citric acid yield are 90 ~ 95%, semi-lactosi clearance 82 ~ 89%.
18. method as claimed in claim 17 is characterized in that: also comprise after the described step (c2) except thalline: by filtration or method for sieving or adopt first and filter or screening is removed thalline in the fermented liquid by membrane filtering method for the first time again;
Described filtration or screening plant are: plate-and-frame filter press, cardboard filter, horizontal filtering machine and vibratory screening apparatus;
Described first time, membrane filter plant was: ceramic membrane, metal pipe type film, organic rolled film, organic tubular membrane and flat sheet membrane, and hold back and be of a size of 2500g/mol ~ 1um.
19. method as claimed in claim 18 is characterized in that: described adopt to filter first or screening again by the first time membrane filtering method also comprise for the second time membrane filtration step, described second time, membrane filter plant was organic rolled film or tubular membrane.
20. method as claimed in claim 19 is characterized in that: described membrane filter plant employing first time ceramic membrane, metal pipe type film, organic rolled film or flat sheet membrane, hold back and be of a size of 50nm ~ 1um; Described second time, membrane filter plant adopted organic rolled film, held back and was of a size of 50 ~ 2500g/mol.
21. method as claimed in claim 19 is characterized in that: described first time membrane filter plant and described second time membrane filter plant adopt polymer organic membrane or mineral membrane; Described polymer organic membrane is: poly (ether sulfone) film, sulfonated polyether sulfone film, polyester film, polysulfone membrane, polyaramide film, polyvinyl alcohol film and poly-piperazine film and combination thereof; Described mineral membrane is: ZrO
2-and Al
2O
3-film; Being configured as of described film: tubular type, rolling, and tubular fibre.
22. the method for claim 1 is characterized in that: the post-processing step of described pectinose fraction feed liquid comprises:
1. decolouring: adopt gac, add-on is 2 ‰ ~ 2%wt, and churning time is 0.5 ~ 2 hour;
2. desalination: adopt ion-exchange, electrodialysis and/or EDI electricity desalination mode;
3. concentrated: that described pectinose fraction feed liquid is concentrated into 50 ~ 85% sugared concentration;
4. crystallization: comprise at least one times crystallization;
5. dry: as to obtain respectively L-pectinose finished product.
23. method as claimed in claim 22 is characterized in that: 1. described step one of decolours specifically in the following ways: a kind of is that the gac of disposable adding capacity stirs decolouring, then filters; Another kind is reverse-flow decoloration process: minute N adding gac, wherein N is the natural number more than or equal to 2, new charcoal is used in last i.e. the N time decolouring, use the old charcoal of using after the N time decolouring for the N-1 time, use the old charcoal of using after the N-1 time decolouring for the N-2 time, all filter after each decolouring, by that analogy, the gac behind the decolorization filtering reclaims as solid waste for the first time.
24. method as claimed in claim 22 is characterized in that: described step 2. desalination comprises: adopt first electrodialysis or EDI electricity desalination and then ion-exchange to carry out desalination.
25. method as claimed in claim 22 is characterized in that: described step is 3. concentrated specifically to be comprised: the sugared concentration of described feed liquid is using triple effect vacuum falling film vaporizer concentrated below 60%; The sugared concentration of described feed liquid is higher than 60% and uses the vacuum single-action concentrated.
26. method as claimed in claim 22 is characterized in that: described step 4. crystallization comprises the crystallization that twice or twice are above, and the sugar that each crystallization obtains after will the massecuite centrifuging with last crystallization dissolves again crystallization after the evaporation concentration again; Wherein each crystallization comprises: the feed liquid after will concentrating is squeezed into horizontal crystallizer tank with whipping appts and cooling device, adopts the mode of decrease temperature crystalline, and the control cooling rate is for per hour lowering the temperature 0.1 ~ 3 ℃; Or when temperature is more than 55 ℃, per hour fall 0.5 ℃, treat then per hour to fall 1 ℃ when temperature is down to below 55 ℃; Described crystallizer tank mixing speed is controlled at 0.5 ~ 20rpm; The crystal seed add-on accounts for 0.5 of liquid glucose quality ~ 10 ‰.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100187996A CN101665524B (en) | 2009-09-30 | 2009-09-30 | Method for producing L-arabinose |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100187996A CN101665524B (en) | 2009-09-30 | 2009-09-30 | Method for producing L-arabinose |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101665524A CN101665524A (en) | 2010-03-10 |
| CN101665524B true CN101665524B (en) | 2013-05-29 |
Family
ID=41802325
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100187996A Active CN101665524B (en) | 2009-09-30 | 2009-09-30 | Method for producing L-arabinose |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101665524B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102771687B (en) * | 2011-05-10 | 2014-09-03 | 陈培豪 | L-arabinose-containing metabolism regulator and production method thereof |
| CN102796830B (en) * | 2012-04-12 | 2014-06-18 | 淮北中润生物能源技术开发有限公司 | Method for producing arabinose and co-producing various products |
| CN102634612B (en) * | 2012-04-28 | 2013-02-13 | 广西大学 | Method for producing high-purity L-arabinose by using bagasse pith as raw materials |
| CN102719511B (en) * | 2012-07-06 | 2015-03-11 | 江苏巨托食品科技有限公司 | Method for extracting L-arabinose from crop byproduct by utilizing multi-strain mixed fermentation |
| NZ743055A (en) * | 2013-03-08 | 2020-03-27 | Xyleco Inc | Equipment protecting enclosures |
| WO2023130594A1 (en) * | 2022-01-06 | 2023-07-13 | 唐传生物科技（厦门）有限公司 | Arabinose as well as preparation and use thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1699587A (en) * | 2005-06-02 | 2005-11-23 | 江南大学 | Process for extracting xylose and xylitol from a xylose mother liquor or a xylose digest |
| CN101372700A (en) * | 2008-07-24 | 2009-02-25 | 上海交通大学 | Method for extracting L-arabinose from xylose mother liquor and biomass acid hydrolysis solution |
| CN101497904A (en) * | 2008-02-01 | 2009-08-05 | 唐传生物科技（厦门）有限公司 | Method for producing xylitol and arabinose at the same time |
-
2009
- 2009-09-30 CN CN2009100187996A patent/CN101665524B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1699587A (en) * | 2005-06-02 | 2005-11-23 | 江南大学 | Process for extracting xylose and xylitol from a xylose mother liquor or a xylose digest |
| CN101497904A (en) * | 2008-02-01 | 2009-08-05 | 唐传生物科技（厦门）有限公司 | Method for producing xylitol and arabinose at the same time |
| CN101372700A (en) * | 2008-07-24 | 2009-02-25 | 上海交通大学 | Method for extracting L-arabinose from xylose mother liquor and biomass acid hydrolysis solution |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101665524A (en) | 2010-03-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101665523B (en) | The production method of L-arabinose and D-xylose pref | |
| CN101659681B (en) | Method for producing wood sugar product | |
| JP4038577B2 (en) | Alcohol production system and alcohol production method | |
| CN100572543C (en) | Utilize corn cob or agriculture and forestry organic waste material to prepare the method for Xylitol | |
| CN101665524B (en) | Method for producing L-arabinose | |
| CN102286571B (en) | Clean and high-efficiency production process for preparing xylose and L-arabinose | |
| CN102268490B (en) | Clean technique for co-producing xylose, xylitol and arabinose from agricultural waste and forest waste | |
| CN101392273B (en) | Clean production process of lactic acid | |
| CN101538589A (en) | New clean method for producing xylitol and arabinose | |
| CN103502460A (en) | Systems and methods for improving fermentation | |
| CN101372700A (en) | Method for extracting L-arabinose from xylose mother liquor and biomass acid hydrolysis solution | |
| CN101555503A (en) | Method for separating and extracting L-arabinose from waste wood sugar mother liquid from wood sugar production | |
| CN101899479B (en) | Production method for preparing xylitol by using agricultural and forestry waste | |
| CN101294169A (en) | Novel technique for extracting lactic acid with sodium salt fermentation electrodialysis | |
| CN101705253A (en) | Method for treating xylose mother solution | |
| CN101921810B (en) | Method for preparing xylitol and L-arabinose mixed crystal from xylose mother liquid | |
| CN107354181A (en) | A kind of method for regulating and controlling debirs cooperative fermentation L lactic acid using cathodic reduction | |
| CN101948183A (en) | Microbial flocculant, preparation method and use thereof | |
| CN110759754B (en) | Harmless treatment and resource utilization method of glucosamine fermentation bacterium residues | |
| CN102703334B (en) | Strain producing erythritol and method for producing erythritol by using strain | |
| CN101823953A (en) | Method for separating lactic acid from fermentation liquor by flocculation and carrying out flocculate comprehensive utilization | |
| SU1373728A1 (en) | Method of cultivating chlorella | |
| EP0062026B1 (en) | Process for producing cellulase and an installation for carrying out the process | |
| CN101525637A (en) | Method for cleanly producing potato ethanol with low viscosity | |
| CN112662710B (en) | Method for producing L-lactic acid by continuous fermentation of lignocellulose |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: JI NAN HEALTANG BIOTECHNOLOGY CO., LTD. Free format text: FORMER OWNER: SHENGQUAN GROUP CO. LTD., JINAN Effective date: 20120213 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20120213 Address after: 250204 Shandong city of Ji'nan province Zhangqiu City Diao Zhen Quan Chemical Industrial Park Applicant after: Ji'nan Healtang Biotechnology Co., Ltd. Address before: 250204 chemical industry park, Diao Town, Ji'nan City, Shandong, Zhangqiu Applicant before: Shengquan Group Co., Ltd., Ji'nan City |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |