CN101665524A

CN101665524A - Method for producing L-arabinose

Info

Publication number: CN101665524A
Application number: CN200910018799A
Authority: CN
Inventors: 唐一林; 江成真; 高绍丰; 崔建丽; 贺芹; 孟海波
Original assignee: Jinan Shengquan Group Share Holding Co Ltd
Current assignee: Ji'nan Healtang Biotechnology Co., Ltd.
Priority date: 2009-09-30
Filing date: 2009-09-30
Publication date: 2010-03-10
Anticipated expiration: 2029-09-30
Also published as: CN101665524B

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, aswell 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

The production method of L-arabinose

Technical field

The present invention relates to the production technology of L-arabinose, is raw material production L-arabinose goods, the method for glucose fermentation products such as by-product ethanol, D-ribose, citric acid simultaneously with hemicellulose hydrolysate, xylose mother liquid and the production waste liquid that contains five-carbon sugar especially.

Technical background

L-arabinose belongs to five-carbon ring aldehydo sugar, exists with arabinan, pectinose sill glycan, Arabic glycosyl 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, and it is synthetic etc. to be used as medicine intermediate, the preparation that is used for biochemical field bacteria culture medium and spices.Xylose pref such as wood sugar, Xylitol more and more are subjected to people's favor as sweetening agent.A lot of medical health care functions of wood sugar, Xylitol are confirmed by scientific research, as lowering blood glucose, prevent functions such as carious tooth.

Plant tissue is made up 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 difference of different plant tissues.

Chinese patent 200910077943.3 discloses a kind of method of utilizing corn cob to produce L-arabinose, disclosed a kind of pectinose, the technology 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) materials such as 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 was not removed the step of glucose and semi-lactosi before chromatographic separation pectinose and Xylitol, can not purify after causing chromatographic separation pectinose and Xylitol.What 4) feed liquid fermentation is adopted is candida tropicalis, and pectinose generates arabitol when removing wood sugar and glucose, thus mass consumption 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 handled with amylase earlier, use the dilute acid hydrolysis corn bran then, 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 certainly will cause the fermentation loss of pectinose like this with the bacterial classification that can utilize five-carbon sugar if most of wood sugars are removed in fermentation.And if, slattern a large amount of wood sugars, economic inadequately environmental protection on the one hand because wood sugar content is more is removed as impurity; 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 crystalline way, thereby cause the pectinose product purity not enough.

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 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 is a raw material with hydrolyzed solution, the xylose mother liquid of agriculture and forestry organic waste material and/or the production waste liquid that contains five-carbon sugar, may further comprise the steps at least:

(a) feed liquid pre-treatment is treated to described raw material the mixed liquor that comprises wood sugar, xylan, L-arabinose, glucose and semi-lactosi at least;

(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 handled or place the chromatographic separation of step (b) after described pectinose fraction feed liquid is carried out the processing of following two steps:

(c1) remove fermentation inhibitor, described fermentation inhibitor is impurity and the assorted bacterium 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 of acid, 128～132 ℃ of insulations of temperature 2.5 hours at 0.5～1%wt; 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 ℃, adds calcium carbonate powders then, rise to 3.3～3.6,, add gac again when mineral acid during at 0.09～0.12%wt up to pH;

5. decolouring for the first time: at first liquid glucose is cooled to 50～52 ℃, add the gac stirring then and reach 60～76% up to sampling detection printing opacity;

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. evaporation for the first time: adopt triple effect or quadruple effect falling-film evaporator that sugar concentration is brought up to 26.0～28.0%;

8. decolouring for the second time: 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 method one of them: a kind of is earlier through anionresin, again through cationic exchange; Another kind is earlier 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.

Reverse-flow decoloration process is adopted in the 5. described decolouring first time of the wherein said step of technique scheme and the 8. described decolouring second time of step respectively: 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 decolouring back exhausted for the N-1 time the N time, use the old carbon of decolouring back exhausted for the N-2 time the N-1 time, by that analogy, all filter after each decolouring, the gac behind the decolorization filtering is as solid useless the recovery 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 corn cob, wheat straw, beet pulp, bagasse, agricultural crop straw, stem leaves of plants root at least, plants skin.

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 mechanical filter equipment earlier, 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 the 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 ℃ a deionized water.

The technique scheme wherein described fermentation inhibitor in the step (c1) comprises impurity and assorted bacterium, impurity wherein comprises the coloring matter of being with phenyl ring, macromolecular pigment, macromolecular compound, heavy metal ion, muriate, colloid and polymkeric substance, and assorted bacterium 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 assorted bacterium, adopt membrane filtration, ultrafiltration or the real method that disappears to be removed.

1. and 2. the wherein said step of technique scheme is order or arrange arbitrarily, perhaps first step 1., the back step 2..

1. the wherein said step of technique scheme adopts the electrodeionization system, and described electrodeionization system comprises EDI electricity desalting system and electrodialysis;

The hyperfiltration process of described step in 2. selects for use 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 for use 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 method:

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, unusual debaryomyces hansenii, 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 a 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, the air of feeding 0.1～0.3vvm when blowing air or fermentation do not begin is when cell concentration reaches 10 ⁸Individual/as during ml, to stop blowing air, carry out anaerobically fermenting; Fermentation time 8～22 hours;

(d) obtain inversion rate of glucose 97.15～98.5% at last, ethanol yield 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 the glucose clearance at last is 95%～98%, and the semi-lactosi clearance is 50%～70%, ethanol yield 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%, lime 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 glucose clearance 96～98.5% at last, 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, earlier aspergillus niger is cultured to logarithm latter stage, then, in fermentor tank, adds concentration and be 20～30% pectinose fraction with glucose, producing citric acid concentration is 5～6%, and transformation efficiency is 92～95%;

(d) obtain glucose clearance 95.6～98.7% at last, 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) and remove thalline: by filtration or method for sieving or for the first time membrane filtering method or adopt earlier 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 machine, 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 earlier filter or screening again by the first time membrane filtering method also comprise membrane filtration step for the second time, 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, the described pectinose fraction feed liquid of removing behind the thalline is carried out the following step:

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. concentrate: described pectinose fraction feed liquid is concentrated into i.e. 50～85% the sugared concentration of hypersaturated state;

4. crystallization: comprise primary crystallization at least;

5. dry: as to obtain the L-arabinose finished product respectively.

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, filters then; Another kind is reverse-flow decoloration process: 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 decolouring back exhausted for the N-1 time the N time, use the old carbon of decolouring back exhausted for the N-2 time the N-1 time, all filter after each decolouring, by that analogy, the gac behind the decolorization filtering is as solid useless the recovery for the first time.

The wherein said step of technique scheme 2. desalination comprises: adopt electrodialysis or EDI electricity desalination and then ion-exchange to carry out desalination earlier.

3. the wherein said step of technique scheme concentrates and specifically comprise: the sugared concentration of described feed liquid is using triple effect vacuum drop film evaporator to concentrate below 60%; The sugared concentration of described feed liquid is higher than 60% and uses the vacuum single-action to concentrate.

The wherein said step of technique scheme 4. crystallization comprises twice or twice above crystallization that each crystallization will be dissolved the sugar that obtains after the centrifuging of last crystalline massecuite crystallization once more after the evaporation concentration again; Wherein each crystallization comprises: the feed liquid after will concentrating is squeezed into the horizontal crystallizer tank that has 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 reduced 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 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 the assorted bacterium of impurity, and fermentation can be carried out smoothly; And removed the assorted sugar that comprises glucose and semi-lactosi at least by fermentation process, make 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 of 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, has not only created new wealth but also has protected environment for society.

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 first technical scheme;

Fig. 2 is the process blocks synoptic diagram of the present invention's second technical scheme;

Fig. 3 is the process blocks synoptic diagram of the present invention's the 3rd technical scheme;

Fig. 4 is a spectrogram before the present invention's first technical scheme chromatographic separation;

Fig. 5 is a spectrogram before the present invention's second technical scheme chromatographic separation;

Fig. 6 is a 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: corn cob, wheat straw, beet pulp, bagasse, agricultural crop straw, stem leaves of plants root, wheat bran, maize peel, or the like, 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 subsequent step again 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 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.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 influence 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.

Below respectively just the difference of Production Flow Chart of the present invention adopt three kinds of technical schemes to be described in detail:

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 handled.

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 is that example describes with the corn cob, and 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, the back is delivered to by belt and is entered 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.Washing back corn cob enters chapelet or high spud angle band rib rotary conveyor after dewatering by vibrating-dewatering screen, be raised then 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 is filled the material back and is begun to be hydrolyzed.

The first step of hydrolysis is a dilute acid pretreatment.Enter the corn cob of hydrolyzer, its cellular skin still unavoidably is attached with firm earth, and corn cob also contains carbohydrate, pigment, pectin, nitrogenous thing and the fat etc. of non-hemicellulose, 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 these impurity in advance before hydrolysis, treatment condition are that 0.05～0.15%wt sulfuric acid was handled 1～3 hour for 110～130 ℃.This condition can not cause hydrolysis of hemicellulose substantially 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 that sulfuric acid, its acid strength is slightly different according to acid power.

Hydrolysis is finished hydrolyzed solution is discharged collection, and waste residue is washed, opens residual cake valve then with the residue emptying.The hydrolyzed solution of collecting is mainly composed 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,, therefore need sulfuric acid is neutralized if be directly used in next process meeting severe corrosion equipment and the difficult removal of sulfuric acid.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, rise to 3.3～3.6 up to pH, 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 bigger 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, decolouring for the first time:

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 makes full use of gac is saved gac, the reverse-flow decoloration process of preferred employing, promptly 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 decolouring back exhausted for the N-1 time the N time, use the old carbon of decolouring back exhausted for the N-2 time the N-1 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 bigger, accounts for the about 3/4ths of total consumption charcoal amount, and the gac behind the decolorization filtering is as solid useless the recovery 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 not enough if the bleacher sampling detects printing opacity behind filter paper filtering, need add fresh gac and reach 60～76% up to sampling detection printing opacity.

Because the many pigments in the wood sugar liquid are easier of charcoal absorption under low temperature relatively, so liquid glucose should cool to 50～52 ℃ before entering bleacher, it is no longer to need cooling before destainer enters during cationic exchange that this temperature also has a benefit.

Feed liquid was processed to be destainer for the first time 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 remove by ion-exchange.Ion-exchange for the first time 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 technologies such as electrodialysis, EDI electricity desalination except that the method for using ion-exchange.Technology such as electrodialysis, electric desalination is traditional desalination process, no longer is described in detail at this.

6, evaporation for the first time:

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 back liquid glucose quality.

General triple effect or the quadruple effect falling-film evaporator of adopting of evaporation sent to decolouring for the second time after vaporizer comes out.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 imitating.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, decolouring for the second time:

Liquid glucose is by after evaporating for the first time, concentration improves, wherein contain the also raising simultaneously of coloring matter concentration of compounds such as phenyl ring class, add that some organic substances produce new coloring matter under the evaporation high temperature action, liquid glucose transmittance after evaporation for the first time drops to about 20%.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.

Decolouring for the second time also can adopt the adverse current decoloration process to reduce gac consumption as decolouring for the first time.For the first time evaporation back liquid glucose temperature is between 60～65 ℃, and decolouring for the second time is to need not liquid glucose is lowered the temperature with decolouring the first time different.Decolouring for the second time should make that printing opacity reaches 90～98%.

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 ion-exchange process continuation for the second time 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 exchange for the second time has multiple way: a kind of is earlier through anionresin, again through cationic exchange; Another kind is earlier 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 removal of foreign ion for the second time can also be used technologies such as electrodialysis, EDI electricity desalination except that the method for using ion-exchange.Technology 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 is meant in traditional xylose production process process, solid (wood sugar crystal) is separated the liquid of removing the back and obtaining 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, have not only created new wealth but also have protected environment for society.

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 simple relatively., specific as follows according to the impurity situation generally through purifying step such as filtration, desalinations:

1, filter:

Liquid glucose through filter type from coarse to fine, is removed oarse-grained mechanical impurity earlier earlier, removes suspended particle and dust etc. again with secondary filter then.At last, use membrane filter plant to remove 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 the 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 influence next step concentratedly darkens liquid glucose and destroys sugar; Contain on the other hand foreign ion especially heavy metal ion can influence the fermentation of subsequent processing.Therefore the foreign ion in the waste liquid need be removed.Desalination generally adopts the mode of ion-exchange or adopts technologies such as electrodialysis, EDI electricity desalination.Technologies 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 the pre-treatment of the present invention for 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 impurity such as salt is arranged, and then feed liquid is carried out following flow process:

Step 120 concentrates

Because the dense too low meeting of sugar influence the separating effect and the working efficiency of chromatographic equipment, and can make the fraction sugar concentration after the separation low excessively, reduce the subsequent handling usage ratio of 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 a concentration.High temperature destroys and saves the steam that evaporation is consumed when avoiding the liquid glucose evaporation concentration, and liquid glucose concentrates general adopt vacuum-evaporation, especially triple effect or the falling film evaporation of quadruple effect vacuum.

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 wood sugar fraction, and pectinose fraction, wood sugar could be separated like this, comprise that the assorted sugar etc. of glucose and semi-lactosi enters wood sugar fraction, pectinose fraction respectively.

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 the safe operation of chromatographic column simultaneously, 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; Do not separate out crystallization for the feed liquid that makes high density, 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 the discharging pump of chromatogram xylose product fluid, pectinose product fluid and salt and glucose simultaneously, system carries out continuous production under automatization control.

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) wood sugar liquid 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 (promptly 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 (promptly 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 a spectrogram before the present invention's first technical scheme chromatographic separation, among the figure: A-organic acid etc., B-glucose, C-wood sugar, D-pectinose, E-ethanol glycerine etc., F-fusel.

Like this, just wood sugar in the liquid glucose and pectinose are separated, obtained the wood sugar fraction, reached the pectinose fraction.

Further treatment scheme with regard to the pectinose fraction describes below:

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 assorted bacterium, and impurity wherein comprises the coloring matter of being with phenyl ring, macromolecular pigment, macromolecular compound, heavy metal ion, muriate, colloid, polymkeric substance etc.; Assorted bacterium wherein mainly is the airborne assorted bacterium of occurring in nature such as yeast, bacterium etc., contains nutritive substances such as glucose in the pectinose fraction, and liquid glucose needs only ingress of air, and airborne assorted bacterium will grow in liquid glucose, breed.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 for example EDI electricity desalting system, electrodialysis etc.

2. for coloring matter, macromolecular compound, polymkeric substance, and assorted bacterium, the present invention adopts membrane filtration, ultrafiltration or the real method that disappears to be removed.

Above-mentioned steps 1. and 2. order can be arranged arbitrarily, wherein preferred first step 1., the back step 2..

Hyperfiltration process in some embodiments of the invention selects for use 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 the real method that disappears to remove impurity and assorted bacterium: 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 for example tubular type, rolling, tubular fibre etc.

Step 1312, fermentation removal of impurities sugar

The pectinose fraction contains 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 change into other low-boiling or in chromatographic fractionation system easily with isolating other products of pectinose, separate assorted sugared in glucose fermentation products such as by-product ethanol, D-ribose, citric acid.

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, unusual debaryomyces hansenii, 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 with 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 are that example describes with the yeast saccharomyces cerevisiae, but can adopt bacterial classification above-mentioned to carry out the fermentation of glucose and semi-lactosi in further embodiments.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 processing parameter of alcoholic acid 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, and 33～45 ℃ of temperature, feeding micro-air when blowing air or fermentation do not begin (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%, ethanol yield 98～99%, pectinose yield 96～100%, semi-lactosi clearance 35～55%; Fermentation time 8～22h.

Example 2,The pectinose fraction uses yeast saccharomyces cerevisiae as follows at the concrete processing parameter that aerobic condition bottom fermentation removal glucose, semi-lactosi generate ethanol, carbonic acid gas and water: 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%, ethanol yield 90～95%, pectinose yield 96～100%.

Example 3,The pectinose fraction uses shikimic acid defective type subtilis as follows at the concrete processing parameter that aerobic condition bottom fermentation removal glucose, semi-lactosi generate D-ribose: 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%; Lime 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 perhaps the concentration that 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 processing 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 earlier with glucose aspergillus niger to be cultured to logarithm latter stage, then, adds concentration and be 20～30% pectinose fraction in fermentor tank.

(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 a pectinose, also contained impurity components such as thalline, salt in certain this fermented liquid.

Step 1313, remove thalline:

Because also contain 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 and make liquid glucose darken, and influence 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 machine, filter, horizontal filtering machine, vibratory screening apparatus etc. can be tackled the thalline in the fermented liquid; Adopt the method for membrane filtration in another embodiment, 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 earlier, like this after film, the flux of film is strengthened, prevent to stop 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 a membrane filter plant again and remove 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 in order to alleviate the difficulty that subsequent handling causes liquid glucose to darken and cause to follow-up decolouring because of Maillard reaction; Removing pigment also is in order to alleviate the difficulty that follow-up decolouring brings; Crystallization inhibitor mainly is macromolecular substance such as oligose, colloid, albumen, the oligose here mainly is meant 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 the crystallization crystal formation.

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 for example 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-pectinose.Natural L-arabinose is likely by the D-wood sugar by the result of uridine diphosphate (UDP) derivative through the enzymatic isomerization reaction.Nature D-pectinose 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 having 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, promptly divide N time and add gac, wherein N is the natural number more than or equal to 2, and promptly new charcoal is used in the N time decolouring for the last time, the N time old carbon of decolouring back exhausted of the N-1 time use, use the old carbon of decolouring back exhausted for the N-2 time the N-1 time, all filter after each decolouring, by that analogy, the gac behind the decolorization filtering is as solid useless the recovery for the first time.Second kind of technology of preferred employing, this technology can significantly reduce cost.The decolouring of this step should make that printing opacity reaches 90～98%.

2. desalination

The effect of desalination mainly is to purify liquid glucose, the salt that nutritive salt that adds in the removal fermenting process and gac are brought into.Desalination generally adopts the mode of ion-exchange or adopts technologies such as electrodialysis, EDI electricity desalination.Technologies 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. concentrate

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 drop film evaporator to concentrate below 60%; Sugar concentration is higher than 60% and uses the vacuum single-action to concentrate.

4. crystallization

Liquid glucose after concentrating is squeezed into crystallizer tank.Crystallizer tank is the horizontal container that has whipping appts and cooling device, stirs to be generally two helical-ribbon types stirrings, and crystallizer tank has chuck and coil pipe, can feed heat-eliminating medium and heating medium.The mode of decrease temperature crystalline is adopted in the crystallization of pectinose.The temperature that concentrates the back massecuite from single-action begins cooling, 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 ℃, reduce 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 the concentration and the temperature fall time of liquid glucose before the crystallization well, make solids content 〉=20% in the massecuite 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.Repeatedly during crystallization, the sugar that obtains after the centrifuging of last crystalline massecuite be dissolved again crystallization once more after the evaporation concentration if desired.

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.

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, be 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 " removing thalline " these three steps place the treatment scheme of pectinose fraction, the technical scheme of Fig. 2 is then carried out " removing fermentation inhibitor " earlier, " fermentation removal of impurities sugar ", and " remove thalline " these three steps, and then obtain the pectinose fraction and carry out subsequent disposal by chromatographic separation.Second technical scheme specifically may further comprise the steps:

Step 210, the feed liquid pre-treatment

Identical with the step 110 of first technical scheme, hemicellulose hydrolysate, xylose mother liquid and the agriculture and forestry organic waste material waste liquid that contains five-carbon sugar are dense about 10～30% through concentrating or be diluted to total reducing sugar sugar behind the purification filtering.

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 removed 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 concentrates

Through carrying out evaporation concentration to sugar dense 50～60% except that 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 because ion with sugar Maillard reaction takes place when heating to alleviate.

Step 260, chromatographic separation

In second technical scheme, the chromatographic separation of the step 130 of this step chromatographic separation and first technical scheme is basic identical.Different is, because liquid glucose has passed through step 220,230 fermentations and removed most glucose, semi-lactosi, remaining a spot of glucose, semi-lactosi, to assign to the content of each fraction slightly different.So the chromatographic separation of step 260 only need separate wood sugar and pectinose gets 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:

(3) D-ribose fraction (promptly 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 (promptly 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 second technical scheme chromatographic separation, among the figure: G-citric acid, B-glucose, C-wood sugar, D-pectinose, 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, but " you are among us and we are among you " is mixed in the inside, but main component is above four kinds of fractions in strict accordance with the position sharp separation of cutting apart among Fig. 5.

Be respectively the treatment scheme of pectinose fraction below:

Step 261, the aftertreatment of L-arabinose

Identical with step 1314.Just the feed liquid of handling is a pectinose fraction feed liquid, no longer repeat specification.

After this step finished, obtaining the pectinose crystal purity was 98～99.8%.Dry back pectinose crystal moisture≤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 chromatographic separation to separate the leavened prod of Xylitol, pectinose and other glucose at last.

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, be accompanied by the growth of bacterial classification then, further metabolism takes place 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 the pathways metabolism of wood sugar to 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 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 concentrating behind the purification filtering or to be diluted to sugar dense about 10～30%.

Step 320 removes fermentation inhibitor

Identical with step 1311, be handled feed liquid difference.

Step 330, fermentation removes glucose

Basic identical with step 1312, be handled feed liquid difference, and only remove glucose, do not need to remove semi-lactosi.Specifically comprise:

In the technical program, the take off assorted 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 control 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, the bacterial classification that this step is removed glucose uses yeast saccharomyces cerevisiae, and concrete processing 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 reduces to 0.1～2%.

Step 340 is removed thalline

Identical with step 1313, be handled feed liquid difference.

Step 350, biological fermentation is produced Xylitol

The bacterial classification that biological fermentation wood sugar of the present invention generates Xylitol for example includes but not limited to that candida tropicalis, Archon are like yeast, not lattice candiyeast, monilia guilliermondii, unusual debaryomyces hansenii, saccharomycopsis fibuligera, Candida parapsilosis and plan candida tropicalis etc.Preferred candida tropicalis, not lattice candiyeast, the unusual debaryomyces hansenii of adopting.Preferred employing candida tropicalis, unusual debaryomyces hansenii.Following examples are that example describes with the candida tropicalis bacterial classification only.

Suddenly remove fermented liquid behind the thalline through previous step and insert a strain candida tropicalis bacterial classification to the wood sugar generation Xylitol that ferments, concrete processing condition are as follows, and per-cent number wherein is a mass percent:

(1) the candida tropicalis bacterial classification is cultivated in first class seed pot according to the prescription and the condition of following seed culture medium, first order seed is inserted the secondary seed jar according to 5～20% inoculum size, cultivate according to following seed culture based formulas and culture condition.Secondary seed is inserted fermentor tank according to 5～20% inoculum size to be required to ferment according to following first fermention medium and technology controlling and process.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 the whole thalline of first fermented liquid through membrane filtration or centrifugal collection, pre-treatment wood sugar fraction (glucose content below 0.5%, 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 removed tropical candidiasis body

Fermented liquid removes tropical candidiasis body, adopts in one embodiment and filters or screening plant, and these equipment comprise: the equipment that plate-and-frame filter press, cardboard filter machine, filter, horizontal filtering machine, vibratory screening apparatus etc. can be tackled the thalline in the fermented liquid; Adopt the method for membrane filtration in another embodiment, 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 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 in order to alleviate the difficulty that subsequent handling causes liquid glucose to darken and cause to follow-up decolouring because of Maillard reaction; Removing pigment also is in order to alleviate the difficulty that follow-up decolouring brings; Crystallization inhibitor mainly is macromolecular substance such as oligose, colloid, albumen, and these materials can make the follow-up crystallization difficulty of sugar, makes 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 the crystallization crystal formation.

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 for example 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 chromatogram purification or directly decolours.

Step 370 concentrates

Carry out evaporation concentration to sugar dense 50～60% through the fermented liquid behind the membrane filtration.The equipment that is adopted 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 because ion with sugar Maillard reaction takes place when heating to alleviate.

Step 380, chromatographic separation

This step and step 130 are basic identical.Different is owing to removed most glucose and semi-lactosi before the chromatographic separation, and remaining a spot of glucose, semi-lactosi, to assign to the content of each fraction slightly different.And the tunning of glucose, semi-lactosi is assigned in the corresponding fraction according to the degree of absorption in chromatogram.

Sugar is dense about 50～60%, and wherein the pending liquid of the Xylitol of xylitol purity 〉=50% 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, 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%;

(3) D-ribose fraction (promptly 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%;

Shown in Fig. 6 color atlas, among the figure: G-citric acid, C-wood sugar, D-pectinose, 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, but main component is above four kinds of fractions in strict accordance with the position sharp separation of cutting apart among Fig. 6.

Step 381, the aftertreatment of L-arabinose

In the 3rd technical scheme of the invention described above, the byproduct that produces for the fermentation that removes glucose, semi-lactosi is as the tunning of glucose such as ethanol, D-ribose, citric acid, semi-lactosi, and the present invention separates removal in the following manner: volatile product such as ethanol was introduced into the ethanol distillation device before fermented liquid purifies the back decolorizing with activated carbon that finishes carries out rectifying and reclaims.

If the distillatory materials that can not volatilize such as D-ribose, citric acid can separate in the following manner.This programme is owing to directly carry out chromatographic separation after the fermentation ends, so materials such as D-ribose, citric acid are assigned in other fraction except that Xylitol, pectinose fraction.And in other fraction, account for main content, therefore can do to purify by the crystalline mode; Perhaps, separate purification with the mode of chromatographic separation.Preferably separate purification 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 help understanding 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, the part that all can change in specific embodiments and applications, in sum, the present disclosure content should not be construed as limitation of the present invention.

Claims

(a) feed liquid pre-treatment is treated to described raw material the mixed feed liquid that comprises wood sugar, xylan, L-arabinose, glucose and semi-lactosi at least;

(c) may further comprise the steps (c1) and (c2), this two step or place before the chromatographic separation of step (b) described mixed liquor handled or place the chromatographic separation of step (b) after described pectinose fraction feed liquid is carried out the processing of following two steps:

2, the method for claim 1 is characterized in that: the feed liquid pre-treatment of the hydrolyzed solution of described agriculture and forestry organic waste material comprises the following steps:

3. hydrolysis: add the dense acid solution of acid, 128～132 ℃ of insulations of temperature 2.5 hours at 0.5～1%wt; Described acid solution comprises certain two kinds and the mixed solution of two or more acid in sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, nitric acid or these acid;

8. decolouring for the second time: add gac and stir;

3, method as claimed in claim 2 is characterized in that: the ion-exchange of the described step 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 method one of them: a kind of is earlier through anionresin, again through cationic exchange; Another kind is earlier 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, as claim 2 or 3 described methods, it is characterized in that: reverse-flow decoloration process is adopted in the 5. described decolouring first time of described step and the 8. described decolouring second time of step respectively: 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 decolouring back exhausted for the N-1 time the N time, use the old carbon of decolouring back exhausted for the N-2 time the N-1 time, by that analogy, all filter after each decolouring, the gac behind the decolorization filtering is as solid useless the recovery for the first time.

5, as any described method of claim 1-4, 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, comprises corn cob, wheat straw, beet pulp, bagasse, agricultural crop straw, stem leaves of plants root at least, plants skin.

6, the method for claim 1 is characterized in that: described xylose mother liquid and/or the described pre-treatment that contains the waste liquid of five-carbon sugar comprise:

7, method as claimed in claim 6 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 is characterized in that: described organic rolled film is held back and is of a size of 200～2500g/mol.

9, as any described method of claim 6-8, it is characterized in that: the described waste liquid that contains five-carbon sugar 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.

10, as any described method of claim 1-9, it 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, as any described method of claim 1-10, it is characterized in that: in described chromatrographic separation step, all enter the 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; Described mixed liquor and process water keep temperature to be not less than 60 ℃; Eluent is 55～75 ℃ a deionized water.

12, as any described method of claim 1-11, it is characterized in that: the described fermentation inhibitor in the step (c1) comprises impurity and assorted bacterium, impurity wherein comprises the coloring matter of being with phenyl ring, macromolecular pigment, macromolecular compound, heavy metal ion, muriate, colloid and polymkeric substance, and assorted bacterium wherein comprises natural airborne yeast and bacterium; The fermentation inhibitor that removes of described step (c1) further may further comprise the steps:

1. and 2. 13, method as claimed in claim 11 is characterized in that: described step is order or arrange arbitrarily, perhaps first step 1., the back step 2..

14, as claim 12 or 13 described methods, it is characterized in that: 1. described step adopts the electrodeionization system, and described electrodeionization system comprises EDI electricity desalting system and electrodialysis;

15, method as claimed in claim 14 is characterized in that: the hyperfiltration process of described step in 2. selects for use mineral membrane to hold back size in 50～200 nanometers, and the polymer organic membrane is held back size at 1000～6000g/mol;

16, as claim 14 or 15 described methods, it is characterized in that: 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.

17, as any described method of claim 1-16, it is characterized in that: 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 method:

18, method as claimed in claim 17 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 a mass percent:

Method is 1.:

(a) at first the sugared concentration of feed liquid is adjusted to 10～40%;

Method is 2.:

(a) at first the sugared concentration of feed liquid is adjusted to 8～30%;

Method is 3.:

(a) substratum and culture condition:

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%, lime 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;

Method is 4.:

19, as any described method of claim 1-18, it is characterized in that: also comprise after the described step (c2) and remove thalline: by filtration or method for sieving or for the first time membrane filtering method or adopt earlier 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 machine, filter, horizontal filtering machine and vibratory screening apparatus;

20, method as claimed in claim 19 is characterized in that: described adopt earlier filter or screening again by the first time membrane filtering method also comprise membrane filtration step for the second time, described second time, membrane filter plant comprised organic rolled film, tubular membrane.

21, as claim 19 or 20 described methods, it 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～1 μ m; Described second time, membrane filter plant adopted organic rolled film, held back and was of a size of 50～2500g/mol.

22, as claim 19,20 or 21 described methods, it 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 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.

23, as any described method of claim 1-22, it is characterized in that: the post-processing step of described pectinose fraction feed liquid, the described pectinose fraction feed liquid of removing behind the thalline is carried out the following step:

4. crystallization: comprise primary crystallization at least;

5. dry: as to obtain the L-arabinose finished product respectively.

Method as claimed in claim 23 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, filters then; Another kind is reverse-flow decoloration process: 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 decolouring back exhausted for the N-1 time the N time, use the old carbon of decolouring back exhausted for the N-2 time the N-1 time, all filter after each decolouring, by that analogy, the gac behind the decolorization filtering is as solid useless the recovery for the first time.

24, method as claimed in claim 23 is characterized in that: described step 2. desalination comprises: adopt electrodialysis or EDI electricity desalination and then ion-exchange to carry out desalination earlier.

25, method as claimed in claim 23 is characterized in that: 3. described step concentrates and specifically comprise: the sugared concentration of described feed liquid is using triple effect vacuum drop film evaporator to concentrate below 60%; The sugared concentration of described feed liquid is higher than 60% and uses the vacuum single-action to concentrate.

26, method as claimed in claim 23 is characterized in that: described step 4. crystallization comprises twice or twice above crystallization that each crystallization will be dissolved the sugar that obtains after the centrifuging of last crystalline massecuite crystallization once more after the evaporation concentration again; Wherein each crystallization comprises: the feed liquid after will concentrating is squeezed into the horizontal crystallizer tank that has 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 reduced 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 ‰.