CN100572543C - Utilize corn cob or agriculture and forestry organic waste material to prepare the method for Xylitol - Google Patents
Utilize corn cob or agriculture and forestry organic waste material to prepare the method for Xylitol Download PDFInfo
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Abstract
The invention provides a kind of method of utilizing corn cob or agriculture and forestry organic waste material such as stalk to produce Xylitol as raw material.This method comprises raw materials pretreatment; The diluted acid of raw material is handled; Solid-liquid separation; The liquid composition that is obtained utilizes yeast fermentation to obtain Xylitol after decolouring, filtration, depickling and RO concentrate.Fermented liquid through degerming, concentrate, after the chromatographic separation, obtain purer Xylitol liquid, decolour then, deliming, concentrate, crystallization, separation, oven dry, obtain solid finished product Xylitol, crystalline mother solution returns chromatographic separation.In addition, the present invention with acidolysis after the solid components that obtains of solid-liquid separation size mixing, behind enzymolysis, be used for ethanol fermentation then; And enzymolysis product filters xylogen slag that the back obtains and can be used as fuel and use, or is used to develop the deep processed product of xylogen.Xylitol production method of the present invention greatly reduces the cost of Xylitol suitability for industrialized production, and makes all the components of raw material all obtain effective utilization.
Description
Technical field
The present invention relates to a kind of method of producing Xylitol.More particularly, the present invention relates to a kind ofly utilize corn cob or agriculture and forestry organic waste material to ferment to produce Xylitol and alcoholic acid method.
Background technology
Xylitol belongs to polyvalent alcohol, is a kind of sweet taste substance with nutritive value, and molecular formula is C5H12O5, and in the white crystal, soluble in water and ethanol, its sugariness is higher than sucrose, also is the normal intermediate of human body sugar metabolism.Xylitol is present in natural various fruit, the vegetables widely, but its content is very low.Commodity Xylitol thermal value, sugariness follow sucrose similar, do not consume Regular Insulin after edible, other has special preventing decayed tooth function, can make diabetics's nutrition agent, therapeutical agent and children's preventing decayed tooth food, Xylitol also possesses many excellent specific properties of similar glycerine and other polyvalent alcohols, thereby is widely used in industries such as national defence, medicine, chemical industry, leather, coating and food.
The method of traditional mode of production Xylitol is to make Xylitol with agricultural such as the cotton seed hull, bagasse, birch sheet that are rich in pentosan and industrial waste through hydrolysis, hydrogenation.(about 6.5 * 106Pa), inflammable and explosive high pressure hydrogen and the nickel catalyzator very high to the solution purity requirement, capital construction investment and process cost height pollute more serious because chemical method needs pure wood sugar, high temperature (115～135 ℃), high pressure.Since Onishi in 1966 and Suzuki have reported that many yeast can be used in by D-xylose production Xylitol, people to corn particularly the research of producing Xylitol of corn cob or stalk fermentation produced great interest.
China is large agricultural country, the corn distributed areas are very wide, Hainan Island, north are arrived to Heilungkiang in south, to the east of Taiwan,, corn planting is arranged all to Xinjiang, the corn annual production reaches 1.23 hundred million tons, press ratio of grain to straw 1: 1 and calculate, maize straw also produces 1.23 hundred million tons every year approximately, and the whole nation total stalk amount every year is about 6～700,000,000 tons.Maize straw is large wastes of crops, also is the renewable resource with great potential, and especially the starting material as the renewable energy resources and Chemicals are subjected to paying attention to widely, but present except that a part is used as the feed of ruminating animal, major part is not utilized.Therefore, with corn or its straw or other agriculture and forestry organic waste material, preferred corn cob is used to produce that Xylitol is significant and wide prospect.
Patent documentation CN 1446784A discloses a kind of method of producing Xylitol with made from bracteal leaf of corn, it produces wood sugar by utilizing made from bracteal leaf of corn to be hydrolyzed, wood sugar is treated again to carry out hydrogenation and produces Xylitol, the used catalyzer of hydrolysis is a hydrochloric acid, this method may further comprise the steps in regular turn: (1) pulverizes made from bracteal leaf of corn, and before and after pulverizing impurity is wherein removed; (2) the made from bracteal leaf of corn water inlet-acid-water treatment after will pulverizing; (3) made from bracteal leaf of corn that will handle is hydrolyzed and produces wood sugar, and used catalyzer is a hydrochloric acid; (4) utilize anionite-exchange resin to remove acid in the wood sugar liquid; (5) utilize gac to remove pigment and a part of nitrogenous substances in the xylose solution; (6) moisture content in the evaporative removal wood sugar liquid; (7) with ion exchange resin the wood sugar after evaporating is purified purification; (8) Xylitol is produced in wood sugar hydrogenation.The reaction formula that wood sugar hydrogenation prepares Xylitol is:
This employing wood sugar hydrogenation is produced the method for Xylitol, the production cost costliness, and use therein nickel catalyzator pollutes the environment.
Another kind method is to adopt biological fermentation to produce the method for Xylitol, in the technology of whole fermentative Production Xylitol, the influence factor that the fermentation hemicellulose hydrolysate is produced Xylitol mainly comprises: other monose in the cycles of concentration of air flow, carbon-nitrogen ratio, hydrolyzed solution, pH, temperature, seed age and inoculum size, the hydrolyzed solution etc.Wherein, dissolved oxygen level can influence the biochemical route in the xylose metabolism.Excessive oxygen supply is beneficial to a large amount of thalline of growth; Under the anaerobic condition, wood sugar can not be utilized; Only could a large amount of accumulation Xylitols under little aerobic condition.In addition, the dissolving properties of Xylitol has determined that crystallisation process is the most complicated, the most rambunctious; Simultaneously, lower Xylitol concentration and complicated material are formed and have further been strengthened operation easier again in the fermented liquid.When fermented maize core or stalk method are produced Xylitol, because the raw material that adopts contains a certain amount of brown pigmentation; And yeast also can produce small amount of coloring matter, heteroproteins and other compound during the fermentation, thereby has reduced the rate of recovery and the purity of product.Therefore, the decolouring of fermented liquid and purifying are the vital tasks before the crystallization.Present process using gac, ion exchange resin etc. have carried out decolouring and purifying to xylitol fermentation liquor, but all still have the not high problem of the Xylitol rate of recovery.
Summary of the invention
For overcoming the problems referred to above that exist among the present Xylitol preparation method, the purpose of this invention is to provide a kind of method of utilizing corn cob (agriculture and forestry organic waste material such as stalk) fermentative Production Xylitol.This method utilizes agriculture and forestry organic waste materials such as corn cob or stalk to produce Xylitol and co-producing ethanol efficiently, has made full use of the various compositions in the agriculture and forestry organic waste materials such as corn cob or stalk.
The method that stalk fermentation of the present invention is produced Xylitol may further comprise the steps:
(1) corn cob or agriculture and forestry organic waste material are carried out pre-treatment;
(2) solid that (1) is obtained carries out the diluted acid processing;
(3) component that (2) were handled is carried out solid-liquid separation;
(4) filter the liquid component that is obtained by step (3);
(5) decolour, filtration, electric drive membrane depickling and RO concentrate;
(6) the wood sugar liquid that step (5) is obtained ferments and obtains Xylitol;
Can further include following steps:
(7) fermented liquid degerming, concentrated;
(8) the Xylitol liquid that contains that step (7) is obtained carries out chromatographic separation;
(9) the Xylitol liquid decolouring that step (8) is obtained, deliming, concentrate, crystallization, separation, oven dry, obtain solid finished product Xylitol, crystalline mother solution returns (8).
Wherein said agriculture and forestry organic waste material can be maize straw, wheat stalk, jowar stalk, cotton seed hull, bagasse, birch sheet etc., wherein is preferably maize straw.
Crop material mainly is made up of plant cell wall, and main component is Mierocrystalline cellulose, hemicellulose, xylogen and crude protein and water etc., and wherein two kinds of main sugared sources are hemicellulose and Mierocrystalline cellulose.Hemicellulose accounts for 20%～25% of stalk gross weight, and cellulose comprises stalk gross weight 35%～40%.The cellulosic structure unit is by β-D-glucosyl group β-1, and the 4-glycosidic link connects the linear glucose high molecular polymer that forms, and each fiber molecule is made up of 800-1200 glucose molecule, because its crystalline texture is difficult to be degraded.Hemicellulose mainly is a wood sugar, and the complicated molecule polymkeric substance formed such as a small amount of pectinose, semi-lactosi, seminose, and hemicellulose easily acid hydrolysis is a monose.And xylogen is to be the polymer aromatics of fundamental unit formation with phenylpropyl alcohol alkane and derivative thereof, is a kind of phenol polymer, plays the gelationus effect, and Mierocrystalline cellulose and hemicellulose are linked together.Therefore,, at first to handle, to obtain the sugared source of xylitol zymolysis production to raw material if obtain to be enough to the wood sugar that industrial fermentation obtains sugar alcohol.
In the method for the invention, corn cob or stalk pre-treatment and acid treatment have been carried out, comprise the polymkeric substance hemicellulose is changed into fermentable sugar, and remove not fermentability material-colloid, pigment and most of ash, pretreated method can comprise: mechanical cleaning, de-iron, washing, poach, diluted acid boil the H as HCl or 0.05-0.2% concentration
2SO
4Deng.
The present invention can adopt finite concentration for example the dilute sulphuric acid of preferred 0.8% concentration of 0.5-2% handle down stalks or corn cobs at 95～125 ℃, make wherein hydrolysis of hemicellulose become to contain the mixed sugar liquid of wood sugar, pectinose, glucose, seminose, semi-lactosi etc.After dilute sulphuric acid is handled, mainly contain Mierocrystalline cellulose and xylogen in the remaining solid, stalk or corn cob destructurized can be improved cellulosic water-disintegrable greatly.
In the method for the invention, pretreated corn cob or the preferred corn cob of stalk be hydrolyzed produce wood sugar, when being hydrolyzed, pretreated corn cob or the preferred corn cob of stalk are placed in the hydrolytic decomposition pot, add the 0.5-2% sulfuric acid of 4-10 times of weight, use steam heating, insulated and stirred hydrolysis 1～3h when temperature reaches 95～125 ℃, hydrolysis finishes, and hydrolyzed solution is cooled to below 50 ℃, filters.Preferred 95～125 ℃ of temperature of temperature during hydrolysis, 110 ℃ is optimum temps; Time is 1～3 hour; Catalyzer is HCl or H
2SO
4Be preferably sulfuric acid (H
2SO
4), pressure is normal pressure or 0.2mpa.
The hydrolysis principle is to contain the pentosan with following structural formula in corn cob or the stalk:
Following formula can be considered partly contracting of the ring pentose molecule polymer that hydroxyl on the four carbon atom of base and another ring pentose molecule forms through dehydrating condensation of waking up, it is hemicellulose, pentosan is water insoluble not to have sweet taste yet, heating can be dissolved further hydrolysis in aqueous acid is arranged, promptly under the effect of catalyzer, the pentose that adds water decomposition and become a lot of individual molecules is a wood sugar, and its reaction formula is as follows:
The method according to this invention, the liquid hydrolyzed solution total sugar concentration that generates is 4.5%～7%, hydrolysis finishes, liquid is discharged from liquid discharge pipe, open the hydrolysis bottom valve then, hydrolysis residue is entered the one-level spiral extract in the machine, carry out solid-liquid separation, liquid collecting, be pooled to from the former liquid glucose that liquid discharge pipe is discharged; Solid is by stirring cage (stir cage top spray from three grades of washing lotions of stirring cage), is transported to deuterostrophies and extracts and carry out solid-liquid separation in the machine, and solid enters three grades of spirals and extracts machine, and liquid goes down to criticize acidolysis as complex acid water.Three grades of isolating wash waters of solid are Cheng Shui, as evaporation condensed water or tap water, extract the solid slag that obtains for three grades, are xylose residue, go to size mixing, and enzymolysis is produced glucose fermentation ethanol.
To separate the wood sugar liquid that obtains then, add the 0.2-0.4% Powdered Activated Carbon by liquid volume, under 75～80 ℃ condition, insulation 30min.Filter the elimination activated carbon particle through plate framework, liquid glucose filters through the liquid precision strainer of 0.2 μ m again.Liquid glucose is further clarified.Decolouring enters the depickling of electric drive membrane separator.With many series connection of electric drive membrane separator, material advances from first, and last goes out; Dense water advances from last, and first goes out.The specific conductivity of liquid glucose is reduced to below the 1000 μ s/cm operational condition: normal temperature, normal pressure by 30000～34000 initial μ s/cm.The liquid glucose that is obtained after the depickling enters the RO membrane concentration, and the concentration after concentrating is 15～20%.Concentrated film is an organic membrane, and working pressure is 3.3～3.8Mpa.
Following table 1 is the main component content behind the corncob acid hydrolysis.
The main component content of table 1 corncob acid hydrolysis liquid glucose
The liquid phase of acid hydrolysis solution behind solid-liquid separation, decolorization filtering, the depickling of electric drive membrane separator and RO membrane concentration of corn cob carried out HPLC to be measured, record hydrolyzed solution and contain wood sugar, glucose, pectinose, the massfraction that they account for total reducing sugars is respectively: 83%, 3.8% and 11.8%.
Seed fermentation: with above xylose solution, mend an amount of maize dextrose syrup, add an amount of nutritive salt and nutrition through the RO membrane concentration, under 110 ℃ condition, sterilization 5min.When treating that seeding tank liquid glucose temperature is reduced to 31 ℃, insert seed, keep 31 ℃, long-pending by seed fermentation liquid: the ventilation of the amount of purifying air=1: 0.5, the cultivation 24～36 hours of ventilating, when yeast density reached 4～500,000,000/ml, seed fermentation promptly finished.Xylitol fermentation of the present invention can adopt single culture or mixed fermentation.The microorganism that can be used for xylose-fermenting liquid method of the present invention can be all microorganisms that wood sugar can be changed into Xylitol, comprise: bacterium, as EnterobacterLiquaefaciens, Myobactenum smegmatis, coryneform bacteria kinds such as (Corymebacterumsp.); Filamentous fungus is as mould, aspergillus, head mold, glue bacillus, Byssochlamys, the red bacterium of lacquer spot or Neurosporaspp; Yeast, as candiyeast (Candida) with performance of comparatively superior conversion xylose production Xylitol, pichia yeast (Pichia), it is the strongest that Candida belongs to the zymic conversion capability, preferably as C.guilliermondii, and C.tropicalis, C.mogii, C.parasilosis.The yeast that other conversion capability is stronger is:
1. Debaryomyces belongs to, as D.hansenii;
2. Pachysolen belongs to, as P.tannophilus;
3. Saccharomyces belongs to;
4. Schyzosaccharomyces belongs to.
The present invention preferably uses candidiasis single culture fermentation, particularly candida tropicalis.
Xylitol fermentation: the wood sugar liquid pump behind the RO membrane concentration is gone in the fermentor tank, add essential nutritive salt and nutrition, with NaOH the PH of substratum is transferred to 5.8～6.0, with steam liquid glucose is heated to 121 ℃, keep sterilization in 25 minutes, must be cooled to 31 ℃, insert the seed in the seeding tank, lead to 0.5 cubic metre sterile air, carry out Yeast proliferation and cultivate by every cubic metre of fermented liquid per minute, cultivate through about 8～12 hours ventilation, after yeast number reaches 4～500,000,000/ml, air quantity is dropped to 0.1 cubic meters per minute M3 fermented liquid, cultivate through 48～60 hours ventilations, treat in the fermented liquid that wood sugar content drops to 0.3% when following, fermentation ends.
The total sugar concentration that enters fermentation is 15～20%, and wherein xylose concentration is 12.5～16.7%, cultivates by the ventilation in early stage, and the most glucose in the total reducing sugar are as yeast growth.Fermentation ends mainly contains wooden grain alcohol and a small amount of pectinose, assorted sugar such as sweet dew, wood sugar and glucose in the fermented liquid.
Transform in the xylitol fermentation at wood sugar of the present invention, can adopt the candida tropicalis fermentation, Xylitol is produced in the wood sugar bio-transformation, its reaction formula is as follows:
The present invention preferably adopts candida tropicalis to carry out high density fermentation, and fermented liquid is obtaining xylitol solution and yeast feed behind membrane sepn.Fermented liquid board-like film of process or ceramic membrane, metallic membrane, membrane pore size is for passing through molecular weight 3～50,000.Filtration pressure is 2～3Kg/cm2, under the condition that temperature is 30～40 ℃, carries out cross flow filter and separates, and seeing through liquid is thick xylitol solution, and the yeast tunicle is held back.Along with the minimizing of the Xylitol total amount in the stoste, zymic concentration is more and more higher, for Xylitol is thoroughly separated with zymic, adds a certain amount of water again in the fermentation that has concentrated, and makes the wood sugar alcohol and water further see through film, enters through in the liquid.
Used film can be board-like film, or metallic membrane, also can be ceramic membrane.
Wherein with the xylitol solution that obtains, its Xylitol concentration is 9～12.5% (W/V), works being mixed into chromatographic fractionation system with crystalline mother solution, carries out Xylitol and assorted sugared separate impurities, to improve the purity of Xylitol.
The condition of chromatographic separation: charging Xylitol concentration 12～15% (W/V), moving phase are water, and temperature is 60 ℃.Used tree lipid acid is cationic.Subsequent processing is removed in the Xylitol segmentation that chromatographic separation is collected, and the sugar segmentation of mixing goes to concentrate, and oven dry is as feed or sell the production caramel colorant, and wastewater treatment is gone in the impurity segmentation.
The Xylitol component that chromatographic separation is collected, through the powder activated carbon decolouring, ion exchange resin desalination, the product that concentrate, crystallization, separation, oven dry obtains qualified wood sugar.Mother liquor returns chromatographic fractionation system.
The decolouring of powder carbon: under 75～80 ℃ of conditions, add sugar and sugar alcohol tailored flour carbon, dosage is that every cubic metre of liquid adds 3～5Kg, and insulation is 30 minutes under condition of stirring.
The ion-exchange desalination: exchange resin refers to and weak base anion-exchange resin that for strongly-acid strong cation exchange tree the resin column blade diameter length ratio is 1: 3～5, and the resin column material is glass reinforced plastic or carbon steel line with rubber, and inlet amount is 1～2 column volume per hour.Working temperature≤50 ℃.Discharging specific conductivity≤5us/cm.
Concentrate: with plate-type evaporator or column tube evaporimeter, quadruple effect, vacuum tightness 0.9～0.5Mpa, top temperature is 85 ℃, solid content is 90% when concentrating discharging.
Crystallization: the material that will concentrate, put into vertical or horizontal crystallizer, be cooled to 58～60 ℃, when making whole temperature of charge uniformity, press 10% of liquid glucose gross weight and add xylitol seed crystals, growing the grain is after 10～12 hours, begin cooling, cooling rate is 0.7 ℃/1 hour, and when temperature dropped to 30～32 ℃, crystallization finished.The cooling water be tap water or frozen water, require water and temperature of charge poor≤5 ℃.Mixing speed 8～10 commentaries on classics in the crystallizer/hour.
Separate: crystallization finishes, and massecuite is put into separation centrifuges, and centrifugal is the full-automatic separation centrifuges of top suspension, and before the adding massecuite, whizzer carries out preheating with 0～80 ℃ of hot water or clean steam to whizzer.After pressing the rated load adding massecuite of whizzer, centrifugal rotational speed is slowly high to 3000 rev/mins, kept 10 minutes, rotating speed is dropped to 1250 rev/mins again, opened automatic wash water valve 3～5 seconds, rotating speed is increased to 3000 rev/mins again, three times so repeatedly.Crystal is emitted in centrifugal end.
Oven dry: crystal by adopting dryer, fluidized-bed, air-flow or the oven dry of vacuum fixation disc type, bake out temperature is not higher than 60 ℃.Weight loss on drying content≤0.5% o'clock, i.e. oven dry finishes.Oven dry finishes, and is up to the standards, and obtains finished product.Finished product is white crystals and crystalline powder, and it is sweet to distinguish the flavor of, free from extraneous odour.
Xylitol is from the fermented liquid to the finished product, and total recovery is 75-80%.
In addition, as shown in Figure 1, the solid phase composition water that obtains in the quick solid-liquid separation of the inventive method washs three grades of spirals and extracts series connection, and is middle with stirring cage conveying filter residue, and adds water spray system on the cage stirring, wash water stirs the cage adding from measuring the back one-level, in the end the one-level spiral is extracted the machine collection, pumps into the second stage and stirs cage, extracts machine from second stage spiral and collects wash water, contain 1～2% total reducing sugar in this wash water, this wash water disacidify is separated complex acid.And first step spiral is extracted the liquid phase that machine comes out and is wood sugar liquid.In the methods of the invention, it can be to concentrate the water that obtains that reclaims through aforementioned RO that last step stirs the used water of cage, and so bob-weight is used again, can reduce pretreated cost greatly, and the production cost of end product is further reduced.Then the xylose residue that obtains is sized mixing and carry out enzymolysis xylose residue is sized mixing, the concentration of sizing mixing is 10～12%, is adjusted into 4.8～5.0 with rare NaOH.Under the condition that temperature is 50 ℃, by fibre weight, cellulase and cellobiose enzyme dosage: 30FPIU cellulase activity/g bone dry fiber element, 15IU cellobiase/gram bone dry fiber element.Enzymolysis time 40-50 hour, the glucogenic yield of fiber enzymolysis was 90%.The reactor that equipment used stirs for band, equipment answers tool well to be incubated, and paddle is a slurry formula leaf, and rotating speed is 50～80 rev/mins, and rotating speed is adjustable.Used enzyme is cellulase and cellobiose enzyme.The composition of the enzymolysis product that obtains is a glucose.The present invention with described enzymolysis product composition after filtering, place fermentor tank to carry out glucose after ethanol fermentation filters enzymolysis, make glucose concn be increased to 20～22% through ultrafiltration, RO membrane concentration and force evaporation concentration, add in the ethanol fermentation jar, the inorganic nutrients sources such as N, P that add trace, the inoculation yeast by 10%.Ventilating early stage to cultivating made Yeast proliferation in 4～6 hours, and when yeast density reached 2～300,000,000, blowing-out entered the metabolism of anaerobism second.34～36 ℃ of leavening temperatures, fermentation period 28～30 hours, fermented bacterium are common pure brewer yeast, autoflocculation yeast or ethanol high yield yeast.In addition, the xylogen slag that is obtained after filtration can be used for fuel or Development and Production xylogen deep processed product.
Xylitol preparation method of the present invention adopts microbial fermentation that the wood sugar of corn cob or stalk acidolysis acquisition is converted into Xylitol.Fermentation method is not high to the purity requirement of wood sugar, and depickling only needs electric drive membrane separator to get final product, and compares with hydrogenation process, not only saves a large amount of ion-exchange resins, and has saved acid and alkali consumption, has avoided a large amount of waste water to produce.Simultaneously, adopt fermentation method, saved the xylose crystalline operation, improved the utilization ratio of wood sugar.This method save the wood sugar purifying from hand over, concentrate, step such as crystallization.By the fermentation, make in the wood sugar assorted sugar--glucose is consumed by yeast in fermentation, improved the purity of Xylitol.By chromatographic separation technology fermented liquid is separated purification, make Xylitol in the fermented liquid reach 80% to the total recovery of finished product Xylitol.In addition, utilize microorganism direct fermentation to produce Xylitol through the xylose hydrolysis fluid of preliminary treatment, have processing condition gentleness, energy consumption low, need not loaded down with trivial details purifying wood molasses, advantage such as the environmental pollution degree is low, quality product is more safe and reliable.In addition, the present invention also changes into solid phase composition xylose residue and can be used as fuel sugared source that use and that be used for ethanol fermentation, thereby makes each composition in the stalk all be fully utilized, and can reduce the production cost of Xylitol significantly.
Description of drawings
Fig. 1. for adopting corn cob or stalk fermentation, the present invention produces the schematic flow sheet of the method for Xylitol.
Embodiment
Below in conjunction with embodiment the present invention is further described, but following embodiment is used for limiting the scope of the invention:
The pre-treatment of embodiment 1. corn cobs
Get the 100Kg corn cob, choose by hand and pick up big assorted, little mixing, add tap water, stir by hand, clean the earth and the dust on corn cob surface.The drop decontaminated water is surveyed the corn cob moisture content more then.Corn cob is added in the 1000L sugar reactor, then in corn cob: the ratio of diluted acid=1: 6 weight ratio adds 0.1% H
2SO
4Solution 600Kg, in the diluted acid of 600Kg, 0.1% sulfuric acid is 0.61Kg, water is 599.39Kg (moisture that sucks in the time of also should deducting the corn cob washing), is heated to 80 ℃ under condition of stirring, stops 1 hour, emits diluted acid water.
Enamel still (production of Zibo industrial enamel factory) anchor formula stirs, rotating speed 60rpm, chuck heating, cooling.
The acidolysis of embodiment 2. corn cobs
Press corn cob then: the part by weight of diluted acid=1: 6 adds 0.8% H
2SO
4Solution 600kg, in the diluted acid of 600kg, 98% sulfuric acid is 4.9Kg, and water is 595.1Kg (attention should be deducted the Total Water that the moisture more contained than commodity corn core has more after 0.1 Diluted Acid Washing), is heated to 110 ℃ under condition of stirring, keeps 2 hours, and acidolysis finishes.
The condition of enamel still is with embodiment 1
The acidolysis of embodiment 3. maize straws
Maize straw is pulverized (by the 3mm sieve aperture), press maize straw: the part by weight of diluted acid=1: 6, the H of adding 0.8%
2SO
4Solution 600kg, in the diluted acid of 600kg, 98% sulfuric acid is 4.9Kg, and water is 595.1Kg, is heated to 110 ℃ under condition of stirring, keeps 2 hours, and acidolysis finishes.
The condition of enamel still is with embodiment 1
Embodiment 4. solid-liquid separation
Acidolysis finishes, and the acidolysis mixture is cooled to below 50 ℃, changes in the separation centrifuges by the 50L plastic tank, and filter bag is installed in the centrifuge drum.Whizzer is that Liaoyang friend's letter pharmaceutical machine Science and Technology Ltd. produces, and maximum speed is 2000rpm, and frequency conversion is adjustable, the rotating speed diameter
Mm, maximum liquid amount 30Kg.When centrifuge speed was 500rpm, beginning was slowly reinforced, allows liquid glucose tell, and xylose residue is issued in rotary drum evenly, in order to avoid cause the whizzer vibration.After the 50L material all adds, cover centrifuge cup, slowly transfer to maximum speed 2000rpm, kept 10 minutes; till not having liquid to discharge, add 50 ℃ of water 3L from the wash water mouth then, solid is washed the repeated washing secondary; in discharge opeing, till the anhydrous discharge, shut down slag dumping.
The processing of embodiment 5. liquid compositions
With separating the wood sugar liquid that obtains, add 0.2-0.4% (W/V) Powdered Activated Carbon by 100 liters of liquid volumes, under 75～80 ℃ condition, be incubated 30 ℃.Filter the elimination activated carbon particle through plate framework, liquid glucose filters through the liquid precision strainer of 0.2um again.Liquid glucose is further clarified.
Decolouring enters the depickling of electric drive membrane separator.Electricity drive membrane separator specification 400 * 600, the experimental installation of totally 80 pairs of negative and positive films.Material circulates depickling, and acid group enters in the dense water with ionic condition.The specific conductivity of liquid glucose is reduced to below the 1000us/cm by initial 32000us/cm.Operational condition: normal temperature, normal pressure.The liquid glucose that is obtained after the depickling enters the RO membrane concentration, and the RO membrane area is 7m
2Concentration after concentrating is 15～20%.Concentrated film is an organic membrane, and working pressure is 3.3～3.8Mpa.
The preparation of embodiment 6. seed fermentations
The seed preparation flow is: from the strain inclined plane to the shake-flask culture, insert seeding tank then, the seed tank culture base consists of wood sugar liquid, yeast powder, the corn steep liquor after above-mentioned the concentrating, and logical sterile air ventilates and cultivates.
Bacterial classification: candida tropicalis
Slant medium: glucose 1%, wood sugar 1%, yeast powder 0.3%, peptone 0.5%, corn cob hydrolyzed solution 3%, agar 2%.
Shake-flask culture base: glucose 1%, wood sugar 2%, yeast powder 0.5%, peptone 0.8%.
Seed tank culture base: corn cob hydrolyzed solution 3%, yeast powder 0.5%, corn steep liquor 0.8%, glucose 1%.
Seed tank culture condition: ventilation volume 1:0.5; Temperature: 28-31 ℃; PH6.0.
Embodiment 7. wood-sugar fermentations prepare Xylitol
Embodiment 4 is handled liquid glucose after concentrating, add in the fermentor tank, add 0.1% ammonium sulfate and 0.3% corn steep liquor, steam heating to 121 ℃ is kept 25min, is cooled to 32 ℃ then, inserts embodiment 5 cultured seed liquid, inoculum size 10%.
Technological condition for fermentation: initial pH6.0; Air quantity adopts two sections ventilations: preceding 10 hours 1: 0.4, reduce to 1: 0.15 then, up to fermentation ends.Leavening temperature: 30-32 ℃; Fermentation period:＜72 hours.
Fermentation ends, the fermented liquid state is: outward appearance: Vandyke brown liquid, proportion 1.06, wet amount of yeast: 4-6%; Xylitol concentration 8-10%; Xylitol is 75%-80% to the wood sugar transformation efficiency.
The processing of embodiment 8. fermented liquids
Fermented liquid is the board-like membrane filtration of process earlier, the yeast in the separate fermentation liquid.Membrane pore size is 50,000 molecular weight, and filtration area is 1m
2Pilot plant.Working pressure: import 0.32Mpa, outlet 0.30Mpa, 35 ℃ of service temperatures.Collect to see through liquid, when yeast concn reaches 20%, add the 3L tap water, dilute dialysis, so triplicate adds dialysis water 9L altogether, makes that Xylitol content is lower than at 1% o'clock in the concentrated solution, and the yeast membrane sepn finishes.
The liquid of collecting that sees through is clarified, and color and luster is darker, and transmittance is 15%.
Remove zymic Xylitol liquid and enter chromatographic separation.The condition of chromatographic separation: charging Xylitol concentration 12～15% (W/V), moving phase are water, and temperature is 60 ℃.Used tree lipid acid is cationic.Subsequent processing is removed in the Xylitol segmentation that chromatographic separation is collected, and the sugar segmentation of mixing goes to concentrate, and oven dry is as feed or sell the production caramel colorant, and wastewater treatment is gone in the impurity segmentation.
The Xylitol component that chromatographic separation is collected, through the powder activated carbon decolouring, ion exchange resin desalination, the product that concentrate, crystallization, separation, oven dry obtains qualified wood sugar.Mother liquor returns chromatographic fractionation system.
The decolouring of powder carbon: under 75～80 ℃ of conditions, add sugar and sugar alcohol tailored flour carbon, dosage is that every cubic metre of liquid adds 3～5Kg, and insulation is 30 minutes under condition of stirring.
The ion-exchange desalination: exchange resin refers to and weak base anion-exchange resin that for strongly-acid strong cation exchange tree the resin column blade diameter length ratio is 1: 3～5, and the resin column material is glass reinforced plastic or carbon steel line with rubber, and inlet amount is 1～2 column volume per hour.Working temperature≤50 ℃.Discharging specific conductivity≤5us/cm.
Concentrate: with plate-type evaporator or column tube evaporimeter, quadruple effect, vacuum tightness 0.9～0.5Mpa, top temperature is 85 ℃, solid content is 90% when concentrating discharging.
Crystallization: the material that will concentrate, put into vertical or horizontal crystallizer, be cooled to 58～60 ℃, when making whole temperature of charge uniformity, press 10% of liquid glucose gross weight and add xylitol seed crystals, growing the grain is after 10～12 hours, begin cooling, cooling rate is 0.7 ℃/1 hour, and when temperature dropped to 30～32 ℃, crystallization finished.The cooling water be tap water or frozen water, require water and temperature of charge poor≤5 ℃.Mixing speed 8～10 commentaries on classics in the crystallizer/hour.
Separate: crystallization finishes, and massecuite is put into separation centrifuges, and centrifugal is the full-automatic separation centrifuges of top suspension, and before the adding massecuite, whizzer carries out preheating with 0～80 ℃ of hot water or clean steam to whizzer.After pressing the rated load adding massecuite of whizzer, centrifugal rotational speed is slowly high to 3000 rev/mins, kept 10 minutes, rotating speed is dropped to 1250 rev/mins again, opened automatic wash water valve 3～5 seconds, rotating speed is increased to 3000 rev/mins again, three times so repeatedly.Crystal is emitted in centrifugal end.
Oven dry: crystal by adopting dryer, fluidized-bed, air-flow or the oven dry of vacuum fixation disc type, bake out temperature is not higher than 60 ℃.Weight loss on drying content≤0.5% o'clock, i.e. oven dry finishes.Oven dry finishes, and is up to the standards, and obtains finished product.Finished product is white crystals and crystalline powder, and it is sweet to distinguish the flavor of, free from extraneous odour.Xylitol is from the fermented liquid to the finished product, and total recovery is 80%.
The processing of embodiment 9. solid phase compositions
The xylose residue that obtains sized mixing carry out enzymolysis xylose residue is sized mixing, the concentration of sizing mixing is 10～12%, is adjusted into 4.8～5.0 with rare NaOH.Under the condition that temperature is 50 ℃, by fibre weight, cellulase and cellobiose enzyme dosage: 30FPIU cellulase activity/g bone dry fiber element, 15IU cellobiase/g bone dry fiber element.Enzymolysis time 48 hours, the glucogenic yield of fiber enzymolysis is 90%.The reactor that equipment used stirs for band, equipment answers tool well to be incubated, and paddle is a slurry formula leaf, and rotating speed is 50～80 rev/mins, and rotating speed is adjustable.Used enzyme is cellulase and cellobiose enzyme.The composition of the enzymolysis product that obtains is a glucose.
The enzymolysis product composition after filtering, place fermentor tank to carry out glucose after ethanol fermentation filters enzymolysis, make glucose concn be increased to 20～22% through ultrafiltration, RO membrane concentration and force evaporation concentration, add in the ethanol fermentation jar, the inorganic nutrients sources such as N, P that add trace, the inoculation yeast by 10%.Ventilating early stage to cultivating made Yeast proliferation in 4～6 hours, and when yeast density reached 2～300,000,000, blowing-out entered anaerobic metabolism.34～36 ℃ of leavening temperatures, fermentation period 28～30 hours, fermented bacterium are common pure brewer yeast, autoflocculation yeast or ethanol high yield yeast.In addition, the xylogen slag that is obtained after filtration can be used for fuel or Development and Production xylogen deep processed product.
Though above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, not departing from the these modifications or improvements basically of spirit of the present invention, all belong to the scope of protection of present invention.
Claims (11)
1, a kind of method of producing Xylitol, this method may further comprise the steps:
(1) agriculture and forestry organic waste material is carried out pre-treatment;
(2) solid that (1) is obtained carries out the diluted acid processing;
(3) component that (2) were handled is carried out solid-liquid separation;
(4) filter the liquid component that is obtained by step (3);
(5) liquid component after step (4) is filtered decolours, filtration, electric drive membrane depickling and RO concentrate;
(6) the solid phase composition that is obtained by step (3) with water washing by RO membrane concentration acquisition, then through size mixing, after enzymolysis and the filtration, the sugared source of acquisition is used for ethanol fermentation;
(7) the wood sugar liquid that step (5) is obtained ferments and obtains Xylitol.
2, according to the method for claim 1, it further may further comprise the steps:
(8) fermented liquid degerming, concentrated;
(9) the Xylitol liquid that contains that step (8) is obtained carries out chromatographic separation;
(10) the Xylitol liquid decolouring that step (9) is obtained, deliming, concentrate, crystallization, separation, oven dry, obtain solid finished product Xylitol, crystalline mother solution returns (9).
3, according to the method for claim 1 or 2, wherein said agriculture and forestry organic waste material is maize straw, wheat stalk, jowar stalk, cotton seed hull, bagasse, birch sheet.
4, method according to claim 1 and 2, wherein said diluted acid are treated to sulphuric acid soln acidolysis corn cob or stalk.
5, according to the method for claim 4, wherein said acid solution is the sulphuric acid soln of 0.5%～2.0% concentration, and the weight ratio of agriculture and forestry organic waste material and used acid solution is 1: 4～10.
6, according to the arbitrary described method of claim 1～2 or 5, this method also is included in cleaning, washing and diluted acid that agriculture and forestry organic waste material is carried out before the acid treatment and boils.
7, according to the method for claim 1 or 5, wherein said fermentation is common pure brewer yeast, autoflocculation yeast or candida tropicalis single culture pure-blood ferment.
8, method according to claim 1 or 5, wherein said fermentation is mixed fermentation, and fermented bacterium is selected from two or more in the following bacterial classification: enterobacteria (EnterobacterLiquaefaciens), shame posterior division bacillus (Myobactenum smegmatis), coryneform bacteria (Corymebacterum sp.), mould (Penicillium), aspergillus (Aspergillus), head mold (Rhizopus), glue bacillus (Zoogloea), the mould genus of silk clothes (Byssochlamys), the lacquer red bacterium of spot (Myrothecium), Neurospora (Neurosporaspp), candiyeast (Candida) or pichia yeast (Pichia).
9, method according to Claim 8, wherein said candiyeast are to cover candiyeast (C.guilliermondii), candida tropicalis (C.tropicalis), not lattice candiyeast (C.mogii) or Candida parapsilosis (C.parasilosis) season.
10, according to the method for claim 1, its step (6) comprises that also the xylogen slag of will size mixing, obtain after enzymolysis and the filtration is as the fuel or the step of producing its deep processed product.
11, according to the method for claim 1 or 10, wherein said enzyme is cellulase and cellobiose enzyme.
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