CN102876732A - Method for preparing high-added-value sugar alcohols by efficiently using wood fiber raw materials - Google Patents
Method for preparing high-added-value sugar alcohols by efficiently using wood fiber raw materials Download PDFInfo
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Abstract
The invention relates to a method for preparing high-added-value sugar alcohols by efficiently using wood fiber raw materials, belonging to the field of biological chemistry. The method comprises the following steps: after pre-processing the wood fiber raw materials, directionally decomposing hemicellulose components in the wood fiber raw materials by using a steam explosion technology, and performing solid-liquid separation to obtain solution rich in xylose; performing chemical treatment to residual solid residues, then decomposing the cellulose components in the residual solid residues by using the steam explosion technology, and performing solid-liquid separation to obtain the solution rich in glucose. The two kinds of sugary solution are respectively cleaned and concentrated, and processed by microbial fermentation, and fermenting liquor is separated, purified, concentrated and crystallize to obtain xylosic alcohol products and erythritol products. The method fully uses the components decomposed into sugars in the wood fiber raw materials and develops a new technology for converting the renewable wood fiber resources into the high-added-value sugar alcohols by using the steam explosion and bioconversion technology.
Description
Technical field
The invention belongs to biological chemical field, particularly utilize steam explosion reproducible wood fibre resource conversion to be become the method for high added value sugar alcohol in conjunction with conversion technology.
Background technology
Lignocellulose raw material is the very abundant cheap renewable resources of occurring in nature, and these three kinds of high molecular polymers of three major polymers: cellulose, hemicellulose and xylogen form, and also contain the compositions such as a small amount of pectin, natural gum, and structure is very complicated.Wherein Mierocrystalline cellulose is the chief component composition of plant cell wall, mainly pass through β-1 by 1000-10000 β-D-glucopyranose, the crosslinked straight-chain polysaccharide that forms of 4-glycosidic link, have the thread insoluble micro-fiber structure that a plurality of molecular layers are arranged in parallel and consist of, basic composition unit is cellobiose.Hemicellulose then generally is combined between Mierocrystalline cellulose and the xylogen as the molecule tamanori, the side chain polysaccharide of the 80-200 polymerization degree that is comprised of structural units such as wood sugar, a small amount of pectinose, semi-lactosi or seminoses is that content is only second to cellulosic saccharan in the plant.Xylogen is wrapped in the surface of Mierocrystalline cellulose and hemicellulose by the network polymer that phenylpropyl alcohol alkane and derivative thereof form, and plays barrier action in hydrolytic process.
Present utilization for lignocellulose raw material mainly concentrates on cellulosic hydrolysis and microbial transformation prepares the biofuel aspects such as ethanol, butanols.Although make great progress, but still fail large-scale industrial production, mainly contain two problems: the one, the pretreated cost of fibrous material is higher; The 2nd, the cellulase hydrolysis cost is higher.Because the pretreated purpose of above-mentioned fibrous material is to remove xylogen and hemicellulose to cellulosic provide protection and destroy crystalline structure between the cellulose macromolecule, to improve cellulosic enzymolysis transformation efficiency, hemicellulose often can not get effective utilization.For the problems referred to above, the theory that the present invention adopts the classification of lignocellulose raw material different components to utilize, for the characteristics of hemicellulose than the easy degraded of Mierocrystalline cellulose, design different steam explosion conditions, hemicellulose and the Mierocrystalline cellulose of degrading successively in the lignocellulose raw material obtain fermentable sugars, thereby improved the degree of utilizing of raw material, reduced the production cost of Mashing process.
Steam explosion (being called for short " vapour is quick-fried ") is rapidly a kind of lignocellulose treatment process of development in recent years.Raw material is with being steam heated to 180-240 ° of C, and dimension is pressed for some time, when unexpected release of pressure spurts, produces secondary steam, and the volume surge is under the effect of mechanical force, with the solid materials structure deteriorate.Process engineering institute of Chinese Academy of Sciences Applied Physics principle prepares xylo-oligosaccharide (CN1233614): the raw material after the quick-fried processing of vapour can obtain the solubility hemicellulose through the water extracting, and its main component is xylo-oligosaccharide, and the hemicellulose transformation efficiency reaches more than 80%.The present invention is on the basis of foregoing invention, before vapour is quick-fried, add organic acid dipping pretreatment technique, reduce the degree of crosslinking between each component in the raw material, increase the palliating degradation degree of hemicellulose in the quick-fried process of vapour, can directly obtain xylose solution through the water extracting, the hemicellulose degradation rate reaches more than 85%, and cellulose degradation seldom simultaneously.For remaining solid slag, adopt chemical treatment to obtain glucose solution in conjunction with steam explosion technology degraded Mierocrystalline cellulose wherein, cellulose degradation rate reaches more than 80%.
Xylitol is a kind of important industrial fine chemicals, glycosyl chemical, food and feed additive, possesses many excellent specific properties.From 1966, Onishi and Suzuki reported first after yeast can be converted into Xylitol with the D-wood sugar, many scholars have carried out the research of preparation of xylitol by fermentation in the world, and many achievements have been declared patent (Chinese patent ZL200710063303.8, ZL200510040133.0; US Patent No. 2011/0003356A1).But the fermentation substrate wood sugar in the existing patent still mainly obtains by the method for high-concentration sulfuric acid hydrolyzed hemicellulose, needs alkali neutralization, decolouring, desalting treatment before fermentation, and process is complicated, the soda acid consumption is large.This patent adopts the organic acid pre-treatment to obtain Xylose in conjunction with steam explosion technology degradation of hemicellulose, its acidity and ionic strength are all well below sulphuric acid hydrolysis, namely can be used for follow-up fermenting process by simple activated carbon decolorizing and ammoniacal liquor adjusting, under the fermentation condition of optimizing, wood sugar to the transformation efficiency of Xylitol greater than 70%.
Erythritol is that molecular weight is minimum, and caloric value is minimum, and (≤1.66kJ/g) sugar alcohol, the dosis tolerata in human body (50g/ days) is also far above other sugar alcohols such as Sorbitol Powder, Xylitols, and sweet taste is pure similar to sucrose, bitter taste without issue.The production of present industrial erythritol mainly is to utilize glucose fermentation.Chinese patent ZL200510102929.6 has reported take refining glucose as carbon source, utilizes the Candida lipolytica fermentation to obtain the method for erythritol; Patent ZL201010611106.7 has reported take Semen Maydis powder as raw material, obtains Glucose Liquid through enzymic hydrolysis, and the fermentation of recycling Candida lipolytica obtains the method for erythritol.Compare with existing patent, the cellulosic component that this patent adopts chemical treatment to degrade in the reproducible lignocellulose raw material in conjunction with the steam explosion technology obtains glucose solution, pass through again purification process, microbial transformation obtains erythritol, thereby avoided the consumption of grain resource, improved the utility value of cellulose resource.
Summary of the invention
A kind of method of efficiently utilizing lignocellulose raw material to prepare the high added value sugar alcohol is characterized in that, comprises the steps:
(1) lignocellulose raw material being crushed to excessively 10-20 mesh sieve, is the organic acid soak at room temperature 1-6h of 0.2%-2% with massfraction.
(2) with pretreated lignocellulose raw material Plate Filtration to water content be dry weight 1-4 doubly, then put into the blast chamber of Steam explosive machine, after dimension is pressed 2-10min under the 0.5-2.5MPa vapor pressure, automatically open explosive valve by Controlling System again and spurt fast material to cyclonic separator.Material is taken out, and after water extraction under 30-60 ° of C 1-3 time, Plate Filtration obtains being rich in the water extraction liquid A of wood sugar.
(3) filter residue in the step (2) being collected, is that the mineral acid of 0.5%-5% soaks 5-10h with massfraction under 40-80 ° of C.Plate Filtration to filter residue water content is 1-4 times of dry weight, then puts into the blast chamber of Steam explosive machine, after dimension is pressed 5-20min under the 1.5-3MPa vapor pressure, automatically opens explosive valve by Controlling System again and spurts fast material to cyclonic separator.Material is taken out, and after water extraction under 30-60 ° of C 1-3 time, Plate Filtration obtains being rich in the water extraction liquid B of glucose.
(4) obtain xylitol fermentation liquor behind the water extraction liquid A process ammonia neutralization that (2) is obtained, activated carbon decolorizing, concentrating under reduced pressure, the microbial fermentation.
(5) obtain fermented erythritol liquor behind the water extraction liquid B process calcium hydroxide neutralization that (3) is obtained, activated carbon decolorizing, concentrating under reduced pressure, the microbial fermentation.
(6) xylitol fermentation liquor that (4) is obtained separates through thalline, obtains xylitol crystal behind the removal of impurities of series connection resin, concentrating under reduced pressure, the crystallizing and drying.
(7) obtain erythritol crystal behind the fermented erythritol liquor process thalline separation that (5) is obtained, membrane separation for removing impurities, concentrating under reduced pressure, the crystallizing and drying.
Lignocellulose raw material can be a kind of in corn cob, maize straw, bagasse, wheat bran, the cotton seed hulls, preferred corn cob.Organic acid can use one or several mixing in formic acid, acetic acid, oxalic acid, the oxalic acid, preferred oxalic acid.By soaking, the degree of crosslinking in the lignocellulose raw material between hemicellulose component and other components descends, and simultaneously micromolecular acid can penetrate in the vegetable cell, the degraded of hemicellulose in the aggravation steam explosion process.
Carry out the first step steam explosion for pretreated raw material and process degraded hemicellulose component wherein.Whole process mainly is to utilize high temperature, high-pressure water vapor to process lignocellulose raw material, and passes through component separation and the structural changes of moment release of pressure process implementation raw material.Because what pre-treatment was adopted is the organic acid of lower concentration, and organic acid PKa value is larger, the hydrogen ion content of the sour generation of dissociating in water is less, therefore can optionally make the glycosidic link fracture in the hemicellulose macromole, and the glycosidic link in the cellulose macromolecule is destroyed seldom.Organic acid can also remove the part xylogen in reaction process simultaneously.
Carry out the second step steam explosion for remaining solid slag after the water extraction and process degraded cellulosic component wherein.Mineral acid can be one or more mixing in sulfuric acid, hydrochloric acid, the nitric acid, preferably sulfuric acid.After the quick-fried processing of vapour in the remaining solid slag hemicellulose level seldom, simultaneously Mierocrystalline cellulose and the decline of xylogen bonding force.The PKa value of mineral acid is less, can dissociate to generate a large amount of hydrogen ions in water, and be combined into oxonium ion with water, and the Sauerstoffatom of glycosidic link in the directtissima cellulose macromolecule makes its protonated rear formation conjugate acid, causes the glucosides bond energy to weaken and ruptures.
Sugar component content adopts efficient liquid phase chromatographic analysis in the water extraction liquid, and testing conditions is: waters sugar pak I chromatographic column, ultrapure water is moving phase, differential refraction detector, 80 ° of C of column temperature, flow velocity 0.5ml/min.Acid and aldehyde matter content adopt efficient liquid phase chromatographic analysis in the water extraction liquid, and testing conditions is: BIO-RAD HPX-87H chromatographic column, 0.018M sulfuric acid are moving phase, UV-detector 210nm, 35 ° of C of column temperature, flow velocity 0.5ml/min.Aldehydes matter content adopts colorimetric method for determining.PH and electricity are led and are adopted pH instrument and conductivity meter to measure.
Detected result such as following table:
Table 1: each component concentration of water extraction liquid
Treatment step for water extraction liquid A is as follows: add ammonia neutralization to pH=5-6 in water extraction liquid.Add the carbohydrate special-purpose activated charcoal (g gac/L water extraction liquid) of 1%-5%, under 40-60 ° of C, stir 10-60min.Plate Filtration is squeezed in the vacuum concentration pot concentrated 5-10 doubly with filter pump.Add nitrogenous source among the water extraction liquid A after process and inorganic salt are configured to all kinds of microbiological culture medias, specifically composed as follows:
(1) solid storage medium: wood sugar 50-100g/L, glucose 5-10g/L, yeast powder 5-10g/L, anhydrous magnesium sulfate 0.1-1.0g/L, agar 10-20g/L.
(2) liquid seed culture medium: wood sugar 10-40g/L, glucose 10-40g/L, yeast powder 5-10g/L, anhydrous magnesium sulfate 0.1-1.0g/L.
(3) fermention medium: wood sugar 100-200g/L, glucose 10-20g/L, yeast powder 5-10g/L, potassium primary phosphate 0.5-5.0g/L, anhydrous magnesium sulfate 0.1-1.0g/L.
The present invention produces the used bacterial classification of Xylitol mainly from Candida tropicalis, Candida guilliermondii, a kind of among the Candida parapsilosis.Preferred candida tropicalis Candida tropicalis.Whole fermenting process is as follows:
(1) primary seed solution of preparation fermentation strain: in aseptic super clean bench, join in the 250ml shaking flask that contains the 40ml-100mL liquid seed culture medium with the bacterial strain in the transfering loop picking one ring solid storage medium, at 28-37 ° of C, cultivate 20-30h in the shaking table of 100-200rpm rotating speed.
(2) secondary seed solution of preparation fermentation strain: primary seed solution is all joined in the 2L seeding tank that contains the 1-1.5L liquid seed culture medium, and at 28-37 ° of C, the 150-250rpm rotating speed is cultivated 10-20h under the 1.0-2.0vvm air flow.
(3) cultured secondary seed solution is driven into pump in the 20L fermentor tank that contains the 10-15L liquid fermentation medium, sets 28-37 ° of C of leavening temperature.It is a more special process that yeast fermentation produces Xylitol: earlier fermentation accounts for the over half of fermentation total time, it is cell aerobic growth process, if this moment, thalline can not obtain sufficient oxygen supply, not only thalli growth is bad, the amount of later stage thalline product enzyme also can be not enough, and bio-transformation will certainly be relatively poor; If but this moment Growth of Cells too vigorous, the carbon source that Growth of Cells consumes is too much, will certainly waste too much substrate and cause that to produce pure rate not high.Fermentation later stage thalli growth is to certain phase, the product enzyme accumulates gradually and increases, enter the alcohol phase that turns, little oxygen environment of fermentation is provided this moment, the one, be conducive to improve the vigor of Xylose reductase, increase productive rate and the speed of fermentation, suppress other the secondary approach of metabolism, the 2nd, this, cell did not need further propagation and vigorous growth in period, to avoid consuming more substrate and nutritive substance.According to the singularity requirement of early stage and later stage fermentation, earlier fermentation is by control mixing speed 400-800rpm, and air flow 1.0-3.0vvm keeps dissolved oxygen between 20%-30%; The fermentation later stage, air flow 0.2-1.0vvm kept dissolved oxygen between 5%-10% by control mixing speed 100-300rpm, and fermentation total time is 40-60h.
Treatment step for water extraction liquid B is as follows: after water extraction liquid is heated to 60-80 ° of C, add the calcium hydroxide pH=4-6 that neutralizes.Plate Filtration is removed calcium sulfate precipitation while hot.Liquid portion adds the carbohydrate special-purpose activated charcoal (g gac/L water extraction liquid) of 1%-5% again, stirs 10-60min under 40-60 ° of C.Plate Filtration is squeezed in the vacuum concentration pot concentrated 10-15 doubly with filter pump.Add nitrogenous source among the water extraction liquid B after process and inorganic salt are configured to all kinds of microbiological culture medias, specifically composed as follows:
Solid storage medium: glucose 50-150g/L, yeast powder 5-10g/L, peptone 1-5g/L, anhydrous magnesium sulfate 0.1-1.0g/L, agar 10-20g/L.
Liquid seed culture medium: glucose 20-100g/L, yeast powder 5-10g/L, peptone 1-5g/L, anhydrous magnesium sulfate 0.1-1.0g/L.
Liquid fermentation medium: glucose 200-400g/L, yeast powder 5-10g/L, peptone 1-5g/L, potassium primary phosphate 0.5-5.0g/L, anhydrous magnesium sulfate 0.1-1.0g/L.
The present invention produces mainly a kind of from clump stalk spore yeast (Moniliella pollinis), the Candida lipolytica (Candida lipolytica) of the used bacterial classification of erythritol.Preferred Candida lipolytica Candida lipolytica.Whole fermenting process is as follows:
(1) primary seed solution of preparation fermentation strain: in aseptic super clean bench, join in the 250ml shaking flask that contains the 30ml-80mL liquid seed culture medium with the bacterial strain in the transfering loop picking one ring solid storage medium, at 28-37 ° of C, cultivate 25-35h in the shaking table of 100-200rpm rotating speed.
(2) secondary seed solution of preparation fermentation strain: primary seed solution is all joined in the 2L seeding tank that contains the 1-1.5L liquid seed culture medium with pump, and at 28-37 ° of C, the 150-250rpm rotating speed is cultivated 15-25h under the 1.5-2.5vvm air flow.
(3) cultured secondary seed solution is all joined in the 20L fermentor tank that contains the 10-15L liquid fermentation medium with pump, set 28-37 ° of C of leavening temperature.By regulating air flow 1.5-2.5vvm, rotating speed 200-800rpm keeps fermenting process dissolved oxygen content at 20%-30%.Fermentation total time is 60-80h.
With xylitol fermentation liquor centrifugal 5-10min under 4 ° of C, 10000rpm.The thalline of collecting can be replied utilization.The centrifugal liquid that obtains is carried out desalination and decolouring processing by strong acidic ion resin, strongly basic anionic resin, weak anion resin successively with the 1-5ml/min flow velocity.Wherein strong acidic ion resin is selected a kind of among 001*7 or the D72, is used for positively charged ion in the adsorptive liquid; Strongly basic anionic resin is selected a kind of among D201 or the D296, is used for negatively charged ion in the adsorptive liquid; Weak anion resin is selected D301, is used for pigment molecular in the adsorptive liquid.Measure pH and the electric conductivity value of different time sections resin flow fluid, collection pH 7.0, electricity are led the following effluent liquid of 200us/cm and are heated to 50-80 ° of C, be adsorbed to saturatedly by calcium type resin cation (R.C.) with the 1-5ml/min flow velocity, wherein calcium type resin cation (R.C.) can be selected a kind of among UBK555 or the DTF-01.Because Xylitol is different from the co-ordination complex degree of stability of calcium ion formation in the resin with the residual assorted sugar that ferments in the liquid, calcium type resin cation (R.C.) is stronger to the adsorptive power of Xylitol, therefore mixes the sugar meeting preferentially by wash-out out in the process that washes with water.Measure assorted sugar and Determination of Xylitol in the different time sections elutriant, collect the elutriant that only contains Xylitol, squeeze into pump that to be concentrated into the Xylitol massfraction in the vacuum concentration pot be 60%-70%.Adopt the gradient cooling method that Xylitol is carried out partial crystallization: be warming up to first 80 ° of C and tie up warm 5-15min, the rate of temperature fall with 4-8 ° of C/min is cooled to 50-60 ° of C again, and the crystal seed that adds solute quality 0.01%-0.1% is tieed up warm 1-2h.And then be cooled to 5-20 ° of C with the rate of temperature fall of 1-4 ° of C/min, stop crystallisation process.Use a small amount of alcohol flushing, behind the Plate Filtration under 40-50 ° of C hot-air seasoning obtain white xylitol crystal.
With fermented erythritol liquor centrifugal 5-10min under 4 ° of C, 10000rpm.The thalline of collecting can be replied utilization.Be to remove the wherein macromolecular substance such as albumen, pigment by ceramic membrane under the 0.1-0.5Mpa condition with the centrifugal liquid that obtains at operation pressure.At 40-60 ° of C, working pressure is to pass through metal nano-filtration membrane under the 3-5MPa condition again, and selectivity sees through erythritol.Solution behind the membrane sepn squeezed into pump to be concentrated into the erythritol massfraction in the vacuum concentration pot be 40%-50%.Adopt Ethanol Method that erythritol is carried out partial crystallization: add the dehydrated alcohol of 4 times of volumes, and add solute quality 0.01%-0.1% erythritol crystal seed, temperature remains on 4-6 ° of C, leaves standstill 10-12h, and erythritol is namely crystallizable.Use a small amount of alcohol flushing, behind the Plate Filtration under 40-50 ° of C hot-air seasoning obtain white erythritol crystal.
Description of drawings
Fig. 1 schema of the present invention.
Embodiment
1. Xylose prepares example
Get 1kg corn cob (dry weight), after the oxalic acid of adding 5L, 1% mass concentration soaked 5h, Plate Filtration to corn cob weight in wet base was 3kg.Wet stock is put into the blast chamber of steam explosion machine, and dimension is pressed 5min in the high pressure steam of 1.5MPa, opens explosive valve and spurts fast material and obtain the corn cob of vapour after quick-fried to the cyclonic separator, and weight in wet base is 5kg.Put it in the extractor, with water extraction 1h under 50 ° of C of water of 10L, with pump solidliquid mixture is driven into again and carries out solid-liquid separation in the plate-and-frame filter press and obtain water extraction liquid A.Xylose concentration is 25.4g/L in efficient liquid phase chromatographic analysis water extraction liquid A, and glucose concn is 1.6g/L, and arabinose concentrations is 2.1g/L, and the hemicellulose degradation rate is 87.3%.
2. Glucose Liquid prepares example
Residue filter residue weight in wet base is 3kg, soak 8h under 60 ° of C of the sulfuric acid that wherein adds 3L, 2% mass concentration after, Plate Filtration to filter residue weight in wet base is 3kg.Wet stock is put into the blast chamber of steam explosion machine, and dimension is pressed 15min in the high pressure steam of 2.5MPa, opens explosive valve and spurts fast material and obtain the corn cob of vapour after quick-fried to the cyclonic separator, and weight in wet base is 5kg.Put it in the extractor, with water extraction 1h under 50 ° of C of water of 10L, with pump solidliquid mixture is driven into again and carries out solid-liquid separation in the plate-and-frame filter press and obtain water extraction liquid B.Xylose concentration is 2.0g/L in efficient liquid phase chromatographic analysis water extraction liquid B, and glucose concn is 31.2g/L, and arabinose concentrations is 1.9g/L, and cellulose degradation rate is 81.2%.
3. xylitol fermentation liquor prepares example
10L water extraction liquid A is driven in the storage tank with pump, adds ammonia neutralization to pH=6.The carbohydrate special-purpose activated charcoal (g gac/L water extraction liquid) of adding 3% stirs 30min under 50 ° of C.Plate Filtration is squeezed in the vacuum concentration pot concentrated 6 times with filter pump.Add nitrogenous source among the water extraction liquid A after process and inorganic salt are configured to all kinds of microbiological culture medias.In the aseptic technique environment, get an environmental protection and exist the candida tropicalis in the solid medium to be linked in the 250ml shaking flask that contains the 50ml seed culture medium, at 30 ° of C, obtain primary seed solution behind the cultivation 24h in the shaking table of 200rpm rotating speed.Above-mentioned 50ml seed is linked in the 2L seeding tank that contains the 1.2L seed culture medium, at 30 ° of C, the 250rpm rotating speed obtains secondary seed solution behind the cultivation 15h under the 1.5vvm air flow again, and this moment, bacterial classification entered the middle and later periods of logarithmic phase.Then cultured 1.2L secondary seed solution is linked in the 20L fermentor tank that contains the 12L fermention medium with pump, wherein xylose concentration is 118g/L.Set 30 ° of C of leavening temperature, control mixing speed 500-600rpm in the earlier fermentation 0-22h, air flow 1.0-1.5vvm makes the thalline Fast Growth enter stationary phase.Control mixing speed 200-300rpm in the fermentation later stage 22-44h, air flow 0.2-0.8vvm makes thalline enter the transition phase fermenting xylose and generates Xylitol.Fermentation 48h stops later on fermentation, and the residue xylose concentration is 4.6g/L in the efficient liquid phase chromatographic analysis xylitol fermentation liquor, and Xylitol concentration is 85.2g/L, and xylitol yield is 72.2%.
4. fermented erythritol liquor prepares example
10L water extraction liquid B is driven in the storage tank with pump, is heated to 70 ° of C, add calcium hydroxide and be neutralized to pH=6.Plate Filtration is removed calcium sulfate precipitation while hot.Liquid portion adds 4% carbohydrate special-purpose activated charcoal (g gac/L water extraction liquid) again, stirs 30min under 50 ° of C.Plate Filtration is squeezed in the vacuum concentration pot concentrated 11 times with filter pump.Add nitrogenous source among the water extraction liquid B after process and inorganic salt are configured to all kinds of microbiological culture medias.In the aseptic technique environment, get an environmental protection and exist the Candida lipolytica in the solid medium to be linked in the 250ml shaking flask that contains the 50ml seed culture medium, at 30 ° of C, obtain primary seed solution behind the cultivation 30h in the shaking table of 200rpm rotating speed.Above-mentioned 50ml seed is linked in the 2L seeding tank that contains the 1.2L seed culture medium, at 30 ° of C, the 250rpm rotating speed obtains secondary seed solution behind the cultivation 20h under the 1.5vvm air flow again, and this moment, bacterial classification entered the middle and later periods of logarithmic phase.Then cultured 1.2L secondary seed solution is linked in the 20L fermentor tank that contains the 12L fermention medium with pump, wherein glucose concn is 306g/L.Set 30 ° of C of leavening temperature, mixing speed 500-600rpm, air flow 2.0-2.5vvm, fermentation 72h stops later on fermentation, the residue glucose concn is 10.5g/L in the efficient liquid phase chromatographic analysis fermented erythritol liquor, and erythritol concentration is 156.9g/L, and erythritol alcohol yield is 51.3%.
5. xylitol crystal prepares example
With 12L xylitol fermentation liquor centrifugal 10min under 4 ° of C, 10000rpm, collect supernatant liquor, be driven into pump in the series connection ion exchange column of three 4L that are filled with resin cation (R.C.) 001*7, resin anion(R.A) D201, D301.Control sample introduction flow velocity is 3ml/min, collect pH about 7.0, electricity lead resin flow fluid under 200us/cm be driven into pump again be adsorbed in the ion exchange column that is filled with DTF-01 calcium type resin cation (R.C.) saturated, carry out wash-out with deionized water to adsorbing saturated calcium type resin cation (R.C.) at last, collect the elutriant 20L only contain Xylitol and be driven into pump that to be concentrated into the Xylitol massfraction in the vacuum concentration pot be 70%.Xylitol solution after concentrated is driven in the crystallizer with pump, is warming up to first 80 ° of C and ties up warm 15min, be down to 55 ° of C with the rate of temperature fall of 5 ° of C/min again, add 0.05% the crystal seed that is equivalent to the Xylitol quality and tie up warm 1h.And then be down to 10 ° of C with the rate of temperature fall of 2 ° of C/min, stop crystallisation process.Use a small amount of alcohol flushing, behind the Plate Filtration under 40 ° of C hot-air seasoning obtain white xylitol crystal.Be 91.4% through high-performance liquid chromatogram determination xylitol crystal yield, purity is 98.5%, reducing sugar≤0.5%.
6. erythritol crystal prepares example
With 12L fermented erythritol liquor centrifugal 10min under 4 ° of C, 10000rpm.Collecting supernatant liquor is to remove the wherein macromolecular substance such as albumen, pigment by ceramic membrane under the 0.2Mpa condition at operation pressure.At 50 ° of C, working pressure is to pass through metal nano-filtration membrane under the 4MPa condition again, and selectivity sees through erythritol.Solution behind the membrane sepn squeezed into pump to be concentrated into the erythritol massfraction in the vacuum concentration pot be 50%.Adopt Ethanol Method that erythritol is carried out partial crystallization: add the dehydrated alcohol of 4 times of volumes, and add solute quality 0.01%-0.1% erythritol crystal seed, temperature remains on 4 ° of C, leaves standstill 12h, and erythritol is namely crystallizable.Use a small amount of alcohol flushing, behind the Plate Filtration under 40 ° of C hot-air seasoning obtain white erythritol crystal.Be 90.2% through high-performance liquid chromatogram determination erythritol crystal yield, purity is 95.5%, reducing sugar≤0.5%.
Claims (8)
1. a method of efficiently utilizing lignocellulose raw material to prepare the high added value sugar alcohol is characterized in that, comprises the steps:
(1) lignocellulose raw material being crushed to excessively 10-20 mesh sieve, is the organic acid soak at room temperature 1-6h of 0.2%-2% with massfraction;
(2) with pretreated lignocellulose raw material Plate Filtration to water content be dry weight 1-4 doubly, then put into the blast chamber of Steam explosive machine, after dimension is pressed 2-10min under the 0.5-2.5MPa vapor pressure, automatically open explosive valve by Controlling System again and spurt fast material to cyclonic separator; Material is taken out, and after water extraction under 30-60 ° of C 1-3 time, Plate Filtration obtains being rich in the water extraction liquid A of wood sugar;
(3) filter residue in the step (2) being collected, is that the mineral acid of 0.5%-5% soaks 5-10h with massfraction under 40-80 ° of C; Plate Filtration to filter residue water content is 1-4 times of dry weight, then puts into the blast chamber of Steam explosive machine, after dimension is pressed 5-20min under the 1.5-3MPa vapor pressure, automatically opens explosive valve by Controlling System again and spurts fast material to cyclonic separator; Material is taken out, and after water extraction under 30-60 ° of C 1-3 time, Plate Filtration obtains being rich in the water extraction liquid B of glucose;
(4) obtain xylitol fermentation liquor behind the water extraction liquid A process ammonia neutralization that (2) is obtained, activated carbon decolorizing, concentrating under reduced pressure, the microbial fermentation;
(5) obtain fermented erythritol liquor behind the water extraction liquid B process calcium hydroxide neutralization that (3) is obtained, activated carbon decolorizing, concentrating under reduced pressure, the microbial fermentation;
(6) xylitol fermentation liquor that (4) is obtained separates through thalline, obtains xylitol crystal behind the removal of impurities of series connection resin, concentrating under reduced pressure, the crystallizing and drying;
(7) obtain erythritol crystal behind the fermented erythritol liquor process thalline separation that (5) is obtained, membrane separation for removing impurities, concentrating under reduced pressure, the crystallizing and drying.
2. method according to claim 1, lignocellulose raw material are a kind of in corn cob, maize straw, bagasse, wheat bran, the cotton seed hulls; One or several mixing in organic acid formic acid, acetic acid, oxalic acid, the oxalic acid.
3. method according to claim 1 is one or more mixing in sulfuric acid, hydrochloric acid, the nitric acid with the mineral acid in the step (3).
4. method according to claim 1, lignocellulose raw material is corn cob.
5. method according to claim 1, step (4) is as follows for the treatment step of water extraction liquid A: add ammonia neutralization to pH=5-6 in water extraction liquid; Add the carbohydrate special-purpose activated charcoal, under 40-60 ° of C, stir 10-60min; Plate Filtration is squeezed in the vacuum concentration pot concentrated 5-10 doubly with filter pump.
6. method according to claim 1 is as follows for the treatment step of water extraction liquid B: as after water extraction liquid is heated to 60-80 ° of C, to add the calcium hydroxide pH=4-6 that neutralizes; Plate Filtration is removed calcium sulfate precipitation while hot; Liquid portion adds the carbohydrate special-purpose activated charcoal again, stirs 10-60min under 40-60 ° of C; Plate Filtration is squeezed in the vacuum concentration pot concentrated 10-15 doubly with filter pump.
7. method according to claim 1 is with xylitol fermentation liquor centrifugal 5-10min under 4 ° of C, 10000rpm; The centrifugal liquid that obtains is carried out desalination and decolouring processing by strong acidic ion resin, strongly basic anionic resin, weak anion resin successively with the 1-5ml/min flow velocity; Wherein strong acidic ion resin is selected a kind of among 001*7 or the D72, is used for positively charged ion in the adsorptive liquid; Strongly basic anionic resin is selected a kind of among D201 or the D296, is used for negatively charged ion in the adsorptive liquid; Weak anion resin is selected D301, is used for pigment molecular in the adsorptive liquid; Measure pH and the electric conductivity value of different time sections resin flow fluid, collection pH 7.0, electricity are led the following effluent liquid of 200us/cm and are heated to 50-80 ° of C, be adsorbed to saturatedly by calcium type resin cation (R.C.) with the 1-5ml/min flow velocity, wherein calcium type resin cation (R.C.) can be selected a kind of among UBK555 or the DTF-01.
8. method according to claim 1 is with fermented erythritol liquor centrifugal 5-10min under 4 ° of C, 10000rpm; Be to remove wherein macromolecular substance by ceramic membrane under the 0.1-0.5Mpa condition with the centrifugal liquid that obtains at operation pressure; At 40-60 ° of C, working pressure is to pass through metal nano-filtration membrane under the 3-5MPa condition again, and selectivity sees through erythritol; Solution behind the membrane sepn squeezed into pump to be concentrated into the erythritol massfraction in the vacuum concentration pot be 40%-50%; Adopt Ethanol Method that erythritol is carried out partial crystallization.
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