CN102876732B - 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 in conjunction with conversion technology, reproducible wood fibre resource conversion to be become to the method for high added value sugar alcohol.
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 by 1000-10000 β-D-glucopyranose, pass through β-1, the crosslinked straight-chain polysaccharide forming of 4-glycosidic link, have the thread insoluble micro-fiber structure that a plurality of molecular layers are arranged in parallel and form, basic composition unit is cellobiose.Hemicellulose is generally combined between Mierocrystalline cellulose and xylogen as molecule tamanori, the side chain polysaccharide of the 80-200 polymerization degree being comprised of structural units such as wood sugar, a small amount of pectinose, semi-lactosi or seminoses is that in plant, content is only second to cellulosic saccharan.The network polymer that xylogen is comprised of phenylpropyl alcohol alkane and derivative thereof, is wrapped in the surface of Mierocrystalline cellulose and hemicellulose, plays barrier action in hydrolytic process.
The current utilization for lignocellulose raw material mainly concentrates on cellulosic hydrolysis and the biofuel aspects such as ethanol, butanols are prepared in microbial transformation.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, cellulase hydrolysis cost is higher.Because the pretreated object of above-mentioned fibrous material is remove xylogen and hemicellulose to cellulosic provide protection and destroy the crystalline structure between 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 hemicellulose compared with the feature of the easy degraded of Mierocrystalline cellulose, design different steam explosion conditions, hemicellulose and the Mierocrystalline cellulose of degrading successively in 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 development in recent years a kind of lignocellulose treatment process rapidly.Raw material is with being steam heated to 180-240 ℃, and dimension is pressed for some time, when unexpected release of pressure spurts, produces secondary steam, and volume surges, under the effect of mechanical force, by solid materials structure deteriorate.Process engineering institute of Chinese Academy of Sciences Applied Physics principle is prepared xylo-oligosaccharide (CN1233614): the raw material after the quick-fried processing of vapour can obtain solubility hemicellulose through water extracting, and its main component is xylo-oligosaccharide, and 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 raw material, increase the palliating degradation degree of hemicellulose in the quick-fried process of vapour, through water extracting, can directly obtain xylose solution, 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 yeast D-wood sugar can be converted into after Xylitol, 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 existing patent still mainly obtains by the method for high-concentration sulfuric acid hydrolyzed hemicellulose, needs alkali neutralization, decolouring, desalting treatment before fermentation, process is complicated, soda acid consumption is large.This patent adopts 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, by simple activated carbon decolorizing and ammoniacal liquor, regulate and can be used for follow-up fermenting process, under the fermentation condition of optimizing, wood sugar is greater than 70% to the transformation efficiency of Xylitol.
Erythritol is that molecular weight is minimum, the sugar alcohol of caloric value minimum (≤1.66kJ/g), and 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, without male offspring bitter taste.The production of current industrial erythritol is mainly to utilize glucose fermentation.Chinese patent ZL200510102929.6 has reported take and has refined glucose as carbon source, utilizes Candida lipolytica fermentation to obtain the method for erythritol; Patent ZL201010611106.7 has reported take Semen Maydis powder as raw material, through enzymic hydrolysis, obtains Glucose Liquid, 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 reproducible lignocellulose raw material in conjunction with 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 high added value sugar alcohol is characterized in that, comprises the steps:
(1) lignocellulose raw material is crushed to and can crosses 10-20 mesh sieve, the organic acid soak at room temperature 1-6h that is 0.2%-2% with massfraction.
(2) 1-4 that is dry weight by pretreated lignocellulose raw material Plate Filtration to water content doubly, then put into the blast chamber of Steam explosive machine, under 0.5-2.5MPa vapor pressure, dimension is pressed after 2-10min, then by Controlling System, automatically opens explosive valve and spurt fast material to cyclonic separator.Material is taken out, and at 30-60 ℃, after water extraction 1-3 time, Plate Filtration obtains being rich in the water extraction liquid A of wood sugar.
(3) filter residue in step (2) is collected, the mineral acid that is 0.5%-5% with massfraction soaks 5-10h at 40-80 ℃.The 1-4 that Plate Filtration to filter residue water content is dry weight doubly, then puts into the blast chamber of Steam explosive machine, and under 1.5-3MPa vapor pressure, dimension is pressed after 5-20min, then by Controlling System, automatically opens explosive valve and spurt fast material to cyclonic separator.Material is taken out, and at 30-60 ℃, after water extraction 1-3 time, Plate Filtration obtains being rich in the water extraction liquid B of glucose.
(4) the water extraction liquid A (2) being obtained obtains xylitol fermentation liquor after ammonia neutralization, activated carbon decolorizing, concentrating under reduced pressure, microorganism fermentation.
(5) the water extraction liquid B (3) being obtained obtains fermented erythritol liquor after calcium hydroxide neutralization, activated carbon decolorizing, concentrating under reduced pressure, microorganism fermentation.
(6) xylitol fermentation liquor (4) being obtained is separated through thalline, after the removal of impurities of series connection resin, concentrating under reduced pressure, crystallizing and drying, obtains xylitol crystal.
(7) fermented erythritol liquor (5) being obtained obtains erythritol crystal after thalline separation, membrane separation for removing impurities, concentrating under reduced pressure, crystallizing and drying.
Lignocellulose raw material can be a kind of in corn cob, maize straw, bagasse, wheat bran, cotton seed hulls, preferably corn cob.Organic acid can be used one or several mixing in formic acid, acetic acid, oxalic acid, oxalic acid, preferably oxalic acid.By soaking, the degree of crosslinking in lignocellulose raw material between hemicellulose component and other components declines, and micromolecular acid simultaneously can penetrate in vegetable cell, the degraded of hemicellulose in aggravation steam explosion process.
For pretreated raw material, carry out the first step steam explosion and process degraded hemicellulose component wherein.Whole process is mainly to utilize high temperature, high-pressure water vapor to process lignocellulose raw material, and by component separation and the structural changes of moment release of pressure process implementation raw material.Due to pre-treatment employing 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 hemicellulose macromole, and the glycosidic link in cellulose macromolecule is destroyed seldom.Organic acid can also remove part xylogen in reaction process simultaneously.
For remaining solid slag after water extraction, carry out second step steam explosion and process degraded cellulosic component wherein.Mineral acid can be one or more mixing in sulfuric acid, hydrochloric acid, nitric acid, preferably sulfuric acid.After the quick-fried processing of vapour in remaining solid slag hemicellulose level seldom, Mierocrystalline cellulose and the decline of xylogen bonding force simultaneously.The PKa value of mineral acid is less, can in water, dissociate and generate a large amount of hydrogen ions, and be combined into oxonium ion with water, and the Sauerstoffatom of glycosidic link in directtissima cellulose macromolecule, makes its protonated rear formation conjugate acid, causes glucosides bond energy weaken and rupture.
In water extraction liquid, sugar component content adopts efficient liquid phase chromatographic analysis, and testing conditions is: waters sugar pak I chromatographic column, ultrapure water is moving phase, differential refraction detector, 80 ℃ of column temperatures, flow velocity 0.5ml/min.In water extraction liquid, acid and aldehyde matter content adopt efficient liquid phase chromatographic analysis, and testing conditions is: BIO-RAD HPX-87H chromatographic column, 0.018M sulfuric acid is moving phase, UV-detector 210nm, 35 ℃ of column temperatures, 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 is as following table:
Table 1: each component concentration of water extraction liquid
Treatment step for water extraction liquid A is as follows: in water extraction liquid, add ammonia neutralization to pH=5-6.The carbohydrate special-purpose activated charcoal (g gac/L water extraction liquid) that adds 1%-5% stirs 10-60min at 40-60 ℃.Plate Filtration, squeezes into filter pump in vacuum concentration pot and concentrates 5-10 doubly.In the water extraction liquid A after processing, add nitrogenous source and inorganic salt to be 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 Xylitol bacterial classification used mainly from Candida tropicalis, Candida guilliermondii, a kind of in Candida parapsilosis.Preferred candida tropicalis Candida tropicalis.Whole fermenting process is as follows:
(1) prepare the primary seed solution of fermentation strain: in aseptic super clean bench, with the bacterial strain in transfering loop picking one ring solid storage medium, join in the 250ml shaking flask containing 40ml-100mL liquid seed culture medium, at 28-37 ℃, in the shaking table of 100-200rpm rotating speed, cultivate 20-30h.
(2) prepare the secondary seed solution of fermentation strain: primary seed solution is all joined in the 2L seeding tank containing 1-1.5L liquid seed culture medium, and at 28-37 ℃, 150-250rpm rotating speed, cultivates 10-20h under 1.0-2.0vvm air flow.
(3) cultured secondary seed solution is driven in the 20L fermentor tank containing 10-15L liquid fermentation medium with pump, sets leavening temperature 28-37 ℃.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 now 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 poor; If but Growth of Cells too vigorous now, the carbon source that Growth of Cells consumes is too much, will certainly waste too much substrate and cause that to produce alcohol rate not high.Fermentation later stage thalli growth is to certain phase, producing enzyme accumulates and increases gradually, enter the alcohol phase that turns, micro-oxygen environment of fermentation is now provided, 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 controlling mixing speed 400-800rpm, and air flow 1.0-3.0vvm, maintains dissolved oxygen between 20%-30%; The fermentation later stage, air flow 0.2-1.0vvm maintained dissolved oxygen between 5%-10% by controlling mixing speed 100-300rpm, and fermentation total time is 40-60h.
Treatment step for water extraction liquid B is as follows: water extraction liquid is heated to after 60-80 ℃, adds calcium hydroxide to neutralize pH=4-6.Plate Filtration, removes calcium sulfate precipitation while hot.Liquid portion adds the carbohydrate special-purpose activated charcoal (g gac/L water extraction liquid) of 1%-5% again, at 40-60 ℃, stirs 10-60min.Plate Filtration, squeezes into filter pump in vacuum concentration pot and concentrates 10-15 doubly.In the water extraction liquid B after processing, add nitrogenous source and inorganic salt to be 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), Candida lipolytica (Candida lipolytica) of erythritol bacterial classification used.Preferred Candida lipolytica Candida lipolytica.Whole fermenting process is as follows:
(1) prepare the primary seed solution of fermentation strain: in aseptic super clean bench, with the bacterial strain in transfering loop picking one ring solid storage medium, join in the 250ml shaking flask containing 30ml-80mL liquid seed culture medium, at 28-37 ℃, in the shaking table of 100-200rpm rotating speed, cultivate 25-35h.
(2) prepare the secondary seed solution of fermentation strain: primary seed solution is all joined in the 2L seeding tank containing 1-1.5L liquid seed culture medium with pump, and at 28-37 ℃, 150-250rpm rotating speed, cultivates 15-25h under 1.5-2.5vvm air flow.
(3) cultured secondary seed solution is all joined in the 20L fermentor tank containing 10-15L liquid fermentation medium with pump, set leavening temperature 28-37 ℃.By regulating air flow 1.5-2.5vvm, rotating speed 200-800rpm maintains fermenting process dissolved oxygen content at 20%-30%.Fermentation total time is 60-80h.
By xylitol fermentation liquor centrifugal 5-10min under 4 ℃, 10000rpm.The thalline of collecting can be replied utilization.The centrifugal liquid obtaining is carried out to desalination and decolouring processing by strong acidic ion resin, strongly basic anionic resin, weak anion resin successively with 1-5ml/min flow velocity.Wherein strong acidic ion resin is selected a kind of in 001*7 or D72, the positively charged ion being used in adsorptive liquid; Strongly basic anionic resin is selected a kind of in D201 or D296, the negatively charged ion being used in adsorptive liquid; Weak anion resin is selected D301, the pigment molecular being used in adsorptive liquid.Measure pH and the electric conductivity value of different time sections resin flow fluid, the effluent liquid that collection pH7.0, electricity are led below 200us/cm is heated to 50-80 ℃, with 1-5ml/min flow velocity, by calcium type resin cation (R.C.), be adsorbed to saturatedly, wherein calcium type resin cation (R.C.) can be selected a kind of in UBK555 or DTF-01.Because the assorted sugar that Xylitol in liquid is residual with fermentation is different from the co-ordination complex degree of stability that calcium ion in resin forms, calcium type resin cation (R.C.) is stronger to the adsorptive power of Xylitol, and therefore in the process washing with water, assorted sugar can be preferentially by wash-out out.Measure assorted sugar and Determination of Xylitol in different time sections elutriant, collect the elutriant that only contains Xylitol, with pump, squeeze into that in vacuum concentration pot, to be concentrated into Xylitol massfraction be 60%-70%.Adopt gradient cooling method to carry out partial crystallization to Xylitol: to be first warming up to 80 ℃ of warm 5-15min of dimension, then to be cooled to 50-60 ℃ with the rate of temperature fall of 4-8 ℃/min, add the crystal seed of solute quality 0.01%-0.1% to tie up warm 1-2h.And then be cooled to 5-20 ℃ with the rate of temperature fall of 1-4 ℃/min, stop crystallisation process.Use a small amount of alcohol flushing, after Plate Filtration, at 40-50 ℃, hot-air seasoning obtains white xylitol crystal.
By fermented erythritol liquor centrifugal 5-10min under 4 ℃, 10000rpm.The thalline of collecting can be replied utilization.By the centrifugal liquid obtaining, at operation pressure, be by ceramic membrane, to remove the wherein macromolecular substance such as albumen, pigment under 0.1-0.5Mpa condition.At 40-60 ℃, working pressure is under 3-5MPa condition, to pass through metal nano-filtration membrane again, and selectivity sees through erythritol.Solution after membrane sepn is squeezed into pump in vacuum concentration pot, to be concentrated into erythritol massfraction be 40%-50%.Adopt Ethanol Method to carry out partial crystallization to erythritol: 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 ℃, standing 10-12h, erythritol is crystallizable.Use a small amount of alcohol flushing, after Plate Filtration, at 40-50 ℃, hot-air seasoning obtains white erythritol crystal.
Accompanying drawing explanation
Fig. 1 schema of the present invention.
Embodiment
1. Xylose is prepared example
Get 1kg corn cob (dry weight), add the oxalic acid of 5L, 1% mass concentration to soak after 5h, Plate Filtration to corn cob weight in wet base is 3kg.Wet stock is put into the blast chamber of steam explosion machine, in the high pressure steam of 1.5MPa, dimension is pressed 5min, opens explosive valve and spurts fast material to obtaining the corn cob of vapour after quick-fried in cyclonic separator, and weight in wet base is 5kg.Put it in extractor, with water extraction 1h at 50 ℃, the water of 10L, then with pump, solidliquid mixture is driven into and in plate-and-frame filter press, carries out solid-liquid separation and obtain water extraction liquid A.In efficient liquid phase chromatographic analysis water extraction liquid A, xylose concentration is 25.4g/L, and glucose concn is 1.6g/L, and arabinose concentrations is 2.1g/L, and hemicellulose degradation rate is 87.3%.
2. Glucose Liquid is prepared example
Residue filter residue weight in wet base is 3kg, adds wherein at 60 ℃, the sulfuric acid of 3L, 2% mass concentration and soaks after 8h, and Plate Filtration to filter residue weight in wet base is 3kg.Wet stock is put into the blast chamber of steam explosion machine, in the high pressure steam of 2.5MPa, dimension is pressed 15min, opens explosive valve and spurts fast material to obtaining the corn cob of vapour after quick-fried in cyclonic separator, and weight in wet base is 5kg.Put it in extractor, with water extraction 1h at 50 ℃, the water of 10L, then with pump, solidliquid mixture is driven into and in plate-and-frame filter press, carries out solid-liquid separation and obtain water extraction liquid B.In efficient liquid phase chromatographic analysis water extraction liquid B, xylose concentration is 2.0g/L, 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 is prepared example
10L water extraction liquid A is driven in storage tank with pump, adds ammonia neutralization to pH=6.Add 3% carbohydrate special-purpose activated charcoal (g gac/L water extraction liquid), at 50 ℃, stir 30min.Plate Filtration, squeezes into filter pump in vacuum concentration pot and concentrates 6 times.In the water extraction liquid A after processing, add nitrogenous source and inorganic salt to be configured to all kinds of microbiological culture medias.In aseptic technique environment, get an environmental protection and exist the candida tropicalis in solid medium to be linked in the 250ml shaking flask containing 50ml seed culture medium, at 30 ℃, obtain primary seed solution after cultivating 24h in the shaking table of 200rpm rotating speed.Above-mentioned 50ml seed is linked in the 2L seeding tank containing 1.2L seed culture medium, at 30 ℃, 250rpm rotating speed, obtains secondary seed solution after cultivating 15h under 1.5vvm air flow again, and now bacterial classification has entered the middle and later periods of logarithmic phase.Then with pump, cultured 1.2L secondary seed solution is linked in the 20L fermentor tank containing 12L fermention medium, wherein xylose concentration is 118g/L.Set 30 ℃ of leavening temperatures, control mixing speed 500-600rpm in earlier fermentation 0-22h, air flow 1.0-1.5vvm, makes thalline Fast Growth enter stationary phase.In fermentation later stage 22-44h, control mixing speed 200-300rpm, air flow 0.2-0.8vvm, makes thalline enter transition phase fermenting xylose and generates Xylitol.Fermentation 48h stops fermentation later, and in efficient liquid phase chromatographic analysis xylitol fermentation liquor, remaining xylose concentration is 4.6g/L, and Xylitol concentration is 85.2g/L, and xylitol yield is 72.2%.
4. fermented erythritol liquor is prepared example
10L water extraction liquid B is driven in storage tank with pump, is heated to 70 ℃, add calcium hydroxide to be neutralized to pH=6.Plate Filtration, removes calcium sulfate precipitation while hot.Liquid portion adds 4% carbohydrate special-purpose activated charcoal (g gac/L water extraction liquid) again, at 50 ℃, stirs 30min.Plate Filtration, squeezes into filter pump in vacuum concentration pot and concentrates 11 times.In the water extraction liquid B after processing, add nitrogenous source and inorganic salt to be configured to all kinds of microbiological culture medias.In aseptic technique environment, get an environmental protection and exist the Candida lipolytica in solid medium to be linked in the 250ml shaking flask containing 50ml seed culture medium, at 30 ℃, obtain primary seed solution after cultivating 30h in the shaking table of 200rpm rotating speed.Above-mentioned 50ml seed is linked in the 2L seeding tank containing 1.2L seed culture medium, at 30 ℃, 250rpm rotating speed, obtains secondary seed solution after cultivating 20h under 1.5vvm air flow again, and now bacterial classification has entered the middle and later periods of logarithmic phase.Then with pump, cultured 1.2L secondary seed solution is linked in the 20L fermentor tank containing 12L fermention medium, wherein glucose concn is 306g/L.Set 30 ℃ of leavening temperatures, mixing speed 500-600rpm, air flow 2.0-2.5vvm, fermentation 72h stops fermentation later, in efficient liquid phase chromatographic analysis fermented erythritol liquor, remaining glucose concn is 10.5g/L, and erythritol concentration is 156.9g/L, and erythritol alcohol yield is 51.3%.
5. xylitol crystal is prepared example
By 12L xylitol fermentation liquor centrifugal 10min under 4 ℃, 10000rpm, collect supernatant liquor, with pump, be driven 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.Controlling sample introduction flow velocity is 3ml/min, collecting pH leads resin flow fluid under 200us/cm at 7.0 left and right, electricity and is adsorbed in being driven into the ion exchange column that is filled with DTF-01 calcium type resin cation (R.C.) with pump more saturated, finally with deionized water, to adsorbing saturated calcium type resin cation (R.C.), carry out wash-out, collect the elutriant 20L only contain Xylitol and with pump, be driven into that in vacuum concentration pot, to be concentrated into Xylitol massfraction be 70%.Xylitol solution after concentrated is driven in crystallizer with pump, is first warming up to 80 ℃ of warm 15min of dimension, then is down to 55 ℃ with the rate of temperature fall of 5 ℃/min, add 0.05% the crystal seed that is equivalent to Xylitol quality to tie up warm 1h.And then be down to 10 ℃ with the rate of temperature fall of 2 ℃/min, stop crystallisation process.Use a small amount of alcohol flushing, after Plate Filtration, at 40 ℃, hot-air seasoning obtains white xylitol crystal.Through high-performance liquid chromatogram determination xylitol crystal yield, be 91.4%, purity is 98.5%, reducing sugar≤0.5%.
6. erythritol crystal is prepared example
By 12L fermented erythritol liquor centrifugal 10min under 4 ℃, 10000rpm.Collecting supernatant liquor is by ceramic membrane, to remove the wherein macromolecular substance such as albumen, pigment under 0.2Mpa condition at operation pressure.At 50 ℃, working pressure is under 4MPa condition, to pass through metal nano-filtration membrane again, and selectivity sees through erythritol.Solution after membrane sepn is squeezed into pump in vacuum concentration pot, to be concentrated into erythritol massfraction be 50%.Adopt Ethanol Method to carry out partial crystallization to erythritol: add the dehydrated alcohol of 4 times of volumes, and add solute quality 0.01%-0.1% erythritol crystal seed, temperature remains on 4 ℃, standing 12h, erythritol is crystallizable.Use a small amount of alcohol flushing, after Plate Filtration, at 40 ℃, hot-air seasoning obtains white erythritol crystal.Through high-performance liquid chromatogram determination erythritol crystal yield, be 90.2%, purity is 95.5%, reducing sugar≤0.5%.
Claims (5)
1. utilize lignocellulose raw material to prepare a method for sugar alcohol, it is characterized in that, comprise the steps:
(1) lignocellulose raw material is crushed to and can crosses 10-20 mesh sieve, the organic acid soak at room temperature 1-6h that is 0.2%-2% with massfraction; Described one or several mixing in formic acid, acetic acid, oxalic acid, oxalic acid for organic acid;
(2) 1-4 that is dry weight by pretreated lignocellulose raw material Plate Filtration to water content doubly, then put into the blast chamber of Steam explosive machine, under 0.5-2.5MPa vapor pressure, dimension is pressed after 2-10min, then by Controlling System, automatically opens explosive valve and spurt fast material to cyclonic separator; Material is taken out, and at 30-60 ℃, after water extraction 1-3 time, Plate Filtration obtains being rich in the water extraction liquid A of wood sugar;
(3) filter residue in step (2) is collected, the mineral acid that is 0.5%-5% with massfraction soaks 5-10h at 40-80 ℃; The 1-4 that Plate Filtration to filter residue water content is dry weight doubly, then puts into the blast chamber of Steam explosive machine, and under 1.5-3MPa vapor pressure, dimension is pressed after 5-20min, then by Controlling System, automatically opens explosive valve and spurt fast material to cyclonic separator; Material is taken out, and at 30-60 ℃, after water extraction 1-3 time, Plate Filtration obtains being rich in the water extraction liquid B of glucose; Described mineral acid is one or more mixing in sulfuric acid, hydrochloric acid, nitric acid;
(4) the water extraction liquid A (2) being obtained obtains xylitol fermentation liquor after ammonia neutralization, activated carbon decolorizing, concentrating under reduced pressure, microorganism fermentation; Specific as follows: in water extraction liquid, to add ammonia neutralization to pH=5-6; Add carbohydrate special-purpose activated charcoal, at 40-60 ℃, stir 10-60min; Plate Filtration, squeezes into filter pump in vacuum concentration pot and concentrates 5-10 doubly;
(5) the water extraction liquid B (3) being obtained obtains fermented erythritol liquor after calcium hydroxide neutralization, activated carbon decolorizing, concentrating under reduced pressure, microorganism fermentation; Specific as follows: water extraction liquid to be heated to after 60-80 ℃, to add calcium hydroxide to neutralize pH=4-6; Plate Filtration, removes calcium sulfate precipitation while hot; Liquid portion adds carbohydrate special-purpose activated charcoal again, at 40-60 ℃, stirs 10-60min; Plate Filtration, squeezes into filter pump in vacuum concentration pot and concentrates 10-15 doubly;
(6) xylitol fermentation liquor (4) being obtained is separated through thalline, after the removal of impurities of series connection resin, concentrating under reduced pressure, crystallizing and drying, obtains xylitol crystal;
(7) fermented erythritol liquor (5) being obtained obtains erythritol crystal after thalline separation, membrane separation for removing impurities, concentrating under reduced pressure, crystallizing and drying.
2. method according to claim 1, lignocellulose raw material is a kind of in corn cob, maize straw, bagasse, wheat bran, cotton seed hulls.
3. method according to claim 1, lignocellulose raw material is corn cob.
4. method according to claim 1, by xylitol fermentation liquor centrifugal 5-10min under 4 ℃, 10000rpm; The centrifugal liquid obtaining is carried out to desalination and decolouring processing by strong acidic ion resin, strongly basic anionic resin, weak anion resin successively with 1-5ml/min flow velocity; Wherein strong acidic ion resin is selected a kind of in 001*7 or D72, the positively charged ion being used in adsorptive liquid; Strongly basic anionic resin is selected a kind of in D201 or D296, the negatively charged ion being used in adsorptive liquid; Weak anion resin is selected D301, the pigment molecular being used in adsorptive liquid; Measure pH and the electric conductivity value of different time sections resin flow fluid, the effluent liquid that collection pH7.0, electricity are led below 200us/cm is heated to 50-80 ℃, with 1-5ml/min flow velocity, by calcium type resin cation (R.C.), be adsorbed to saturatedly, wherein calcium type resin cation (R.C.) can be selected a kind of in UBK555 or DTF-01.
5. method according to claim 1, by fermented erythritol liquor centrifugal 5-10min under 4 ℃, 10000rpm; By the centrifugal liquid obtaining, at operation pressure, be by ceramic membrane, to remove wherein macromolecular substance under 0.1-0.5Mpa condition; At 40-60 ℃, working pressure is under 3-5MPa condition, to pass through metal nano-filtration membrane again, and selectivity sees through erythritol; Solution after membrane sepn is squeezed into pump in vacuum concentration pot, to be concentrated into erythritol massfraction be 40%-50%; Adopt Ethanol Method to carry out partial crystallization to erythritol.
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| CN104031946A (en) * | 2013-03-06 | 2014-09-10 | 国网新源控股有限公司北京非粮醇电联产技术研发中心 | Detoxification treatment-free cellulosic ethanol production method |
| CN103243031B (en) * | 2013-05-10 | 2014-06-18 | 天津科技大学 | High-permeability-resistant aureobasidium pullulans strain and application thereof |
| CN103290068B (en) * | 2013-05-10 | 2014-06-18 | 天津科技大学 | Method for producing erythritol by utilizing hypertonicity-resistant Aureobasidium pullulans |
| CN104404803B (en) * | 2014-08-29 | 2016-08-17 | 济南米铎碳新能源科技有限公司 | Straw component separates and the method for straw component complete utilization |
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| CN108610235A (en) * | 2016-12-09 | 2018-10-02 | 中国科学院大连化学物理研究所 | A kind of steam explosion Hydrogenation for sugar alcohol method |
| CN108611443A (en) * | 2016-12-09 | 2018-10-02 | 中国科学院大连化学物理研究所 | A kind of method of corncob production monosaccharide |
| CN113512566A (en) * | 2021-05-25 | 2021-10-19 | 浙江华康药业股份有限公司 | System and method for co-producing erythritol and liquid sorbitol by using corn starch |
| CN114276885B (en) * | 2022-01-05 | 2024-05-17 | 江西海富生物工程有限公司 | Method for preparing ethanol from fresh fructus momordicae |
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