Summary of the invention
In order to address the above problem, after having the object of the present invention is to provide the fractionation method of the full component of a kind of forestry cellulose biomass and having utilized separation, component prepares fuel alcohol and xylo-oligosaccharide.The present invention relates to by the biorefinery technology, forestry cellulose biomass is converted into bio-fuel and the wood sugars bio-based chemicals such as fuel alcohol.Ethanol is a kind of water white transparency, volatile, easy firing, nonconducting liquid, can add to according to a certain percentage in gasoline, and be the main substitute of following gasoline.Wood sugar is a kind of white crystalline powder, and is soluble in water, is a kind of chemicals commonly used, can be used for producing xylitol or as food additives.Xylo-oligosaccharide claim again wood oligose be by 2~7 wood sugar molecules with 3-1, the functional polymerization sugar that 4 glycosidic bonds are combined into, it can optionally promote the proliferation activity of intestinal bifidobacteria, is important nutrient and healthcare products.The present invention adopts forestry cellulose biomass exactly, and its classification of carrying out full component is separated, and each component that separation is obtained is converted into bio-fuel and high added value bio-based chemicals, realizes the maximization of the utilization of resources; Can reduce China to the dependence of Imported oil, reduce the pollution to environment; Also can promote to set up new forms of energy industrial sector and Biochemical Industry, change the mode of Economic Growth in China, realize society and economic sustainable development.
For reaching above-mentioned purpose, the present invention adopts following technical scheme:
The fractionation method of the full component of a kind of forestry cellulose biomass comprises the steps:
A) pulverizing, immersion and the press filtration of the fresh material of forestry cellulose biomass or dry (being purchased from Zhangzhou sugar Refinery of Fujian Prov.);
B) solid phase after press filtration is partly used dipping by lye, adds oxidant, and first extracting under middle temperature obtains secondary liquid phase and secondary solid phase two parts after the secondary press filtration; The secondary solid phase partly continues to be soaked in alkali lye, at high temperature extracting, three solid phases and three liquid phase two parts of obtaining after three press filtrations; Wherein three solid phase Main Ingredients and Appearances are coarse product of cellulose, and three liquid phase Main Ingredients and Appearances are hemicellulose and lignin degrading mixed liquor; Add oxidant in middle temperature alkali treatment process, can accelerate the decomposition of lignin, the physical arrangement of lignocellulose is dissociated, be conducive to the hemicellulose component and the lignin component enters aqueous slkali, for the separation fully of three components in cellulose biomass lays the foundation.
C) the liquid phase pressing filtering liquid (comprising secondary liquid phase and three liquid phases) of warm alkali oxidation extracting and the extracting of high temperature alkali in the merging, through NF membrane (Correspondent/Hydranautics/businessmans such as Tao Shi provide), that pressing filtering liquid is concentrated, adding final concentration in concentrate is alcohol more than 50%, static rear filtration or centrifugation are precipitated thing and supernatant; Sediment is just the hemicellulose crude product;
D) with step c) in the supernatant that obtains transfer to acidity, static rear filtration or centrifugation, precipitation is the lignin crude product.
Described alkali lye employing concentration is 1%~7% NaOH, KOH, Na
2CO
3In a kind of; Described oxidant employing concentration is 1%~5% O
3, H
2O
2, KMnO
4In a kind of.
It is extracting 2~4 hours under 40~60 ℃ of conditions that temperature is adopted in described middle temperature extracting; It is extracting more than at least 1 hour under 100~160 ℃ of conditions that temperature is adopted in described high temperature extracting.
Described step c) in, pressing filtering liquid is concentrated into more than 5 times, until hemicellulose and lignin solid concentration reach more than 10%, recycle of alkali liquor is more than 80%; And step c) and steps d) in quiescent time be 1~5 hour; Steps d) in adjustment of acidity to pH be 3~4.
The coarse product of cellulose that described separation obtains utilizes cellulase that coarse product of cellulose is degraded to glucose on the one hand for the preparation of cellulase or hemicellulase on the other hand, produces alcohol after culture propagation; Separate the hemicellulose crude product obtain and utilize hemicellulase that it is degraded to wood sugar and xylo-oligosaccharide chemicals, after separating-purifying as food additives or produce the raw material of xylitol; The lignin that separation obtains utilizes lignin can make degradable, reproducible polymer as dispersant, adsorbent/strippant, petroleum recovery auxiliary agent, asphalt emulsifier.
After a kind of utilization separates, component prepares fuel alcohol, and the coarse product of cellulose that described separation obtains utilizes cellulase that coarse product of cellulose is degraded to glucose on the one hand for the preparation of cellulase or hemicellulase on the other hand, produces alcohol after culture propagation; The preparation method of described cellulase or hemicellulase is: with described coarse product of cellulose, adopt the method for solid state fermentation koji, inoculate respectively cellulase producing strain or produce the hemicellulase bacterial strain, solid state fermentation is cultivated after 3 days and is gathered in the crops cellulase or hemicellulase.
Described cellulase producing strain adopts a kind of in Aspergillus glaucus or these 2 kinds of fungies of mould; Produce the hemicellulase bacterial strain and adopt a kind of in aspergillus niger or mould these the 2 kinds of fungies of wood.
Described coarse product of cellulose and cellulase with in 5: 1-1: 1 ratio is mixed, add appropriate water, making solid-to-liquid ratio is 1: 10, the saccharified liquid after 50 ℃ of enzymolysis obtained cellulase hydrolysis more than 12 hours, and the saccharified liquid after cellulase hydrolysis is concentrated into sugared concentration more than 15% through NF membrane; Saccharified liquid after concentrated is directly used in fermentation and produces alcohol.
After a kind of utilization separates, component prepares xylo-oligosaccharide: the hemicellulose crude product that described separation obtains with hemicellulase in 5: 1-1: after 1 ratio is mixed, add the water of 5~6 times of bulking values of hemicellulose crude product, 60 ℃ of reactions 5~16 hours, add the activated carbon decolorizing agent to decolour, then by solids removed by filtration impurity; Saccharified liquid after decolorization filtering by the ion exchange resin desalination, is then carried out film and concentrates; Carry out the xylo-oligosaccharide liquid that spray drying is made Powdered xylo-oligosaccharide or passed through NF membrane simmer down to high concentration after being concentrated into the saccharified liquid after decolouring and desalination more than 15%.
The invention has the beneficial effects as follows: the present invention has set up ripe biorefinery technology cellulose biomass has been carried out classification separation and Efficient Conversion, three kinds of components in cellulose biomass is carried out the classification separating-purifying obtain cellulose, hemicellulose, lignin component; Then fully use each component, produce bio-fuel and bio-based chemicals: at first separate obtaining cellulose from cellulose biomass, utilize cellulase that cellulose degradation is glucose, produce alcohol after culture propagation; Utilize hemicellulase that xylan degrading is the chemicals such as wood sugar and xylo-oligosaccharide, after separating-purifying as food additives or produce the raw material of xylitol; Lignin can be used as dispersant, adsorbent/strippant, petroleum recovery auxiliary agent, asphalt emulsifier, utilizes lignin can make degradable, reproducible polymer.In separating, the hemicellulose classification adopt two-step method to extract, warm oxidative extraction in elder generation, and rear high temperature extracts, and can increase substantially the recovery rate of hemicellulose, and the actual extracting rate can reach more than 95% of theoretical recovery rate.In the hemicellulose extractive process, the handling procedure of temperature-high temperature in employing-middle temperature can improve the efficiency of utilization of technical process.Modern Membrane Technology is applied to the technical process such as recycle of alkali liquor, saccharified liquid component separate, saccharified liquid is concentrated, dehydration of alcohol, but the energy consumption of decrease production process and cost.
In sum, technical scheme of the present invention can realize the maximum resource utilization to the full component of cellulose biomass, increases substantially living value-added content of product, promotes the economic benefit of Biomass Industry, avoids the wasting of resources.The change of bootable economic restructuring simultaneously and Industry Development Pattern.The present invention has integrated catalyzed by biological enzyme and chemical treatment method, with both advantages together, can greatly reduce the pollution to environment, increase substantially production efficiency.And increase substantially the economic benefit of whole industrial chain, improve more than 10 times than the economic benefit of independent production of cellulose alcohol, provide a feasible way for scale development utilizes cellulose biomass.
The specific embodiment
The present invention is further detailed explanation below in conjunction with accompanying drawing 1.
Embodiment 1
The fractionation method of the full component of a kind of forestry cellulose biomass that the present embodiment adopts comprises the steps:
1, the fresh material of forestry cellulose biomass or dry after crushed, first soak then press filtration with clear water;
2, the NaOH dipping by lye of the solid phase part after processing through 1 take concentration as 1%, solid-to-liquid ratio is 1: 10 (WN) left and right, adding concentration is 5% O
3Oxidant first 60 ℃ of lower extractings of middle temperature 2 hours, obtains secondary liquid phase and secondary solid phase two parts after the secondary press filtration; The secondary solid phase partly continues to be soaked in 1% NaOH alkali lye, and solid-to-liquid ratio is 1: 10 (WN) left and right, in 80 ℃ of lower extractings of high temperature more than at least 1 hour, and three solid phases and three liquid phase two parts of obtaining after three press filtrations; Wherein three solid phases partly are mainly coarse product of cellulose, and three liquid phase Main Ingredients and Appearances are hemicellulose and lignin degrading mixed liquor.
3, the liquid phase pressing filtering liquid (comprising secondary liquid phase and three liquid phases) of warm alkali oxidation extracting and the extracting of high temperature alkali in the merging, through NF membrane, that pressing filtering liquid is concentrated more than 5 times, until hemicellulose and lignin solid concentration reach more than 10%, recycle of alkali liquor is more than 80%; Adding final concentration in concentrate is alcohol more than 50%, filters or centrifugation after static 1~5 hour, is precipitated thing and supernatant; Sediment is the hemicellulose crude product;
4, the supernatant that obtains in step 3 is transferred to acid pH 3~4, filter or centrifugation after static 1~5 hour, precipitation is the lignin crude product.The lignin that separation obtains utilizes lignin can make degradable, reproducible polymer as dispersant, adsorbent/strippant, petroleum recovery auxiliary agent, asphalt emulsifier.
The preparation of cellulase and hemicellulase
The solid phase coarse product of cellulose that separation is obtained is soaked in 40 ℃ of warm water, adds appropriate hydrochloric acid, regulates the pH value near neutral.Get wherein a part for the preparation of cellulase and hemicellulase, another part is as the raw material of saccharification.The preparation of cellulase and hemicellulase takes the method for solid state fermentation koji to carry out, take Aspergillus glaucus as cellulase producing strain, with aspergillus niger as producing the hemicellulase bacterial strain, add the wheat bran of certain proportion (dry weight 5: 1) or soya-bean cake as the nutrition component in the solid phase coarse product of cellulose, and add a certain proportion of water (solid-to-liquid ratio is about 3: 1), inoculation cellulase producing strain or product hemicellulase bacterial strain, cultivating about 3 days under suitable condition, obtain solid-state cellulase or solid-state hemicellulase.
After utilizing separation, component is carried out saccharification of cellulose and fermentation wine-making essence
The solid-state coarse product of cellulose that separation obtains is mixed in the ratio of 5: 1 with solid-state cellulase, add appropriate water, making solid-to-liquid ratio is 1: 10, and more than 12 hours, the saccharified liquid of gained is concentrated into sugared concentration more than 15% through NF membrane at 50 ℃ of enzymolysis.Add appropriate soya-bean cake in saccharified liquid after concentrated as the nitrogen nutrition component, and add the inorganic salts component, comprise potassium, sodium, calcium, magnesium, sulphur; And regulate the pH value to neutral, the fermentation tank of packing into carries out sterilization treatment, access distillery yeast by 10% (v/v) inoculum concentration after cooling, after fermentation ends (more than 50h), first zymotic fluid is distilled the alcohol that obtains 95% left and right, and then obtaining absolute alcohol by the film isolation technics of dewatering, purposes acts as a fuel.
After utilizing separation, component prepares xylo-oligosaccharide
Be eluted to pH nearly neutral (pH=7 left and right) under double coarse product of cellulose normal temperature, remove residual alkali lye, collect the solid phase part, add the water of 5 times of bulking values, add zytase to carry out saccharification in the ratios of 5: 1 and decompose, constant temperature (60 ℃) water-bath 5~16 hours; The hemicellulose saccharified liquid mainly comprise wood sugar, xylo-oligosaccharide etc., enzymolysis liquid is imported bleacher, add the activated carbon decolorizing agent to decolour, then remove solid impurity by filtering (plate compression etc.); By the ion exchange resin desalination, the light yellow clear liquid of the indices of xylo-oligosaccharide to be reached (QB-T_2984-2008_ xylo-oligosaccharide) carries out film after projection ratio 〉=60% and concentrates with the saccharified liquid after decolorization filtering; Carry out spray drying after being concentrated into the saccharified liquid after decolouring and desalination more than 15% and make xylo-oligosaccharide powder XOS2-7 〉=70 (in butts), XOS2-5 〉=50% (in butt), or the xylo-oligosaccharide liquid XOS2-7 by NF membrane simmer down to high concentration 〉=70 (in butts), XOS2-5 〉=50% (in butt).
Embodiment 2
The fractionation method of the full component of a kind of forestry cellulose biomass that the present embodiment adopts comprises the steps:
1, the forestry cellulose biomass dry after crushed, first soaks then press filtration with clear water;
2, the KOH dipping by lye of the solid phase part after processing through 1 take concentration as 7%, solid-to-liquid ratio is 1: 10 (WN) left and right, adding concentration is 5% H
2O
2Oxidant first 60 ℃ of lower extractings of middle temperature 2~4 hours, obtains secondary liquid phase and secondary solid phase two parts after the secondary press filtration; The secondary solid phase partly continues to be soaked in 7% KOH alkali lye, and solid-to-liquid ratio is 1: 10 (WN) left and right, in 140 ℃ of lower extractings of high temperature more than at least 1 hour, and three solid phases and three liquid phase two parts of obtaining after three press filtrations; Wherein three solid phases partly are mainly coarse product of cellulose, and three liquid phase Main Ingredients and Appearances are hemicellulose and lignin degrading mixed liquor.
3, the liquid phase pressing filtering liquid (comprising secondary liquid phase and three liquid phases) of warm alkali oxidation extracting and the extracting of high temperature alkali in the merging, through NF membrane, that pressing filtering liquid is concentrated more than 5 times, until hemicellulose and lignin solid concentration reach more than 10%, recycle of alkali liquor is more than 80%; Adding final concentration in concentrate is alcohol more than 50%, filters or centrifugation after static 5 hours, is precipitated thing and supernatant; Sediment is the hemicellulose crude product;
4, the supernatant that obtains in step 3 is transferred to acid pH 3~4, filter or centrifugation after static 5 hours, precipitation is the lignin crude product.The lignin that separation obtains utilizes lignin can make degradable, reproducible polymer as dispersant, adsorbent/strippant, petroleum recovery auxiliary agent, asphalt emulsifier.
The preparation of cellulase and hemicellulase
The solid phase coarse product of cellulose that separation is obtained is soaked in 60 ℃ of warm water, adds appropriate sulfuric acid, regulates the pH value near neutral.Get wherein a part for the preparation of cellulase and hemicellulase, another part is as the raw material of saccharification.The preparation of cellulase and hemicellulase takes the method for solid state fermentation koji to carry out, take mould as cellulase producing strain, mould as producing the hemicellulase bacterial strain with wood, add the wheat bran of certain proportion (dry weight 51: 1) or soya-bean cake as the nutrition component in the solid phase coarse product of cellulose, and add a certain proportion of water (solid-to-liquid ratio is about 3: 1), inoculation cellulase producing strain or product hemicellulase bacterial strain, cultivating about 3 days under suitable condition, obtain solid-state cellulase or solid-state hemicellulase.
After utilizing separation, component is carried out saccharification of cellulose and fermentation wine-making essence
The solid-state coarse product of cellulose that separation obtains is mixed in the ratio of 1: 1 with solid-state cellulase, add appropriate water, making solid-to-liquid ratio is 1: 10, and more than 12 hours, the saccharified liquid of gained is concentrated into sugared concentration more than 15% through NF membrane at 50 ℃ of enzymolysis.Add appropriate soya-bean cake in saccharified liquid after concentrated as the nitrogen nutrition component, and add the inorganic salts component, comprise potassium, sodium, calcium, magnesium; And regulate the pH value to neutral, the fermentation tank of packing into carries out sterilization treatment, access distillery yeast by 10% (v/v) inoculum concentration after cooling, after fermentation ends (more than 50h), first zymotic fluid is distilled the alcohol that obtains 95% left and right, and then obtaining absolute alcohol by the film isolation technics of dewatering, purposes acts as a fuel.
After utilizing separation, component prepares xylo-oligosaccharide
Be eluted to pH nearly neutral (pH=7 left and right) under double coarse product of cellulose normal temperature, remove residual alkali lye, collect the solid phase part, add the water of 5~10 times of bulking values, add zytase to carry out saccharification in the ratio of 1: 1 and decompose, constant temperature (60 ℃) water-bath 5~16 hours; The hemicellulose saccharified liquid mainly comprise wood sugar, xylo-oligosaccharide etc., enzymolysis liquid is imported bleacher, add the activated carbon decolorizing agent to decolour, then remove solid impurity by filtering (plate compression etc.); By the ion exchange resin desalination, the light yellow clear liquid of the indices of xylo-oligosaccharide to be reached (QB-T-2984-2008_ xylo-oligosaccharide) carries out film after projection ratio 〉=60% and concentrates with the saccharified liquid after decolorization filtering; Carry out spray drying after being concentrated into the saccharified liquid after decolouring and desalination more than 15% and make xylo-oligosaccharide powder XOS2-7 〉=70 (in butts), XOS2-5 〉=50% (in butt), or the xylo-oligosaccharide liquid XOS2-7 by NF membrane simmer down to high concentration 〉=70 (in butts), XOS2-5 〉=50% (in butt).
Embodiment 3
The fractionation method of the full component of a kind of forestry cellulose biomass that the present embodiment adopts comprises the steps:
1, the forestry cellulose biomass dry after crushed, first soaks then press filtration with clear water;
2, the Na of the solid phase part after processing through 1 take concentration as 4%
2CO
3Dipping by lye, solid-to-liquid ratio are 1: 10 (W/V) left and right, and adding concentration is 4% KMnO
4Oxidant first 50 ℃ of lower extractings of middle temperature 3 hours, obtains secondary liquid phase and secondary solid phase two parts after the secondary press filtration; It is 4% Na that the secondary solid phase partly continues to be soaked in concentration
2CO
3In, solid-to-liquid ratio is 1: 10 (WN) left and right, in 100 ℃ of lower extractings of high temperature more than at least 1 hour, and three solid phases and three liquid phase two parts of obtaining after three press filtrations; Wherein three solid phases partly are mainly coarse product of cellulose, and three liquid phase Main Ingredients and Appearances are hemicellulose and lignin degrading mixed liquor.
3, the liquid phase pressing filtering liquid (comprising secondary liquid phase and three liquid phases) of warm alkali oxidation extracting and the extracting of high temperature alkali in the merging, through NF membrane, that pressing filtering liquid is concentrated more than 5 times, until hemicellulose and lignin solid concentration reach more than 10%, recycle of alkali liquor is more than 80%; Adding final concentration in concentrate is alcohol more than 50%, filters or centrifugation after static 3 hours, is precipitated thing and supernatant; Sediment is the hemicellulose crude product;
4, the supernatant that obtains in step 3 is transferred to acid pH 3~4, filter or centrifugation after static 3 hours, precipitation is the lignin crude product.The lignin that separation obtains utilizes lignin can make degradable, reproducible polymer as dispersant, adsorbent/strippant, petroleum recovery auxiliary agent, asphalt emulsifier.
The preparation of cellulase and hemicellulase
The solid phase coarse product of cellulose that separation is obtained is soaked in 50 ℃ of warm water, adds appropriate hydrochloric acid, regulates the pH value near neutral.Get wherein a part for the preparation of cellulase and hemicellulase, another part is as the raw material of saccharification.The preparation of cellulase and hemicellulase takes the method for solid state fermentation koji to carry out, with mould as cellulase producing strain, with aspergillus niger as producing the hemicellulase bacterial strain, add the wheat bran of certain proportion (dry weight 3: 1) or soya-bean cake as the nutrition component in the solid phase coarse product of cellulose, and add a certain proportion of water (solid-to-liquid ratio is about 3: 1), inoculation cellulase producing strain or product hemicellulase bacterial strain, cultivating about 3 days under suitable condition, obtain solid-state cellulase or solid-state hemicellulase.
After utilizing separation, component is carried out saccharification of cellulose and fermentation wine-making essence
The solid-state coarse product of cellulose that separation obtains is mixed in the ratio of 3: 1 with solid-state cellulase, add appropriate water, making solid-to-liquid ratio is 1: 10, and more than 12 hours, the saccharified liquid of gained is concentrated into sugared concentration more than 15% through NF membrane at 50 ℃ of enzymolysis.Add appropriate soya-bean cake in saccharified liquid after concentrated as the nitrogen nutrition component, and add the inorganic salts component, comprise potassium, sodium, calcium, magnesium; And regulate the pH value to neutral, the fermentation tank of packing into carries out sterilization treatment, access distillery yeast by 10% (v/v) inoculum concentration after cooling, after fermentation ends (more than 50h), first zymotic fluid is distilled the alcohol that obtains 95% left and right, and then obtaining absolute alcohol by the film isolation technics of dewatering, purposes acts as a fuel.
After utilizing separation, component prepares xylo-oligosaccharide
Be eluted to pH nearly neutral (pH=7 left and right) under double coarse product of cellulose normal temperature, remove residual alkali lye, collect the solid phase part, add the water of 5~10 times of bulking values, add zytase to carry out saccharification in the ratios of 3: 1 and decompose, constant temperature (60 ℃) water-bath 5~16 hours; The hemicellulose saccharified liquid mainly comprise wood sugar, xylo-oligosaccharide etc., enzymolysis liquid is imported bleacher, add the activated carbon decolorizing agent to decolour, then remove solid impurity by filtering (plate compression etc.); By the ion exchange resin desalination, the light yellow clear liquid of the indices of xylo-oligosaccharide to be reached (QB-T_2984-2008_ xylo-oligosaccharide) carries out film after projection ratio 〉=60% and concentrates with the saccharified liquid after decolorization filtering; Carry out spray drying after being concentrated into the saccharified liquid after decolouring and desalination more than 15% and make xylo-oligosaccharide powder XOS2-7 〉=70 (in butts), XOS2-5 〉=50% (in butt), or the xylo-oligosaccharide liquid XOS2-7 by NF membrane simmer down to high concentration 〉=70 (in butts), XOS2-5 〉=50% (in butt).
Each embodiment of the present invention has started brand-new cellulose biomass and utilized theory: full component separating technology and full constituent utilize technique; Invent brand-new isolation technics, on the pretreated basis with alkaline process, by adding oxidant and assistant, by increasing the high temperature extraction step, promoted being separated from each other of cellulose biomass component; Secondly using membrane separating technology is realized reclaiming to alkali, realizes concentrated to hemicellulose and lignin extraction component; To have invented solid-state fermentation technology to prepare special cellulase again, utilizing cellulase to carry out saccharification to the cellulose component decomposes, the saccharified liquid product alcohol that ferments after film is concentrated into sugared concentration more than 15%, zymotic fluid dewaters through distillation and film, and product is absolute alcohol; Invented solid-state fermentation technology and prepared special hemicellulase, utilized hemicellulase to carry out saccharification to xylan, saccharified liquid separates and concentrated, desalination, decolouring and spray drying through film, obtains the xylo-oligosaccharide product.