CN102261007A - A method for fractional separation of full components of agricultural and forestry cellulose biomass and preparation of fuel alcohol and xylooligosaccharides by using the separated components - Google Patents
A method for fractional separation of full components of agricultural and forestry cellulose biomass and preparation of fuel alcohol and xylooligosaccharides by using the separated components Download PDFInfo
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Abstract
本发明公开了一种农林纤维素生物质全组份的分级分离包括如下步骤a)农林纤维素生物质的干物质的粉碎、浸泡和压滤；b)压滤后的固相部分用碱液浸泡，加氧化剂，抽提，固相为纤维素粗品；c)经纳滤膜将压滤液浓缩，在浓缩液中加入终浓度为50％以上的酒精，静止后过滤或离心分离，得到沉淀物和上清液；沉淀物就为半纤维素粗品；d)将步骤c)中得到的上清液调至酸性，过滤分离，沉淀则为木质素粗品，及其利用分离后组份制备燃料酒精和低聚木糖。本发明做到资源利用的最大化；可以减少我国对进口石油的依赖，减少对环境的污染；还可推动建立新能源工业产业和生物化工产业，改变我国经济增长的方式，实现社会和经济的可持续发展。
The present invention discloses a method for graded separation of all components of agricultural and forestry cellulose biomass, including the following steps: a) crushing, soaking and filter pressing of dry matter of agricultural and forestry cellulose biomass; b) soaking the solid phase after filter pressing with alkali solution, adding oxidant, extracting, and the solid phase is crude cellulose; c) concentrating the filter press liquid through a nanofiltration membrane, adding alcohol with a final concentration of more than 50% to the concentrated liquid, filtering or centrifuging after standing, and obtaining a precipitate and a supernatant; the precipitate is a crude hemicellulose; d) adjusting the supernatant obtained in step c) to acidity, filtering and separating, and the precipitate is a crude lignin product, and using the separated components to prepare fuel alcohol and oligoxylose. The present invention maximizes resource utilization; can reduce my country's dependence on imported oil and reduce pollution to the environment; can also promote the establishment of new energy industry and biochemical industry, change the way of my country's economic growth, and achieve sustainable social and economic development.
Description
Technical field
The present invention relates to the fractionation method of the full component of a kind of agricultural cellulose biomass and utilize separation back component to prepare fuel alcohol and xylo-oligosaccharide.
Background technology
Natural wooden fiber's element is a renewable resource the abundantest on the earth, and cellulose biomass mainly comprises cellulose, hemicellulose and lignin, and the three closely combines by a certain percentage.Cellulose is to pass through 3-1 by many glucose molecules, the high glycan of the straight chain that the 4-glycosidic bond is formed by connecting, and the degree of polymerization can descend after preliminary treatment, obtains hexoses such as glucose after the complete hydrolysis, produces fuel alcohol through fermentation by saccharomyces cerevisiae again; Hemicellulose is the general name that has the polysaccharide of side chain, and its construction unit comprises pentose base, hexose-based, saccharic acid base and own phthalidyl, and wherein pentose is mainly the wooden pool and arabinose; Lignin is to be only second to the abundantest cellulosic organic high molecular compound in the plant kingdom, with the complex nonlinear, that random fashion connects to form, is difficult to the macromolecule amorphous substance of hydrolysis by phenylpropyl alcohol alkane unit under the effect of acid.
At present utilization to the cellulose component is mainly emphasized in the utilization of cellulose biomass, and it is relative with the utilization of lignin component less to hemicellulose, and do not utilize the biorefinery technology that the full component of cellulose biomass is carried out classification and separate, do not realize the recycling of the full component of living beings and the maximization of benefit.Produce in the alcohol process utilizing cellulose biomass, normal chemical method and the biological method of adopting degraded to cellulose biomass, its product comprises multiple mixed sugar such as glucose, wood sugar, utilize the mixed sugar product alcohol that ferments again, because the product that obtains is single, its added value is not high, and economic benefit is lower, lacks the market competitiveness; Produce in the xylo-oligosaccharide process utilizing cellulose biomass, usually adopt the extracting of one-step method alkali, directly in extract, add the acid neutralization then, add the alcohol precipitation hemicellulose, the defective of this method be that the recovery rate of hemicellulose is lower, the alkali consumption is big or middle and the time acid big, the hemicellulose precipitation of consumption the time alcohol consumption big, owing to adopt traditional technology, separating effect is relatively poor, energy consumption is big, cost is higher in follow-up technical process.
Summary of the invention
In order to address the above problem, to have the object of the present invention is to provide the fractionation method of the full component of a kind of agricultural cellulose biomass and utilized separation back component to prepare fuel alcohol and xylo-oligosaccharide.The present invention relates to the agricultural cellulose biomass is converted into bio-fuel and wood sugars bio-based chemicals such as fuel alcohol by the biorefinery technology.Biological alcohol is a kind of water white transparency, volatile, easy firing, nonconducting liquid, can add to according to a certain percentage in the 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 common chemical product, 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 of 4 glycosidic bond be combined intos, it can optionally promote the proliferation activity of intestinal bifidobacteria, is important nutrient and healthcare products.The present invention adopts the agricultural 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 the dependence of China, reduce pollution environment to Imported oil; Also can promote to set up new forms of energy industrial sector and biochemical industry 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 agricultural cellulose biomass comprises the steps:
A) pulverizing, immersion and the press filtration of the fresh material of agricultural cellulose biomass or dry (purchasing) in Zhangzhou sugar Refinery of Fujian Prov.;
B) solid phase after the press filtration is partly used dipping by lye, adds oxidant, and extracting under middle temperature earlier 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 the alkali lye, extracting at high temperature, 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; In middle temperature alkali treatment process, add oxidant, can quicken the decomposition of lignin, the physical arrangement of lignocellulose is dissociated, help the hemicellulose component and the lignin component enters aqueous slkali, for the separation fully of three components in the 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) pressing filtering liquid is concentrated, the adding final concentration is the alcohol more than 50% in concentrate, filter or centrifugation static back, obtains sediment and supernatant; Sediment is the hemicellulose crude product just;
D) supernatant that obtains in the step c) is transferred to acidity, filter or centrifugation static back, and precipitation then 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.
To adopt temperature be extracting 2～4 hours under 40～60 ℃ of conditions for warm extracting in described; It is extracting more than at least 1 hour under 100～160 ℃ of conditions that temperature is adopted in described high temperature extracting.
Pressing filtering liquid is concentrated into more than 5 times in the described step c), reaches more than 10% up to hemicellulose and lignin solid concentration, and alkali lye reclaims more than 80%; And be 1～5 hour the quiescent time in step c) and the step d); In the step d) adjustment of acidity to pH be 3～4.
The coarse product of cellulose that described separation obtains is used to prepare cellulase or hemicellulase on the one hand, utilizes cellulase that coarse product of cellulose is degraded to glucose on the other hand, produces alcohol behind culture propagation; Separate the hemicellulose crude product obtain and utilize hemicellulase that it is degraded to wood sugar and xylo-oligosaccharide chemicals, through separating the raw material of back of purifying as food additives or production xylitol; The lignin that separation obtains utilizes lignin can make degradable, reproducible polymer as dispersant, adsorbent/strippant, petroleum recovery auxiliary agent, asphalt emulsifier.
A kind of utilization separates the back component and prepares fuel alcohol, and the coarse product of cellulose that described separation obtains is used to prepare cellulase or hemicellulase on the one hand, utilizes cellulase that coarse product of cellulose is degraded to glucose on the other hand, produces alcohol behind 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 the cellulase-producing bacterial strain respectively or produce the hemicellulase bacterial strain, solid state fermentation is cultivated results cellulase or hemicellulase after 3 days.
Described cellulase-producing bacterial 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 and by 5: 1-1: 1 mixed, add an amount of water, making solid-to-liquid ratio is 1: 10, the saccharification liquid after 50 ℃ of enzymolysis obtained cellulase hydrolysis more than 12 hours, and the saccharification liquid behind the cellulase hydrolysis is concentrated into sugared concentration more than 15% through NF membrane; Saccharification liquid after concentrating is directly used in fermentation and produces alcohol.
A kind of utilization separates the back component and prepares xylo-oligosaccharide: hemicellulose crude product that described separation obtains and hemicellulase are by 5: 1-1: after 1 the 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 and decolour, then by solids removed by filtration impurity; Saccharification liquid behind the decolorization filtering by the ion exchange resin desalination, is carried out film then 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 saccharification liquid after decolouring and the 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 the conversion, three kinds of components in the cellulose biomass is carried out classification separation purification obtain cellulose, hemicellulose, lignin component; Fully use each component then, produce bio-fuel and bio-based chemicals: at first from cellulose biomass, separate obtaining cellulose, utilize cellulase that cellulose degradation is glucose, behind culture propagation, produce alcohol; Utilize hemicellulase that xylan degrading is chemicals such as wood sugar and xylo-oligosaccharide, through the raw material of back of separate purifying as food additives or production 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 the elder generation, and back 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 the employing-middle temperature can improve the efficiency of utilization of technical process.Modern membrane separation technique is applied to technical process such as alkali lye reclaims, saccharification liquid component separates, saccharification liquid concentrates, dehydration of alcohol, can reduce the energy consumption and the cost of production process significantly.
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 living beings Industrial economic benefit, 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 significantly reduce pollution to environment, increase substantially production efficiency.And increase substantially the economic benefit of whole industry chain, improve more than 10 times, provide a feasible way for scale development utilizes cellulose biomass than the economic benefit of independent production of cellulose alcohol.
Description of drawings
Fig. 1 is a process route chart of the present invention.
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 agricultural cellulose biomass that present embodiment adopted comprises the steps:
1, the fresh material of agricultural cellulose biomass or dry soak press filtration then earlier after crushed with clear water;
2, will be 1% NaOH dipping by lye with concentration through 1 post-treatment solid phase part, solid-to-liquid ratio be about 1: 10 (WN), adds concentration and be 5% O
3Oxidant earlier 60 ℃ of following 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% the NaOH alkali lye, and solid-to-liquid ratio is about 1: 10 (WN), in 80 ℃ of following 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 concentrates pressing filtering liquid more than 5 times through NF membrane, reaches more than 10% up to hemicellulose and lignin solid concentration, and alkali lye reclaims more than 80%; The adding final concentration is the alcohol more than 50% in concentrate, filters or centrifugation after static 1～5 hour, obtains sediment and supernatant; Sediment is the hemicellulose crude product;
4, the supernatant that obtains in the step 3 is transferred to acid pH 3～4, filter or centrifugation after static 1～5 hour, precipitation then 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 an amount of hydrochloric acid, regulates the pH value near neutral.Get wherein that a part is used to prepare 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 the Aspergillus glaucus is the cellulase-producing bacterial strain, with aspergillus niger as producing the hemicellulase bacterial strain, in the solid phase coarse product of cellulose, add the wheat bran of certain proportion (dry weight 5: 1) or soya-bean cake as the nutrition component, and add a certain proportion of water (solid-to-liquid ratio is about 3: 1), inoculation cellulase-producing bacterial strain or product hemicellulase bacterial strain, under suitable condition, cultivated about 3 days, obtain solid-state cellulase or solid-state hemicellulase.
Utilize separation back component to carry out saccharification of cellulose and fermentation preparing alcohol
Solid-state coarse product of cellulose that separation is obtained and solid-state cellulase add an amount of water by 5: 1 mixed, and making solid-to-liquid ratio is 1: 10, and more than 12 hours, the saccharification liquid of gained is concentrated into sugared concentration more than 15% through NF membrane at 50 ℃ of enzymolysis.Add an amount of soya-bean cake in the saccharification liquid after concentrating 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, distillery yeast is inserted by 10% (v/v) inoculum concentration in the cooling back, after the fermentation ends (more than the 50h), earlier zymotic fluid is distilled the alcohol that obtains about 95%, and then obtaining absolute alcohol by film dehydration isolation technics, purposes acts as a fuel.
Utilize separation back component to prepare xylo-oligosaccharide
Be eluted to pH nearly neutral (about pH=7) under the 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 zytases in 5: 1 ratios and carry out saccharification and decompose, constant temperature (60 ℃) water-bath 5～16 hours; Hemicellulose saccharification liquid mainly comprise wood sugar, xylo-oligosaccharide etc., enzymolysis liquid is imported bleacher, add the activated carbon decolorizing agent and decolour, remove solid impurity by filtration (plate compression etc.) then; Saccharification liquid behind the decolorization filtering by the ion exchange resin desalination, is waited to reach the light yellow clear liquid of every index (QB-T_2984-2008_ xylo-oligosaccharide) of xylo-oligosaccharide, carry out film behind the projection ratio 〉=60% and concentrate; Carry out spray drying after being concentrated into the saccharification liquid after decolouring and the desalination more than 15% and make xylo-oligosaccharide powder XOS2-7 〉=70 (in butts), XOS2-5 〉=50% (in butt), or xylo-oligosaccharide liquid XOS2-7 〉=70 (in the butts) by NF membrane simmer down to high concentration, XOS2-5 〉=50% (in butt).
Embodiment 2
The fractionation method of the full component of a kind of agricultural cellulose biomass that present embodiment adopted comprises the steps:
1, agricultural cellulose biomass dry soaks press filtration then earlier after crushed with clear water;
2, will be 7% KOH dipping by lye with concentration through 1 post-treatment solid phase part, solid-to-liquid ratio be about 1: 10 (WN), adds concentration and be 5% H
2O
2Oxidant earlier 60 ℃ of following 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% the KOH alkali lye, and solid-to-liquid ratio is about 1: 10 (WN), in 140 ℃ of following 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 concentrates pressing filtering liquid more than 5 times through NF membrane, reaches more than 10% up to hemicellulose and lignin solid concentration, and alkali lye reclaims more than 80%; The adding final concentration is the alcohol more than 50% in concentrate, filters or centrifugation after static 5 hours, obtains sediment and supernatant; Sediment is the hemicellulose crude product;
4, the supernatant that obtains in the step 3 is transferred to acid pH 3～4, filter or centrifugation after static 5 hours, precipitation then 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 an amount of sulfuric acid, regulates the pH value near neutral.Get wherein that a part is used to prepare 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 the mould is the cellulase-producing bacterial strain, mould with wood as producing the hemicellulase bacterial strain, in the solid phase coarse product of cellulose, add the wheat bran of certain proportion (dry weight 51: 1) or soya-bean cake as the nutrition component, and add a certain proportion of water (solid-to-liquid ratio is about 3: 1), inoculation cellulase-producing bacterial strain or product hemicellulase bacterial strain, under suitable condition, cultivated about 3 days, obtain solid-state cellulase or solid-state hemicellulase.
Utilize separation back component to carry out saccharification of cellulose and fermentation preparing alcohol
Solid-state coarse product of cellulose that separation is obtained and solid-state cellulase add an amount of water by 1: 1 mixed, and making solid-to-liquid ratio is 1: 10, and more than 12 hours, the saccharification liquid of gained is concentrated into sugared concentration more than 15% through NF membrane at 50 ℃ of enzymolysis.Add an amount of soya-bean cake in the saccharification liquid after concentrating 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, distillery yeast is inserted by 10% (v/v) inoculum concentration in the cooling back, after the fermentation ends (more than the 50h), earlier zymotic fluid is distilled the alcohol that obtains about 95%, and then obtaining absolute alcohol by film dehydration isolation technics, purposes acts as a fuel.
Utilize separation back component to prepare xylo-oligosaccharide
Be eluted to pH nearly neutral (about pH=7) under the 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 in 1: 1 ratio and carry out saccharification and decompose, constant temperature (60 ℃) water-bath 5～16 hours; Hemicellulose saccharification liquid mainly comprise wood sugar, xylo-oligosaccharide etc., enzymolysis liquid is imported bleacher, add the activated carbon decolorizing agent and decolour, remove solid impurity by filtration (plate compression etc.) then; Saccharification liquid behind the decolorization filtering by the ion exchange resin desalination, is waited to reach the light yellow clear liquid of every index (QB-T-2984-2008_ xylo-oligosaccharide) of xylo-oligosaccharide, carry out film behind the projection ratio 〉=60% and concentrate; Carry out spray drying after being concentrated into the saccharification liquid after decolouring and the desalination more than 15% and make xylo-oligosaccharide powder XOS2-7 〉=70 (in butts), XOS2-5 〉=50% (in butt), or xylo-oligosaccharide liquid XOS2-7 〉=70 (in the butts) by NF membrane simmer down to high concentration, XOS2-5 〉=50% (in butt).
Embodiment 3
The fractionation method of the full component of a kind of agricultural cellulose biomass that present embodiment adopted comprises the steps:
1, agricultural cellulose biomass dry soaks press filtration then earlier after crushed with clear water;
2, will with concentration be 4% Na through 1 post-treatment solid phase part
2CO
3Dipping by lye, solid-to-liquid ratio are about 1: 10 (W/V), and adding concentration is 4% KMnO
4Oxidant earlier 50 ℃ of following 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 about 1: 10 (WN), in 100 ℃ of following 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 concentrates pressing filtering liquid more than 5 times through NF membrane, reaches more than 10% up to hemicellulose and lignin solid concentration, and alkali lye reclaims more than 80%; The adding final concentration is the alcohol more than 50% in concentrate, filters or centrifugation after static 3 hours, obtains sediment and supernatant; Sediment is the hemicellulose crude product;
4, the supernatant that obtains in the step 3 is transferred to acid pH 3～4, filter or centrifugation after static 3 hours, precipitation then 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 an amount of hydrochloric acid, regulates the pH value near neutral.Get wherein that a part is used to prepare 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 the cellulase-producing bacterial strain, with aspergillus niger as producing the hemicellulase bacterial strain, in the solid phase coarse product of cellulose, add the wheat bran of certain proportion (dry weight 3: 1) or soya-bean cake as the nutrition component, and add a certain proportion of water (solid-to-liquid ratio is about 3: 1), inoculation cellulase-producing bacterial strain or product hemicellulase bacterial strain, under suitable condition, cultivated about 3 days, obtain solid-state cellulase or solid-state hemicellulase.
Utilize separation back component to carry out saccharification of cellulose and fermentation preparing alcohol
Solid-state coarse product of cellulose that separation is obtained and solid-state cellulase add an amount of water by 3: 1 mixed, and making solid-to-liquid ratio is 1: 10, and more than 12 hours, the saccharification liquid of gained is concentrated into sugared concentration more than 15% through NF membrane at 50 ℃ of enzymolysis.Add an amount of soya-bean cake in the saccharification liquid after concentrating 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, distillery yeast is inserted by 10% (v/v) inoculum concentration in the cooling back, after the fermentation ends (more than the 50h), earlier zymotic fluid is distilled the alcohol that obtains about 95%, and then obtaining absolute alcohol by film dehydration isolation technics, purposes acts as a fuel.
Utilize separation back component to prepare xylo-oligosaccharide
Be eluted to pH nearly neutral (about pH=7) under the 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 zytases in 3: 1 ratios and carry out saccharification and decompose, constant temperature (60 ℃) water-bath 5～16 hours; Hemicellulose saccharification liquid mainly comprise wood sugar, xylo-oligosaccharide etc., enzymolysis liquid is imported bleacher, add the activated carbon decolorizing agent and decolour, remove solid impurity by filtration (plate compression etc.) then; Saccharification liquid behind the decolorization filtering by the ion exchange resin desalination, is waited to reach the light yellow clear liquid of every index (QB-T_2984-2008_ xylo-oligosaccharide) of xylo-oligosaccharide, carry out film behind the projection ratio 〉=60% and concentrate; Carry out spray drying after being concentrated into the saccharification liquid after decolouring and the desalination more than 15% and make xylo-oligosaccharide powder XOS2-7 〉=70 (in butts), XOS2-5 〉=50% (in butt), or xylo-oligosaccharide liquid XOS2-7 〉=70 (in the butts) by NF membrane simmer down to high concentration, 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 technology; Invented brand-new isolation technics, on pretreated basis,,, promoted being separated from each other of cellulose biomass component by increasing the high temperature extraction step by adding oxidant and assistant with alkaline process; Secondly using membrane separating technology is realized reclaiming to alkali, and hemicellulose and lignin extraction component are realized concentrating; Be to have invented solid-state fermentation technology to prepare special cellulase again, utilizing cellulase that the cellulose component is carried out saccharification decomposes, the saccharification liquid product alcohol that after film is concentrated into sugared concentration more than 15%, ferments, zymotic fluid dewaters through distillation and film, and product is an absolute alcohol; Invented solid-state fermentation technology and prepared special hemicellulase, utilized hemicellulase that xylan is carried out saccharification, saccharification liquid separates and concentrated, desalination, decolouring and spray drying through film, obtains the xylo-oligosaccharide product.
Claims (9)
1. the fractionation method of the full component of agricultural cellulose biomass is characterized in that comprising the steps:
A) elder generation of the dry of agricultural cellulose biomass soaks and press filtration through pulverizing, clear water;
B) solid phase after the press filtration is partly used dipping by lye, adds oxidant, and extracting under middle temperature earlier 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 the alkali lye, extracting at high temperature, 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;
C) the liquid phase pressing filtering liquid of warm alkali oxidation extracting and the extracting of high temperature alkali in the merging concentrates pressing filtering liquid through NF membrane, and the adding final concentration is the alcohol more than 50% in concentrate, and filter or centrifugation static back, obtains sediment and supernatant; Sediment is the hemicellulose crude product just;
D) supernatant that obtains in the step c) is transferred to acidity, filter or centrifugation static back, and precipitation then is the lignin crude product.
2. the separation method of the full component of a kind of agricultural cellulose biomass as claimed in claim 1 is characterized in that: described agricultural cellulose biomass adopts stalk, bagasse, Chinese silvergrass, forestry processing waste.
3. the separation method of the full component of a kind of agricultural cellulose biomass as claimed in claim 1 is characterized in that: described alkali lye employing concentration is 1%～7% NaOH, KOH, Na
2CO
3In a kind of; Described oxidant employing concentration is 1%～5% H
2O
2, O
3, KMnO
4In a kind of.
4. the separation method of the full component of a kind of agricultural cellulose biomass as claimed in claim 1 is characterized in that: to adopt temperature be extracting 2～4 hours under 40～60 ℃ of conditions for warm extracting in described; It is extracting more than at least 1 hour under 100～160 ℃ of conditions that temperature is adopted in described high temperature extracting.
5. the separation method of the full component of a kind of agricultural cellulose biomass as claimed in claim 1, it is characterized in that: pressing filtering liquid is concentrated into more than 5 times in the described step c), reach more than 10% up to hemicellulose and lignin solid concentration, alkali lye reclaims more than 80%; And be 1～5 hour the quiescent time in step c) and the step d); In the step d) adjustment of acidity to pH be 3～4.
6. one kind is utilized claim 1 separation back component to prepare fuel alcohol, it is characterized in that: the coarse product of cellulose that described separation obtains is used to prepare cellulase or hemicellulase on the one hand, utilize cellulase that coarse product of cellulose is degraded to glucose on the other hand, behind culture propagation, produce alcohol; The preparation method of described cellulase or hemicellulase is: with described coarse product of cellulose, adopt the method for solid state fermentation koji, inoculate the cellulase-producing bacterial strain respectively or produce the hemicellulase bacterial strain, solid state fermentation is cultivated results cellulase or hemicellulase after 3 days.
7. utilization as claimed in claim 6 separates the back component and prepares fuel alcohol, it is characterized in that: described cellulase-producing bacterial 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.
8. prepare fuel alcohol as claim 6 or 7 described utilizations separation back components, it is characterized in that: described coarse product of cellulose and cellulase and by 5: 1-1: 1 mixed, add an amount of water, making solid-to-liquid ratio is 1: 10, saccharification liquid after 50 ℃ of enzymolysis obtained cellulase hydrolysis more than 12 hours, the saccharification liquid behind the cellulase hydrolysis is concentrated into sugared concentration more than 15% through NF membrane; Saccharification liquid after concentrating is directly used in fermentation and produces alcohol.
9. one kind is utilized claim 1 separation back component to prepare xylo-oligosaccharide, it is characterized in that: hemicellulose crude product that described separation obtains and hemicellulase are by 5: 1-1: after 1 the 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 and decolour, then by solids removed by filtration impurity; Saccharification liquid behind the decolorization filtering by the ion exchange resin desalination, is carried out film then 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 saccharification liquid after decolouring and the desalination more than 15%.
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