CN103790056A - Method for pretreating cellulosic biomass - Google Patents
Method for pretreating cellulosic biomass Download PDFInfo
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Abstract
The invention relates to relates to a method for pretreating cellulosic biomass, which comprises the following steps: before or after the cellulosic biomass is mechanically crushed, or when the cellulosic biomass is mechanically crushed, the cellulosic biomass is contacted with a chemical drug capable of degrading the cellulosic biomass, and the heat generated due to mechanical crushing is used for increasing the temperature of a mixture of the cellulosic biomass and the chemical drug.
Description
Technical field
The present invention relates to chemical field and bioenergy field.Particularly, the present invention relates to the method for a kind of pretreatment of fiber element biolobic material (cellulosic biomass), before it is included in Mechanical Crushing cellulose series biomass, simultaneously or afterwards, described cellulose series biomass is contacted with chemicals that can degraded cellulose biolobic material, and the heat that utilizes described Mechanical Crushing to produce improves the temperature of the mixture of described cellulose series biomass and described chemicals.
Background technology
Along with the day of petrochemical industry resource is becoming tight, by living resources, the exploitation that particularly the wood fiber biomass feedstock conversion such as agriculture and forestry organic waste material (such as maize straw, straw, wheat straw, bagasse, timber) is liquid fuel more and more become the focus of research.Be the reproducible liquid fuels such as ethanol, butanols, biodiesel by these discarded object biomass conversions; not only can solve problem of environmental pollution; and can also alleviate the energy crisis of growing tension; and reducing the discharge of greenhouse gases, this is significant for the Mode of Circular that creates sustainable development.
Cellulose series biomass is converted into committed step of liquid fuel is, by physics or chemical action pretreatment of fiber element biolobic material, is easy to substrate degraded by enzymes (for example, glucan, xylan etc.) to be translated into.Owing to lacking economically viable method and apparatus, the cost of preliminary treatment saccharifying is always high, has seriously hindered the utilization of cellulose series biomass to commercialized development.
Conventional method for pretreatment of fiber element biolobic material mainly comprises, uses the mechanical treatment process of pulverizer or vibratory milling, uses the method for chemical treatment of reactor or digester etc.These methods are in the time of pretreatment of fiber element biolobic material, and energy consumption is high, chemical cost amount is large, causes the high cost of preliminary treatment saccharifying.
Researchers have carried out a large amount of research work and have come development of new, effective lignocellulose pretreatment method.But current developed method mostly relates under high temperature, high pressure and/or high liquid-solid ratio condition and uses chemicals, processes cellulose series biomass by chemical action.
For example, Jilin light industry designing institute has developed a kind of preprocess method (Chinese patent application CN101134970), it is by spray sodium carbonate alkaline solution, then pass into oxygen and steam, and to keep temperature be 100-165 ℃, pressure is 1.6-2.5MPa, carrys out pretreatment of fiber element biolobic material.
Sinopec Group and Nanjing University of Technology's joint development a kind of combined pretreatment method of lignocellulose (Chinese patent application CN101230546), it comprises, at 50-200 ℃, carry out sour circular treatment, then under alkaline solution exists, in ball mill, carry out ball milling.
The preprocess method (Chinese patent application CN101056720) of Iogen Energy Corp. of Canada exploitation comprises, use roll squeezer extruding to remove a part of water and the solable matter in cellulose series biomass, the diluted acid that is then 8-20% by concentration at the temperature of 160-280 ℃ carries out preliminary treatment.
Engineering college of Southern Yangtze University has developed the method (Chinese patent application CN1327972) that uses concentrated acid pretreatment of fiber element biolobic material under normal pressure, but the liquid-solid ratio that the method is used is 10: 1～20: 1, infiltrating time was up to 10～18 hours, and chemical consumption is large and consuming time.
Above-mentioned preprocess method is all mainly processed living beings by chemical method, and its severe reaction conditions and water consumption are large, and cost is high and be unfavorable for environmental protection.
Sky, Henan hat (Chinese patent application CN101200734) and process engineering research institute of the Chinese Academy of Sciences (Chinese patent application CN1806945) have developed the method for carrying out pretreatment of fiber element biolobic material by steam blasting separately.Steam explosion is relatively more conventional at present a kind of biomass pretreatment method, and it comprises, raw material is joined in the reaction vessel that is called as steam reaction chamber, passes into steam until reach the temperature or the pressure that need, keeps a period of time, then accident explosion decompression.Although this method can be hydrolyzed into monose by most of half fiber, the removal efficiency of lignin is not high.In addition, although this method is not used chemicals, steam consumption is large, and equipment requirement is high, is difficult to large-scale industrialization.
US4461648 (Foody) has described a kind of preprocess method that sulfuric acid preimpregnation and steam blasting are combined.The method can reduce temperature and the Reaction time shorten of steam blasting, but, sour corrosion under hot conditions has increased the cost of equipment, and intermittent operation and higher steam consumption quantity (not recyclable) all cause expense too high, is difficult to realize industrialization.
US4237226 (Grethlein etc.) has described a kind of continuous preprocess method, it comprises, cellulose series biomass is made to the solid suspension of about 5-10% in water, this suspension is heated to reaction temperature and injects the concentrated sulfuric acid, then by injecting live steam, the suspension through acidifying is further heated.The liquid-solid ratio of this preprocess method is high, and need to consume a large amount of steam.
Chinese patent application CN101182551A (Zhang Xiaoyang) discloses a kind of alkali preprocessing plant fibre of using to produce the method for fuel alcohol.In the method, the concentration of the NaOH using is 0.5%-5%, and reaction temperature is below 100 ℃, but the liquid-solid ratio of the method high (8-12:1), and the time consuming is also longer.
Chinese patent application CN101121175A (Han Nong) discloses a kind of preprocess method that uses alkali and ozone.In the method, the dry of stalk accounts for the 3%-15% of feed liquid total amount, and lime accounts for the 0.3%-1% of feed liquid total amount, and mixed feed liquid is processed with ozone.The method has improved lignin and the cellulosic degradation rate of stalk in subsequent processing steps, but the high cost of ozone, is not suitable for suitability for industrialized production.
Chinese patent application CN102010882A (Bao Jie) discloses a kind of method of at high temperature using dilute acid pretreatment lignocellulosic material, it only needs the water consumption that the limit is low, the liquid-solid ratio using reaches 1:3-2:1, but it need to add the steam of 140 ℃-250 ℃, and maintain 1-120 minute (min).
Chinese patent application CN101255479 has described a kind of efficiently saccharifying method that chemical treatment is combined with mechanical disintegration, it comprises lignocellulose raw material is carried out to coarse crushing (20-60 order), then add the aqueous slkali of 0.1%-3% until liquid-solid ratio is 4:1-12:1, and proceed the broken 1-4 of wet-milling hour (h).Carry out the preliminary treatment under normal temperature condition although the method does not need to add steam, because 20-60 order is arrived in raw material coarse crushing by needs, and wet grinding time is long, and therefore, water consumption is large, and mechanical energy consumption is high, can not realize continuous preliminary treatment, is difficult to industrialization.
Therefore, the problem existing in the method for pretreatment of fiber element biolobic material can be summed up as: 1) energy consumption of steam blasting processing is high, and delignification difficulty is difficult for realizing and produces continuously and industrialization; 2) conventional acid or the condition harshness of alkali treatment, water consumption is large, and energy consumption is high, and easily produces accessory substance; 3) efficiency of simple mechanical treatment (for example pulverizing or wet grinding) is low, and energy consumption is high, is difficult to large-scale production.
Therefore, this area is in the urgent need to the method for development of new, effective pretreatment of fiber element biolobic material, to promote cellulose series biomass to be converted into the suitability for industrialized production of liquid fuel.
Summary of the invention
relational language
In this application, except as otherwise noted, otherwise Science and Technology noun used herein has the implication that those skilled in the art understand conventionally.And laboratory operation step used herein is widely used conventional steps in corresponding field.Meanwhile, in order to understand better the present invention, provide definition and the explanation of relational language below.
As used herein, term " cellulose series biomass " refers to, the living beings that contain cellulose and/or hemicellulose, it for example can derive from, agricultural wastes (such as maize straw, wheat stalk stalk, straw, wheat straw, bagasse etc.), trade waste (fibrous residue in such as slurrying and paper mill), forestry waste (such as timber, wood sawdust etc.) and urban waste (such as waste paper, wrapping paper etc.).
As used herein, term " cellulose " refers to, the complicated polysaccharide of one being formed by connecting by β-Isosorbide-5-Nitrae-glycosidic bond by glucose unit, and it can comprise thousands of glucose units conventionally.Cellulose is the chief component composition of plant cell wall, and is therefore extensively present in each Plants.
As used herein, term " hemicellulose " refers to that several dissimilar polysaccharide mixture of combining closely with cellulose in plant cell wall comprises xylan, xyloglucan and gala glucomannan etc.
As used herein, term " preliminary treatment " or " processing " cellulose series biomass refer to, cellulose series biomass are converted into the process being for example easy to, for example, by the substrate (glucan, xylan) of various enzymes (cellulase, β glucuroide and zytase) enzymolysis by chemistry and/or physical method.
As used herein, the term chemicals of degraded cellulose biolobic material " can " refers to such chemical reagent, and it can be degraded to cellulose series biomass the sugar being easy to by enzymolysis.This type of chemical reagent is well known to those skilled in the art (referring to for example, " reparation technology of alcohol fuel and example ", Chemical Industry Press, the chief editors such as Liu Ronghou, wherein discuss in detail the chemical reagent for pretreatment of fiber element biolobic material), include but not limited to sulfuric acid, phosphoric acid, formic acid, acetic acid, NaOH, sodium carbonate, vulcanized sodium, sodium sulfite, hydrogen peroxide etc.
As used herein, term " Mechanical Crushing cellulose series biomass " refers to, uses mechanical force to make cellulose series biomass fragmentation.Described mechanical force can for example derive from equipment well known to those skilled in the art, for example extruder, squeezer, pulverizer etc.A particularly preferred equipment is double-screw extrusion machine.
Double-screw extrusion machine is the equipment of knowing in prior art, and it is commercially available acquisition, the Twin Screw Extrusion for example being produced by French Clextral company.The schematic diagram of the main body of double-screw extrusion machine can be referring to for example Fig. 1, its conventionally by two axially parallels, be engaged with each other and the screw rod of rotating in same direction forms, the spiral on described screw rod is forward and reverse alternately, and on reverse acting spiral, has several skewed slots.In a preferred method of the invention, biomass material is entered the main body of double-screw extrusion machine by charging aperture, and is transported to crush zone.Then, in crush zone, material is pushed to reverse acting spiral under the effect of transport screw, and compressed under the squeezing action of forward and reverse acting spiral.Because the squeezing action of transport screw is larger than reverse acting spiral, material is forced to from the skewed slot of reverse acting spiral, by entering next crush zone, to carry out further attrition crushing.So repeatedly, material passes through multiple crush zones continuously, thereby by Mechanical Crushing.In this extrusion process, between fiber and spiral in material, between fiber and fiber, produce very large mechanical force (, frictional force), cause fiber generation conquassation, break and fibrillation effect.The specific area that this has increased cellulose series biomass greatly, has improved the accessibility of biology enzyme to it in chemicals and subsequent step, has improved the degradation efficiency of chemicals and the degradation efficiency of enzyme.
In addition,, in the extrusion process of double-screw extrusion machine, huge mechanical force (, frictional force) causes producing a large amount of heat, thereby has greatly improved the temperature of material.Therefore, can be in extrusion process, before or after, add chemicals by charging aperture and/or inlet, and utilize the amount of heat producing to improve the temperature of reactant mixture, promote the degradation of chemicals to material.Especially, in double helix extrusion process, the mechanical thermal that utilizes the friction between fiber and spiral and between fiber and fiber to produce, be enough to the temperature of reactant mixture to bring up to 100 ℃ of left and right, thereby without carrying out extra heating, can make the chemicals adding fully mix and fast reaction with broken cellulose series biomass.
In addition, unless specialize, concentration used herein refers to mass percent concentration.
For example, the concentration of cellulose series biomass refers to, carries out the mass percent concentration of cellulose series biomass in pretreated mixture, and it can calculate by following formula:
The quality (g) of the concentration=cellulose series biomass of cellulose series biomass/the carry out gross mass (g) × 100% of pretreated mixture
For example, the final concentration of chemical reagent refers to, for the mass percent concentration of the whole solution chemical reagent of pretreatment of fiber element biolobic material, it can calculate by following formula:
The quality (g) of the final concentration=chemical reagent of chemical reagent/for gross mass (the g) × 100%=of the whole solution of pretreatment of fiber element biolobic material (gross mass of the chemical reagent solution of the initial mass percent concentration of chemical reagent × use)/for gross mass × 100% of the whole solution of pretreatment of fiber element biolobic material
As used herein, formed together with cellulose series biomass and carried out pretreated mixture for the whole solution of pretreatment of fiber element biolobic material.
As used herein, term " enzymolysis efficiency of glucose (or wood sugar) " refers to, the amount of the glucose (or wood sugar) in enzymolysis product accounts for the percentage of glucose (or wood sugar) equivalent containing in enzymolysis raw material.Glucose (or wood sugar) equivalent containing in enzymolysis raw material can be measured by method well known to those skilled in the art, for example, use NREL/TP-510-42618 method (http://www.nrel.gov/biomass/pdfs/42618.pdf) to measure.Therefore, the enzymolysis efficiency of glucose or wood sugar can for example calculate by following formula:
Enzymolysis efficiency=(quality of the glucose in enzymolysis product)/(quality/0.9 of the glucan containing in enzymolysis raw material) × 100% of glucose
Enzymolysis efficiency=(quality of the wood sugar in enzymolysis product)/(quality/0.88 of the xylan containing in enzymolysis raw material) × 100% of wood sugar
As used herein, term " total reducing sugar yield " refers to, the monose quality sum that the cellulose series biomass of unit mass obtains after preliminary treatment and enzymolysis, and it can for example calculate by following formula:
Total reducing sugar yield=(the wood sugar quality that glucose quality+enzymolysis that enzymolysis obtains obtains)/(quality of cellulose series biomass)
As used herein, term " the preliminary treatment rate of recovery of material " refers to, the quality of pretreated material accounts for the percentage of the quality of cellulose series biomass before preliminary treatment, and it can for example calculate by following formula:
Quality × 100% of cellulose series biomass before the quality/preliminary treatment of the preliminary treatment rate of recovery=pretreated material of material
detailed description of the present invention
In this application, inventor has developed the method for novel, effective pretreatment of fiber element biolobic material, has solved the problem existing in this area as discussed above.Particularly, the method according to this invention combines physical method and chemical method, that is, and and before Mechanical Crushing, simultaneously or add afterwards chemicals, increase on the one hand the contact area of chemicals and living beings by Mechanical Crushing, thereby promote the effect of chemicals; The friction mechanism heat of utilizing on the other hand physics extrusion process to produce improves the temperature of reaction system, thereby promotes the effect of chemicals.Method of the present invention for example, processing cellulose series biomass when (maize straw), and not only energy consumption is low, water consumption is few, and the product obtaining (, pretreated material) is easy to be degraded by various enzymes, and enzymolysis efficiency is high.
Therefore, in one aspect, the invention provides a kind of method of pretreatment of fiber element biolobic material, it comprises, before Mechanical Crushing cellulose series biomass, simultaneously or afterwards, described cellulose series biomass is contacted with chemicals that can degraded cellulose biolobic material, and the heat that utilizes described Mechanical Crushing to produce improves the temperature of the mixture of described cellulose series biomass and described chemicals.
In a preferred embodiment, the heat that described Mechanical Crushing produces is brought up at least 50 ℃ by the temperature of described mixture, preferably at least 55 ℃, at least 60 ℃, at least 65 ℃, at least 70 ℃, at least 75 ℃, at least 80 ℃, at least 85 ℃, at least 90 ℃, at least 95 ℃, at least 96 ℃, at least 97 ℃, at least 98 ℃, at least 99 ℃ or higher.As well known to those skilled in the art, the rising of temperature of reaction system can strengthen the degradation of chemicals to cellulose series biomass.
In a preferred embodiment, under normal pressure, carry out method of the present invention.
In a preferred embodiment, described chemicals is selected from sulfuric acid, phosphoric acid, formic acid, acetic acid, NaOH, sodium carbonate, vulcanized sodium, sodium sulfite, hydrogen peroxide or its combination.In a preferred embodiment, described cellulose series biomass is contacted with at least 2 kinds of chemicalss.In a further preferred embodiment, described cellulose series biomass is contacted with at least 2 kinds of chemicalss simultaneously.For example, cellulose series biomass can be contacted with hydrogen peroxide with NaOH simultaneously.In another preferred embodiment, described cellulose series biomass is contacted with at least 2 kinds of chemicalss successively.For example, cellulose series biomass first can be contacted with sulfuric acid, and then cellulose series biomass is contacted with NaOH.Optionally, can between adjacent 2 contacts, carry out washing step, to avoid influencing each other between different chemicals.
In a preferred embodiment, use extruder, squeezer or pulverizer carry out Mechanical Crushing to cellulose series biomass.In a preferred embodiment, carry out Mechanical Crushing cellulose series biomass with double-screw extrusion machine.
In a preferred embodiment, cellulose series biomass derives from agricultural wastes (such as maize straw, wheat stalk stalk, straw, wheat straw, bagasse etc.), trade waste (fibrous residue in such as slurrying and paper mill), forestry waste (such as timber, wood sawdust etc.), urban waste (such as waste paper, wrapping paper etc.) or its combination.
In a preferred embodiment, before described cellulose series biomass is contacted with described chemicals, wash described cellulose series biomass with water, and the concentration of the cellulose series biomass after washing is at least 40%, for example at least 50%, at least 60%, at least 70%, at least 80% or at least 90%.
In a preferred embodiment, in described mixture, the concentration of cellulose series biomass is about 25%-40%, for example, and 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38% or 39%.
In a preferred embodiment, described mixture temperature being raise is placed in attemperator.In a further preferred embodiment, described mixture is placed in to attemperator, carries out at least 10 minutes, preferably at least 20 minutes, at least 0.5 hour, at least 1 hour, at least 2 hours, at least 3 hours, at least 4 hours, at least 5 hours, at least 6 hours, at least 7 hours, at least 8 hours, at least 9 hours, at least 10 hours or longer time.
In a preferred embodiment, the NaOH that is 2%-25% by described cellulose series biomass with final concentration contacts.In another preferred embodiment, the sulfuric acid that is 0.25%-36% by described cellulose series biomass with final concentration contacts.In another preferred embodiment, the hydrogen peroxide that is 3%-15% by described cellulose series biomass with final concentration contacts.
In a preferred embodiment, the product obtaining according to preprocess method of the present invention can further experience other steps, for example boiling step, steam blasting step or enzymolysis step.In a further preferred embodiment, described enzyme is selected from cellulase, β glucuroide, zytase or its combination.
In yet another aspect, the invention provides a kind of method that cellulose series biomass is converted into monose, it comprises the following steps:
1) cellulose series biomass is experienced to preprocess method of the present invention;
2) by pretreated cellulose series biomass experience enzymolysis.
In a preferred embodiment, in step 1) before, optionally, described cellulose series biomass is experienced to broken step.
In a preferred embodiment, described enzyme is selected from cellulase, β glucuroide, zytase or its combination.
In a preferred embodiment, carry out step 2) before, optionally, by pretreated cellulose series biomass experience washing step.
The beneficial effect of the invention
Compared with prior art, technical scheme of the present invention has following beneficial effect:
(1) in the process of Mechanical Crushing, add chemicals, realized physics, chemistry effect altogether to cellulose series biomass, processing method is simple;
(2) Mechanical Crushing has increased the contact area of chemicals and cellulose series biomass, is conducive to fully mixing of chemicals and cellulose series biomass, and rapid osmotic is to fibrous inside, improves reaction efficiency;
(3) cellulose series biomass is under physics extruding and broken effect, for example, due to the friction between fiber and equipment (double-screw extrusion machine) and between fiber and fiber, produce a large amount of friction mechanism heat, thereby do not need extra heating, also can improve the temperature of reaction system, promote the effect of chemicals;
(4) method of the present invention utilizes friction mechanism heat to improve the temperature of reaction system, and without extra heating, thereby the utilization ratio of energy is higher, energy consumption is lower.
(5) in a preferred embodiment of the invention, double helix attrition crushing can more effectively destroy the combination between fibre composition, break hemicellulose and lignin being coated fiber, make fiber generation fibrillation, thereby more effectively increase the specific area (specific surface) of cellulose series biomass, improve the accessibility of biology enzyme to it, greatly improved enzymolysis efficiency;
(6) method of the present invention can be under the temperate condition of lower temperature (normal pressure, and conventionally not higher than 100 ℃) carry out, not only obtain the high sugared yield degraded by enzymes that is easy to, and reduced the generation that follow-up step of converting is had to the accessory substance of negative effect;
(7) method of the present invention can be carried out under High Concentration Situation, and liquid-solid ratio is low, and water consumption is few, has not only saved water resource, and has reduced and act on ineffective energy consumption waterborne.
Accompanying drawing explanation
Fig. 1 has shown the schematic diagram of the main body of double-screw extrusion machine, wherein, exemplified double-screw extrusion machine comprises a charging aperture, a discharging opening, three inlets and three liquid outlets, and wherein, charging aperture is for loading pending cellulose series biomass and various chemicals, inlet is used for loading various chemicalss, and liquid outlet is for discharging liquid that processing procedure produces or undesired, and discharging opening is for collecting treated cellulose series biomass.But, it will be apparent to those skilled in the art that double-screw extrusion machine can comprise still less as required or more inlet and liquid outlet.For example, inlet and liquid outlet can be at least 1 respectively independently, at least 2, and at least 3, at least 4, at least 5, at least 10, at least 15, at least 20 or more.For example, can not there is not inlet, and directly add chemicals from charging aperture, or before loading, by cellulose series biomass and various chemicals premixed.
The in the situation that of illustrated double-screw extrusion machine, biomass material is entered the main body of double-screw extrusion machine by charging aperture, and is transported to crush zone.Then, in crush zone, material is pushed to reverse acting spiral under the effect of transport screw, and compressed under the squeezing action of forward and reverse acting spiral.Because the squeezing action of transport screw is larger than reverse acting spiral, material is forced to from the skewed slot of reverse acting spiral, by entering next crush zone, to carry out further attrition crushing.So repeatedly, material passes through 3 crush zones continuously, and finally discharges from discharging opening.In extrusion process, can add chemicals via charging aperture or any or multiple inlet, realize the physics and chemistry of material is acted on altogether; And can discharge produce or undesired liquid in processing procedure via discharging opening or any or multiple liquid outlet.
The specific embodiment
Below in conjunction with embodiment, the preferred embodiments of the invention are described in detail, but it will be understood by those skilled in the art that the following example is only for the present invention is described, rather than restriction to scope of the present invention.According to the following detailed description of the preferred embodiment of the invention, it is obvious that various objects of the present invention and favourable aspect will become to those skilled in the art.
Unless specialized, otherwise the various chemical analysis methods and the detection method that in embodiment, use, all to carry out (referring to for example according to method well-known to those skilled in the art, the method of the analysis that NREL provides and test organisms matter, http://www.nrel.gov/biomass/analytical_procedures.html); The condition that the use of various enzymes is recommended according to goods producer.The unreceipted person of production firm of the reagent using or instrument, being can be by the conventional products of commercial acquisition.Those skilled in the art know, and embodiment describes the present invention with way of example, and are not intended to limit the present invention's scope required for protection.
Embodiment 1
Air-dry maize straw is cut to 3-5cm with chopper, and is loaded in double-screw extrusion machine (sky, Hebei is just screening pulping equipment Co., Ltd, TEP80) by charging aperture.Add water by charging aperture, wash, and the content of water in the material that can be extruded by liquid outlet adjustment.In the present embodiment, control the content of water, making material concentration was approximately 50% (quality of the water, comprising is equivalent to the quality of 1 times of over dry material).Adding concentration by inlet 3 is 6% sodium hydroxide solution, and can suitably adjust by liquid outlet and inlet final concentration and the consumption of sodium hydroxide solution.In the present embodiment, control the consumption of sodium hydroxide solution, make material concentration further drop to for approximately 33% (quality of the sodium hydroxide solution, using is equivalent to the quality of 1 times of over dry material).
The rotating speed of the main shaft of double-screw extrusion machine is set to 375rpm.Collecting concentration from discharging opening is approximately 33% pretreated material, and it is placed in heat insulation tank to 2 hours (h).After measured, in preprocessing process, the temperature of material reaches 94 ℃.After leaving standstill, material washing is extremely neutral, then analyze its chemical composition according to the method for describing in NREL/TP-510-42618 (http://www.nrel.gov/biomass/pdfs/42618.pdf), and according to the description of manufacturer, use high performance liquid chromatography (HPLC, Model 1200, Agilent Technologies, USA) detect the content of its carbohydrate.
Result shows, contains following ingredients (calculating by mass fraction): glucan (55.2%), xylan (22.5%), lignin (8.6%) in pretreated material.This shows, after method preliminary treatment of the present invention, the lignin in maize straw is removed effectively.
At pH4.8, at 50 ℃, use the cellulase (Celluclast1.5L) of 20FPU/g substrate and the β glucuroide (Novozyme 188) of 5IU/g substrate, the concentration of substrate with 2% is by pretreated material enzymolysis 48h.According to the description of manufacturer, use high performance liquid chromatography (HPLC, Model 1200, Agilent Technologies, USA) enzyme analysis hydrolysis products, and calculate the enzymolysis efficiency of glucose, enzymolysis efficiency and the total reducing sugar yield of wood sugar.
Result demonstration, the preliminary treatment rate of recovery of initial material is 63.6%; In the enzymolysis product of pretreated material, the enzymolysis efficiency of glucose is 81.3%, and the enzymolysis efficiency of wood sugar is 88.4%; The total reducing sugar yield of initial material is the initial material of 0.46g monose/g.This shows, maize straw, can be easily degraded by enzymes after the method according to this invention preliminary treatment, and the enzymolysis efficiency of monose and total reducing sugar yield all very high.
Embodiment 2
Air-dry maize straw is tentatively crushed to 1-3cm with pulverizer, and is loaded in double-screw extrusion machine (sky, Hebei is just screening pulping equipment Co., Ltd, TEP80) by charging aperture.Add water by charging aperture, wash, and the content of water in the material that can be extruded by liquid outlet adjustment.In the present embodiment, control the content of water, making material concentration is approximately 45%.Adding concentration by inlet 3 is 10% sodium hydroxide solution, and can suitably adjust by liquid outlet and inlet final concentration and the consumption of sodium hydroxide solution.In the present embodiment, control the consumption of sodium hydroxide solution, make material concentration further drop to for approximately 35% (quality of the sodium hydroxide solution, using is equivalent to the quality of 0.6 times of over dry material).
The rotating speed of the main shaft of double-screw extrusion machine is set to 375rpm.Collecting concentration from discharging opening is approximately 35% pretreated material, and it is placed in heat insulation tank to 1 hour (h).After measured, in preprocessing process, the temperature of material reaches 98 ℃.After leaving standstill, material washing is extremely neutral, then analyze its chemical composition according to the method for describing in NREL/TP-510-42618 (http://www.nrel.gov/biomass/pdfs/42618.pdf), and according to the description of manufacturer, use high performance liquid chromatography (HPLC, Model 1200, Agilent Technologies, USA) detect the content of its carbohydrate.
Result shows, the preliminary treatment rate of recovery of material is 61.7%, and in pretreated material, contain following ingredients (calculating by mass fraction): glucan (61.5%), xylan (21.0%), lignin (8.6%).This shows, after method preliminary treatment of the present invention, the lignin in maize straw is removed effectively.
At pH4.8, at 50 ℃, use the cellulase (Celluclast1.5L) of 20FPU/g substrate and the β glucuroide (Novozyme 188) of 5IU/g substrate, the concentration of substrate with 2% is by pretreated material enzymolysis 48h.According to the description of manufacturer, use high performance liquid chromatography (HPLC, Model 1200, Agilent Technologies, USA) enzyme analysis hydrolysis products, and calculate the enzymolysis efficiency of glucose, enzymolysis efficiency and the total reducing sugar yield of wood sugar.
Result demonstration, in enzymolysis product, the enzymolysis efficiency of glucose is 89.0%, the enzymolysis efficiency of wood sugar is 84.6%; The total reducing sugar yield of initial material is the initial material of 0.50g monose/g.This shows, maize straw, can be easily degraded by enzymes after the method according to this invention preliminary treatment, and the enzymolysis efficiency of monose and total reducing sugar yield all very high.
Embodiment 3
Air-dry maize straw is tentatively crushed to 1-3cm with pulverizer, and is loaded in double-screw extrusion machine (sky, Hebei is just screening pulping equipment Co., Ltd, TEP80) by charging aperture.Add water by charging aperture, wash, and the content of water in the material that can be extruded by liquid outlet adjustment.In the present embodiment, control the content of water, making material concentration is approximately 50%.Adding concentration by inlet 2 is 1% sulfuric acid solution, and can suitably adjust by liquid outlet and inlet final concentration and the consumption of sulfuric acid solution.In the present embodiment, control the consumption of sulfuric acid solution, make material concentration further drop to for approximately 35% (quality of the sulfuric acid solution, using is equivalent to the quality of 0.8 times of over dry material).
The rotating speed of the main shaft of double-screw extrusion machine is set to 375rpm.Collecting concentration from discharging opening is approximately 35% pretreated material, and it is placed in heat insulation tank to 3 hours (h).After measured, in preprocessing process, the temperature of material reaches 96 ℃.After leaving standstill, material washing is extremely neutral, and reclaim the pentose (rate of recovery of pentose is 25.1%, the pentose equivalent in relatively initial material) in cleaning solution.Then be 8% NaOH to adding final concentration in material, control liquid-solid ratio is 10:1, and at 105 ℃, continues reaction 2h in reactor.Cooling and washing material, regulates pH value to 4.8.Then analyze its chemical composition according to the method for describing in NREL/TP-510-42618 (http://www.nrel.gov/biomass/pdfs/42618.pdf), and according to the description of manufacturer, use high performance liquid chromatography (HPLC, Model 1200, Agilent Technologies, USA) detect the content of its carbohydrate.
Result shows, the preliminary treatment rate of recovery of material is 54.7%, and in pretreated material, contain following ingredients (calculating by mass fraction): glucan (50.1%), xylan (21.6%), lignin (12.9%).This shows, after method preliminary treatment of the present invention, from initial material stripping part xylan and most of lignin.
At pH4.8, at 50 ℃, use the cellulase (Celluclast1.5L) of 20FPU/g substrate and the β glucuroide (Novozyme 188) of 5IU/g substrate, the concentration of substrate (pressing mass fraction calculates) with 2% is by pretreated material enzymolysis 48h.According to the description of manufacturer, use high performance liquid chromatography (HPLC, Model 1200, Agilent Technologies, USA) enzyme analysis hydrolysis products, and calculate the enzymolysis efficiency of glucose, enzymolysis efficiency and the total reducing sugar yield of wood sugar.
Result demonstration, in enzymolysis product, the enzymolysis efficiency of glucose is 93.2%, the enzymolysis efficiency of wood sugar is 87.6%; The total reducing sugar yield of initial material is the initial material of 0.50g monose/g.This shows, maize straw, can be easily degraded by enzymes after the method according to this invention preliminary treatment, and the enzymolysis efficiency of monose and total reducing sugar yield all very high.
Embodiment 4
Air-dry maize straw is cut to 3-5cm with chopper, and water washs, be then loaded in double-screw extrusion machine (sky, Hebei is just screening pulping equipment Co., Ltd, TEP185) by charging aperture.Utilize front two sections of spirals of double-screw extrusion machine, part moisture and the air in stalk removed in extruding, and the concentration that makes material is approximately 50%.
Adding concentration by inlet 3 is 8% sulfuric acid solution, and can suitably adjust by liquid outlet and inlet final concentration and the consumption of sulfuric acid solution.In the present embodiment, control the consumption of sulfuric acid solution, make material concentration further drop to for approximately 33% (quality of the sulfuric acid solution, using is equivalent to the quality of 1 times of over dry material).
The rotating speed of the main shaft of double-screw extrusion machine is set to 375rpm.Collecting concentration from discharging opening is approximately 33% pretreated material.After measured, the temperature of extruder discharging opening place material reaches 95 ℃.This material is placed to 3 hours (h) in heat insulation tank.After leaving standstill, material washing is extremely neutral, and reclaim the pentose (rate of recovery of pentose is 51.2%, the pentose equivalent in relatively initial material) in cleaning solution.Then be 6% NaOH to adding final concentration in material, control liquid-solid ratio is 10:1, and at 105 ℃, continues reaction 2h in reactor.Cooling and washing material, regulates pH value to 4.8.Then analyze its chemical composition according to the method for describing in NREL/TP-510-42618 (http://www.nrel.gov/biomass/pdfs/42618.pdf), and according to the description of manufacturer, use high performance liquid chromatography (HPLC, Model 1200, Agilent Technologies, USA) detect the content of its carbohydrate.
Result shows, the preliminary treatment rate of recovery of material is 50.2%, and in pretreated material, contain following ingredients (calculating by mass fraction): glucan (68.8%), xylan (13.1%), lignin (7.2%).This shows, after method preliminary treatment of the present invention, most of lignin and hemicellulose in maize straw are dissolved.
At pH4.8, at 50 ℃, use the cellulase (Celluclast1.5L) of 15FPU/g substrate and the β glucuroide (Novozyme 188) of 5I U/g substrate, the concentration of substrate with 6% is by pretreated material enzymolysis 48h.According to the description of manufacturer, use high performance liquid chromatography (HPLC, Model 1200, Agilent Technologies, USA) enzyme analysis hydrolysis products, and calculate the enzymolysis efficiency of glucose, enzymolysis efficiency and the total reducing sugar yield of wood sugar.
Result demonstration, in enzymolysis product, the enzymolysis efficiency of glucose is 91.3%, the enzymolysis efficiency of wood sugar is 93.8%; The total reducing sugar yield of initial material is the initial material of 0.566g monose/g.This shows, maize straw, can be easily degraded by enzymes after the method according to this invention preliminary treatment, and the enzymolysis efficiency of monose and total reducing sugar yield all very high.
Embodiment 5
The poplar sheet water that size is about to 4cm*4cm washs, and is then loaded in double-screw extrusion machine (sky, Hebei is just screening pulping equipment Co., Ltd, TEP80) by charging aperture.Utilize front two sections of spirals of double-screw extrusion machine, part moisture and the air in wood chip removed in extruding, and the concentration that makes material is approximately 60%.
Adding concentration by inlet 3 is 43% sodium hydroxide solution, and can suitably adjust by liquid outlet and inlet final concentration and the consumption of sodium hydroxide solution.In the present embodiment, control the consumption of sodium hydroxide solution, make material concentration further drop to for approximately 40% (quality of the sodium hydroxide solution, using is equivalent to the quality of 0.83 times of over dry material).
The rotating speed of the main shaft of double-screw extrusion machine is set to 350rpm.Collecting mass dryness fraction from discharging opening is approximately 40% pretreated material.After measured, the temperature of extruder discharging opening place material reaches 98 ℃.This material is placed to 1 hour (h) in heat insulation tank.After leaving standstill, material washing is extremely neutral, then analyze its chemical composition according to the method for describing in NREL/TP-510-42618 (http://www.nrel.gov/biomass/pdfs/42618.pdf), and according to the description of manufacturer, use high performance liquid chromatography (HPLC, Model 1200, Agilent Technologies, USA) detect the content of its carbohydrate.
Result shows, the preliminary treatment rate of recovery of material is 78.6%, and in pretreated material, contain following ingredients (calculating by mass fraction): glucan (51.8%), xylan (19.2%), lignin (20.3%).This shows, after method preliminary treatment of the present invention, part hemicellulose and lignin in poplar sheet are dissolved.
At pH4.8, at 50 ℃, use the cellulase (Celluclast1.5L) of 25FPU/g substrate and the β glucuroide (Novozyme 188) of 15IU/g substrate, the concentration of substrate with 8% is by pretreated material enzymolysis 72h.According to the description of manufacturer, use high performance liquid chromatography (HPLC, Model 1200, Agilent Technologies, USA) enzyme analysis hydrolysis products, and calculate the enzymolysis efficiency of glucose, enzymolysis efficiency and the total reducing sugar yield of wood sugar.
Result demonstration, in enzymolysis product, the enzymolysis efficiency of glucose is 85.3%, the enzymolysis efficiency of wood sugar is 78.1%; The total reducing sugar yield of initial material is the initial material of 0.52g monose/g.This shows, poplar sheet, can be easily degraded by enzymes after the method according to this invention preliminary treatment, and the enzymolysis efficiency of monose and total reducing sugar yield all very high.
The all publications that relate in this description, comprise that patent, patent application and other lists of references integrate with in full herein by reference with it, for any object, for example, provide the other detailed content about enforcement of the present invention.
Although the specific embodiment of the present invention has obtained detailed description, those skilled in the art will appreciate that according to disclosed all instructions, can carry out various modifications and changes to details, and these change all within protection scope of the present invention.Four corner of the present invention is provided by claims and any equivalent thereof.
Claims (10)
1. the method for a pretreatment of fiber element biolobic material, it comprises, before Mechanical Crushing cellulose series biomass, simultaneously or afterwards, described cellulose series biomass is contacted with chemicals that can degraded cellulose biolobic material, and the heat that utilizes described Mechanical Crushing to produce improves the temperature of the mixture of described cellulose series biomass and described chemicals.
2. the process of claim 1 wherein that the heat that described Mechanical Crushing produces brings up at least 50 ℃ by the temperature of described mixture, preferably at least 55 ℃, at least 60 ℃, at least 65 ℃, at least 70 ℃, at least 75 ℃, at least 80 ℃, at least 85 ℃, at least 90 ℃, at least 95 ℃, at least 96 ℃, at least 97 ℃, at least 98 ℃, at least 99 ℃ or higher.
3. the method for claim 1 or 2, wherein said method is carried out under normal pressure.
4. the method for any one in claim 1-3, wherein said chemicals is selected from sulfuric acid, phosphoric acid, formic acid, acetic acid, NaOH, sodium carbonate, vulcanized sodium, sodium sulfite, hydrogen peroxide or its combination;
Preferably, described cellulose series biomass is contacted with at least 2 kinds of chemicalss.
5. the method for any one in claim 1-4, is wherein used extruder, and squeezer or pulverizer preferably carry out Mechanical Crushing with double-screw extrusion machine to cellulose series biomass;
Preferably, described cellulose series biomass derives from agricultural wastes (such as maize straw, wheat stalk stalk, straw, wheat straw, bagasse etc.), trade waste (fibrous residue in such as slurrying and paper mill), forestry waste (such as timber, wood sawdust etc.), urban waste (such as waste paper, wrapping paper etc.) or its combination.
6. the method for any one in claim 1-5, wherein before described cellulose series biomass is contacted with described chemicals, wash described cellulose series biomass with water, and the concentration of the cellulose series biomass after washing is at least 40%, for example at least 50%, at least 60%, at least 70%, at least 80% or at least 90%.
7. the method for any one in claim 1-6, in wherein said mixture, the concentration of cellulose series biomass is about 25%-40%, for example, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38% or 39%.
8. the method for any one in claim 1-7, the described mixture wherein temperature being raise is placed in attemperator, preferably, this step is carried out at least 10 minutes, and preferably at least 20 minutes, at least 0.5 hour, at least 1 hour, at least 2 hours, at least 3 hours, at least 4 hours, at least 5 hours, at least 6 hours, at least 7 hours, at least 8 hours, at least 9 hours, at least 10 hours or longer time.
9. the method for any one in claim 1-8, wherein, further experiences other steps by pretreated cellulose series biomass, for example boiling step, steam blasting step or enzymolysis step;
Preferably, the enzyme using in described enzymolysis step is selected from cellulase, β glucuroide, zytase or its combination.
10. a method that cellulose series biomass is converted into monose, it comprises the following steps:
1) right to use requires the method for any one in 1-9, and described cellulose series biomass is carried out to preliminary treatment;
2) by pretreated cellulose series biomass experience enzymolysis;
Optionally, in step 1) before, described cellulose series biomass is experienced to broken step;
Optionally, carry out step 2) before, by pretreated cellulose series biomass experience washing step;
Preferably, step 2) in use enzyme be selected from cellulase, β glucuroide, zytase or its combination.
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