CN103898180B - A kind of method adopting cellulose containing raw material to prepare reducing sugar - Google Patents
A kind of method adopting cellulose containing raw material to prepare reducing sugar Download PDFInfo
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Abstract
The invention provides a kind of method adopting cellulose containing raw material to prepare reducing sugar. The method that described employing cellulose containing raw material prepares reducing sugar is hydrolyzed after including mixing pretreated cellulose containing raw material with cellulase, wherein, the method of described pretreatment carries out micro-wave digestion after including mixing described cellulose containing raw material with alkaline solution, the condition of described micro-wave digestion include temperature be 50-200 DEG C, pressure is 0.05-2MPa, microwave frequency be 0.5-5GHz, time is 1-60 minute. Adopt method provided by the invention can improve the productivity of reducing sugar.
Description
Technical field
The present invention relates to a kind of method adopting cellulose containing raw material to prepare reducing sugar.
Background technology
The primary raw material producing the regenerated biological energy such as alcohol fuel, biodiesel, hydrogen and biogas at present is the starch based biomass such as Semen Maydis, Maninot esculenta crantz., these raw materials are utilized to carry out commercial production, not only can cause and strive the unfavorable situation of grain with people, it is negatively affected to human lives and production, and the restriction of the conditions such as grain resource yield, the place of production and transport can be subject to, it is difficult to meet growing bioenergy demand. Cellulose containing raw material mainly includes agricultural crop straw and wild draft and xylophyta, is be distributed the most extensively on the earth and one of the most cheap Renewable resource, is highly suitable as the raw materials for production of regenerated biological energy. At present, whole nation straw theoretical resources amount is about 8.4 hundred million tons, can collect stock number and be about 700,000,000 tons.
In prior art, with cellulose containing raw material for raw material, utilize fermentable to produce regenerated biological energy and be broadly divided into two steps: cellulose containing raw material is hydrolyzed into reducing sugar by (1); (2) reducing sugar is changed into the target organism energy through fermentable. But, forming network structure at the inside of cellulose containing raw material, hemicellulose and lignin by covalent bond, cellulose is wrapped wherein, is difficult to contact with extraneous enzyme.If directly with cellulase hydrolysis, reducing sugar yield is generally below 20%. Therefore, it is generally the case that before cellulose containing raw material cellulase is hydrolyzed, it is necessary to cellulose containing raw material is carried out pretreatment. Pretreatment refers to that changed into from its natural structure by cellulose containing raw material can the process of effective water formal similarity. Cellulose containing raw material is after pretreatment, the composite construction of cellulose-hemicellulose-lignin is destroyed, hemicellulose and lignin portion fracture are dissolved, so that cellulosic degree of crystallinity reduces, the specific surface area contacted with cellulase increases, and more effectively can be become, by cellulase hydrolysis, the reducing sugar utilized that can ferment.
At present, cellulose containing raw material generally adopts steam explosion or adopts acid solution to carry out pretreatment. Such as, CN101387084A discloses the method for the raw material of a kind of steam blasting cellulose-containing, the raw material of cellulose is delivered in heat preservation pressure device by the method continuously, keep 3-10 minute, the raw material making the part cellulose in this device every the 5-12 second is discharged into normal pressure, thus destroying the lignin sheath embedding cellulose and hemicellulose in the raw material of cellulose. CN101148830A discloses a kind of method that plant carries out steam explosion-microwave coupling processing separation straw component, after the method comprises the steps: that straw is carried out steam explosion pretreatment by (1), adding 40-60 DEG C of warm water and moisten washing of rising, cleaning mixture staticly settles acquisition hemicellulose; (2) vapour after washing being exposed straw dehydration to water content is 3-5mL/g, after adding glycerol mixing afterwards, carries out intermittent microwave treatment; It is disposed, adds hot water thermal insulating stirring and dissolving 30-90min; With 40-60 DEG C of water washing, filter 23-5 times, filter cake is crude fibre; The addition of described glycerol is the glycerol that every gram of straw siccative adds 5-7mL; (3) by filtrate through staticly settling acquisition lignin. CN101434977A discloses a kind of cellulose sugar refining technology, and this technique adopts the mode of expelling-expansion pretreatment and cellulase compounding hydrolysis to obtain total sugar liquid. Wherein, described expelling-expansion pretreatment mainly utilizes heat effect and mechanical effect, make each interlayer portion lignin, cellulose, hydrolysis of hemicellulose in stalk cell wall, thus changing the distribution of iuntercellular lignin, increasing its specific surface area and improve hydrolysis efficiency.
But when adopting said method to the pretreatment of cellulose containing raw material, the lignin sheath embedding cellulose and hemicellulose in cellulose containing raw material can not be sufficiently destroyed, thus resulting in pretreated cellulose containing raw material is hydrolyzed sugaring or be hydrolyzed bioenergy processed time, the productivity of reducing sugar is relatively low.
Summary of the invention
The invention aims to overcome the existing method of employing to prepare the defect that reducing sugar yield is relatively low, and a kind of method adopting cellulose containing raw material to prepare reducing sugar that can improve reducing sugar yield is provided.
The invention provides a kind of method adopting cellulose containing raw material to prepare reducing sugar, the method is hydrolyzed after including mixing pretreated cellulose containing raw material with cellulase, wherein, the method of described pretreatment carries out micro-wave digestion after including mixing described cellulose containing raw material with alkaline solution, the condition of described micro-wave digestion include temperature be 50-200 DEG C, pressure is 0.05-2MPa, microwave frequency be 0.5-5GHz, time is 1-60 minute.
Present inventors discovered unexpectedly that, by the synergism that alkaline solution processes with micro-wave digestion, it is possible to significantly improve the productivity of reducing sugar. speculate its reason, it is likely due to: on the one hand, ��-1 in cellulose, 4-glycosidic bond has the character of acetal bonds, alkali is extremely sensitive, after described cellulose containing raw material is mixed homogeneously with alkaline solution, ��-1, 4-glycosidic bond ruptures, the degree of polymerization reduces, again the crushed products micro-wave digestion after mixing homogeneously with alkaline solution is processed, the surface texture of cellulose containing raw material and the cellulose-hemicellulose-lignin composite construction of inside can be destroyed extremely fully, the dissolving so that hemicellulose and lignin fully rupture, cellulosic degree of crystallinity reduces, and part hemicellulose is resolved into xylose, the monosaccharide such as mannose, and then it is hydrolyzed into glucose under the effect of cellulase.On the other hand, the micro-wave digestion that exists for of alkaline solution provides more favorable condition, is sufficiently destroyed thus being more beneficial for the lignin sheath by embedding cellulose and hemicellulose. In addition, the microwave digestion time that method provided by the invention adopts was less than 60 minutes, it is possible to be effectively reduced alkaline solution and the glucose and xylose in reducing sugar is degraded into the probability to the material that the subsequent applications such as fermentation are harmful to such as 5 hydroxymethyl furfural, furfural, formic acid further. Further, the present invention adopts microwave heating to substitute conventional vapor and heating in water bath, and reaction carries out in hermetic container, and not only energy consumption is low, condition is relatively mild, but also can shorten the process time, and reduces production cost.
A preferred embodiment of the invention, when by the water content control of described cellulose containing raw material when less than 2 weight %, not only it is more beneficial for obtaining the crushed products that particle diameter is less, and can also substantially more destroy the surface texture of cellulose containing raw material and the cellulose-hemicellulose-lignin composite construction of inside, thus improving the productivity of reducing sugar further.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, is used for explaining the present invention, but is not intended that limitation of the present invention together with detailed description below. In the accompanying drawings:
Fig. 1 is the process chart that employing cellulose containing raw material provided by the invention prepares reducing sugar;
Fig. 2 is the micro-structure diagram of the cellulose containing raw material obtained after adopting micro-wave digestion in embodiment 1.
Detailed description of the invention
Hereinafter the specific embodiment of the present invention is described in detail. It should be appreciated that detailed description of the invention described herein is merely to illustrate and explains the present invention, it is not limited to the present invention.
The method that employing cellulose containing raw material provided by the invention prepares reducing sugar is hydrolyzed after including mixing pretreated cellulose containing raw material with cellulase, wherein, the method of described pretreatment carries out micro-wave digestion after including mixing described cellulose containing raw material with alkaline solution, the condition of described micro-wave digestion include temperature be 50-200 DEG C, pressure is 0.05-2MPa, microwave frequency be 0.5-5GHz, time is 1-60 minute.
Wherein, described micro-wave digestion rotates principle of heating mainly by microwave plasma conduction and polar molecule, and adopts material inside and outside simultaneously mode of heating to realize the purpose of sample rapid damage, decomposition, and it is fast and the advantage such as be heated evenly that it has firing rate. Described micro-wave digestion can carry out in existing various microwave dissolvers, will not be described in great detail at this.
According to the present invention, as long as although carrying out micro-wave digestion after being mixed with alkaline solution by the cellulose containing raw material after pulverizing, and control to be 50-200 DEG C in temperature by the condition of described micro-wave digestion, pressure is 0.05-2MPa, microwave frequency is 0.5-5GHz, time is 1-60 minute, just can be effectively improved the productivity of reducing sugar, but in order to make to avoid the glucose and xylose in reducing sugar to be degraded into 5 hydroxymethyl furfural further, bran aldehyde, the material that formic acid etc. are harmful to subsequent applications such as fermentations, and improve the productivity of reducing sugar further, under preferable case, the condition of described micro-wave digestion includes temperature and is 100-150 DEG C, pressure is 0.1-0.8MPa, microwave frequency is 2-3GHz, time is 5-30 minute.
In the present invention, described pressure refers both to gauge pressure.
According to the present invention, the kind of described cellulose containing raw material can be the conventional selection of this area, for example, it is possible to the various industrial waste raw materials of the rich cellulose such as straw and corn cob, bagasse, Herba Eichhorniae of including the various crops such as Semen Maydis, Semen Tritici aestivi, Oryza sativa L. and Caulis Sacchari sinensis and wild herb. Under preferable case, described cellulose containing raw material is selected from one or more in corn straw, wheat stalk, rice straw, Caulis Sacchari sinensis straw, Sorghum vulgare Pers. straw, cotton stalk, beanstalk and Herba Eichhorniae.
According to the present invention, in order to increase the contact area of cellulose containing raw material and alkaline solution and improve the productivity of reducing sugar, under preferable case, the method for described pretreatment is additionally included in before being mixed with alkaline solution by described cellulose containing raw material, is pulverized by described cellulose containing raw material.
According to the present invention, the method of described pulverizing and condition can be all the conventional selection of this area, as long as the granule that particle diameter is less can be obtained, thus being more beneficial for follow-up processing with alkaline solution and micro-wave digestion, generally can carry out in pulverizer, concrete method is known for those skilled in the art, will not be described in great detail at this. Additionally, the particle diameter of crushed products after crushed can also carry out selecting and changing in wider scope, it is possible to rationally selected by the power and grinding time adjusting pulverizer, it is preferable that less than 550 microns. As a rule, the particle diameter of crushed products is more little, is more conducive to follow-up process, but pulverization conditions also has higher requirement; The particle diameter of crushed products is more big, it is possible to reduces the condition pulverized, but is unfavorable for that follow-up alkaline solution and micro-wave digestion process, therefore, combined factors from every side considers, it is more preferred to, it is 200-400 micron by the particle diameter that described cellulose containing raw material pulverizes the crushed products obtained.
Water content in described cellulose containing raw material is not particularly limited by the present invention, it is possible to for the conventional selection of this area. But the inventors found that, when by described cellulose containing raw material containing water management when less than 2 weight %, not only contribute to obtain the crushed products that particle diameter is less, can also be further ensured that adopts alkaline solution to process and in the process of micro-wave digestion in follow-up, destroy fully flat for the lignin sheath embedding cellulose and hemicellulose in cellulose containing raw material, thus more significantly increasing the productivity of reducing sugar. It is therefore preferable that in situation, the water content of described cellulose containing raw material is less than 2 weight %. Unless specifically indicated, the water content of cellulose containing raw material of the present invention each means the difference of the initial weight W1 and the weight W2 drying the cellulose containing raw material to constant weight at 105 DEG C of cellulose containing raw material, with the percentage by weight of the initial weight W1 of cellulose containing raw material, i.e. water content (weight %)=(W1-W2)/W1 �� 100%.
Would be likely to occur bigger difference according to the present invention, the raw material of different batches cellulose or the water content of different types of cellulose containing raw material, be generally 5-60 weight %. Therefore, in order to obtain the water content cellulose containing raw material less than 2 weight %, it is generally required to cellulose containing raw material higher for water content is dried at 60-120 DEG C, so that portion of water evaporation, thus water content is controlled in above-mentioned scope.
According to the present invention, the purpose that described crushed products contacts with alkaline solution is so that, and the cellulose-hemicellulose-lignin composite construction of the surface texture of cellulose containing raw material and inside is by partial destruction, thus being more beneficial for follow-up micro-wave digestion.The kind of described alkaline solution is known to the skilled person, such as, alkali therein can be selected from one or more in sodium hydroxide, potassium hydroxide, Lithium hydrate, barium hydroxide, aluminium hydroxide, manganous hydroxide, zinc hydroxide, sodium carbonate, potassium carbonate, lithium carbonate and ammonia. The concentration of above alkaline solution can carry out selecting and changing in wider scope, for instance, can be generally 0.1-5 weight %.
According to the present invention, the consumption of described alkaline solution reasonably can select according to the consumption of crushed products, and as a rule, the weight ratio of described crushed products and alkaline solution can be 0.05-20:100, it is preferred to 1-10:100. Needing description, the consumption of alkaline solution described herein includes water content therein.
As well known to those skilled in the art, described cellulase is compound enzyme, at least includes C1Fiber type element enzyme, Cx fiber type element enzyme and three kinds of enzymes of cellobiase.
C1Enzyme can make the cellulose of crystallization be changed into amorphous cellulose.
CXFiber type element enzyme is divided into again CX1Fiber type element enzyme and CX2Fiber type element enzyme two kinds. CX1Fiber type element enzyme is endo-type cellulase, it is possible to from hydration amorphous cellulose element intramolecular action in ��-Isosorbide-5-Nitrae-glycosidic bond, generates cellodextrin and cellobiose. CX2Fiber type element enzyme is a kind of circumscribed-type cellulase, it is possible to act on ��-Isosorbide-5-Nitrae-glycosidic bond from the non-reducing end of hydration non-cellulose molecule, cuts off ��-Isosorbide-5-Nitrae-glycosidic bond one by one and generates glucose.
Cellobiase then acts on cellobiose, makes cellobiose hydrolysis generate glucose.
Described cellulase can be commercially available, for instance, it is possible to purchased from the cellulase of Chemical Reagent Co., Ltd., Sinopharm Group.
According to the present invention, the step being hydrolyzed after being mixed with cellulase by pretreated cellulose containing raw material can be completed by the various methods that this area is conventional. As a rule, the consumption of cellulase is The more the better, but for cost consideration, with the dry weight basis of every gram of cellulose containing raw material, the consumption of described cellulase is preferably 1-10 weight %, is more preferably 1-5 weight %.
According to the present invention, the condition of described hydrolysis can be the conventional selection of this area, and as a rule, the condition of described hydrolysis includes the pH of the temperature of hydrolysis, time of hydrolysis and hydrolysis. The temperature of described hydrolysis can be any optimum temperature of cellulase, is generally 20-60 DEG C, more preferably 35-45 DEG C. On the time theory of described hydrolysis, the longer the better, but considers utilization rate of equipment and installations, and the time of described hydrolysis is preferably 48-120 hour, more preferably 60-100 hour. The pH value of described hydrolysis can be the suitableeest any action pH of cellulase, is generally 3-7, and more preferably pH value is 4-5. Owing in hydrolytic process, the fluctuation of pH value is little, therefore the pH value of described hydrolysis can adopt acidic materials to be adjusted according to method commonly used in the art before adding cellulase. Described acidic materials can be the material of the existing various pH value that can regulate cellulose containing raw material, for instance, it is possible to for one or more in HCl, sulphuric acid, sulfurous acid, nitric acid, phosphoric acid, selenic acid, perchloric acid, fluohydric acid gas, hydrogen bromide and hydrogen iodide. Above-mentioned acidic materials directly can use with pure state, it is also possible to uses with its aqueous solution form. When using as an aqueous solution, it is preferable that concentration is 5 weight % to saturated concentration.
According to the present invention, can not be dissolved in alkaline solution and the material that can not be hydrolyzed owing to pretreated cellulose containing raw material containing, after the end of the hydrolysis, these materials still exist in solid form, therefore, the method preparing reducing sugar provided by the invention also includes hydrolyzate is carried out solid-liquid separation, to be removed from reducing sugar by these solids.
A kind of detailed description of the invention according to the present invention, as described in Figure 1, the method that employing cellulose containing raw material provided by the invention prepares reducing sugar includes drying to water content therein less than 2 weight % cellulose containing raw material, and the cellulose containing raw material after drying is pulverized, make the particle diameter of the crushed products obtained less than 550 microns, then described crushed products is mixed homogeneously with alkaline solution (concentration is 0.1-5 weight %) and carried out micro-wave digestion under microwave action, the micro-wave digestion product cellulase obtained is hydrolyzed, and the hydrolyzate obtained is carried out solid-liquid separation, obtain reducing sugar.
Hereinafter will be described the present invention by embodiment.
In following example and comparative example, the theoretical yield �� 100%=(of the actual production �� reducing sugar of productivity (the %)=reducing sugar of reducing sugar contains the volume of the solution of the concentration of reducing sugar in the solution of reducing sugar �� containing reducing sugar) �� (in cellulose containing raw material hemicellulose level �� 1.136 in content of cellulose �� 1.111+ cellulose containing raw material) �� 100%. Wherein, in solution containing reducing sugar, the concentration of reducing sugar adopts DNS method to be measured, specifically, using 1.0mL deionized water as blank sample, take the solution containing reducing sugar of 1.0mL in test tube, and boil 5min after adding 3,5-edlefsen's reagents (DNS reagent) mix homogeneously of 2.0mL, quickly it is separately added into 10mL deionized water after cooling. Then using blank sample as reference solution, under 540nm wavelength, measure its absorbance, the concentration of wherein reducing sugar after contrasting with standard curve, can be drawn. Wherein, described standard curve is obtained by following method: is dried to constant weight in 105 DEG C by anhydrous glucose, accurately weighs 100mg glucose constant volume in 100mL volumetric flask, be made into the Glucose standards solution that concentration is 1.0mg/mL. Take 0.0mL respectively, 0.2mL, 0.4mL, 0.6mL, 0.8mL and 1.0mL standard solution add in teat glass, add deionized water 1.0mL, 0.8mL, 0.6mL, 0.4mL, 0.2mL and 0.0mL, it is configured to the solution that cumulative volume is 1.0mL, Glucose standards solution concentration respectively 0.0mg/mL, 0.2mg/mL, 0.4mg/mL, 0.6mg/mL, 0.8mg/mL and 1.0mg/mL, then in every teat glass, add 3, the 5-edlefsen's reagents of 2.0mL. Shake up after reagent is mixed, heat 5 minutes in boiling water bath, be quickly cooled to room temperature (25 DEG C) with cold water after taking-up, then be separately added into 10mL distilled water, the OD value under ultraviolet-visible spectrophotometric determination 540nm wavelength after shaking up. Each concentration of glucose adopts 3 parallel sampless, and OD value is averaged, and draws the function relation figure of concentration of glucose correspondence OD value, and fits to once linear equation, obtains the standard curve of concentration of reduced sugar correspondence OD value. Wherein, described 3, the compound method of 5-edlefsen's reagent is as follows: takes 91g sodium potassium tartrate tetrahydrate and is dissolved in 500mL deionized water, sequentially adds 3,5-dinitrosalicylic acids and the 20g sodium hydroxide of 3.15g, heated and stirred is so as to dissolve, it is subsequently adding 2.5g re-distilled phenol and 2.5g anhydrous sodium sulfite, cooling after all dissolving, and it is settled to 1000mL, being stored in brown reagent bottle, ambient temperatare just can use after putting 2 weeks. In cellulose containing raw material, cellulose and hemicellulose level adopt and are measured purchased from the Full-automatic fiber analyzer that model is Fibertec2010 of FOSS company of Sweden.
Embodiment 1
This embodiment is for illustrating the method that employing cellulose containing raw material provided by the invention prepares reducing sugar.
Rice straw is dried at 100 DEG C so that it is in water content be 1.5 weight %. And the rice straw obtained is ground into the particle diameter powder less than 212 microns, mix homogeneously by the weight ratio of 2:100 with the sodium hydroxide solution that concentration is 1.0 weight % again, then at microwave dissolver (purchased from Shanghai EU Apparatus Technology Development Co., Ltd., model is WX-8000, lower with) at 100 DEG C, carry out micro-wave digestion 5 minutes. Wherein, the microwave frequency used by micro-wave digestion is 2.45GHz, and pressure used is 0.1MPa. The microstructure of the cellulose containing raw material obtained after micro-wave digestion is as shown in Figure 2. From figure 2 it can be seen that the Surface and internal structure of the cellulose containing raw material after micro-wave digestion is destroyed fully. The micro-wave digestion product obtained is transferred in hydrolysis vessels, and with the sulfuric acid solution that concentration is 5 weight %, its pH value is adjusted to 4.5, it is subsequently adding the cellulase of the 4 weight % that weight is cellulose containing raw material dry weight used (purchased from Chemical Reagent Co., Ltd., Sinopharm Group, model is the examination of BR(Shanghai)), it is hydrolyzed 84 hours at 45 DEG C. After hydrolysis terminates, solids removed by filtration residue, obtain the solution containing reducing sugar. After measured, the productivity of reducing sugar is 90.2%.
Embodiment 2
This embodiment is for illustrating the method that employing cellulose containing raw material provided by the invention prepares reducing sugar.
Corn straw is dried at 105 DEG C so that it is in water content be 1.8 weight %. And the corn straw smashing obtained is become the particle diameter powder less than 270 microns, then mix homogeneously by the weight ratio of 4:100 with the potassium hydroxide solution that concentration is 2 weight %, then in microwave dissolver, at 150 DEG C, carry out micro-wave digestion 30 minutes. Wherein, the microwave frequency used by micro-wave digestion is 2.45GHz, and pressure used is 0.8MPa. The micro-wave digestion product obtained is transferred in hydrolysis vessels, and with the hydrochloric acid that concentration is 5 weight %, its pH value is adjusted to 4.8, it is subsequently adding the cellulase of the 3 weight % that weight is cellulose containing raw material dry weight used (purchased from Yakult company of Japan, model is OnozukaR-10), it is hydrolyzed 96 hours at 40 DEG C. After hydrolysis terminates, solids removed by filtration residue, obtain the solution containing reducing sugar. After measured, the productivity of reducing sugar is 93.3%.
Embodiment 3
This embodiment is for illustrating the method that employing cellulose containing raw material provided by the invention prepares reducing sugar.
Wheat stalk is dried at 95 DEG C so that it is in water content be 1.6 weight %. And the wheat stalk obtained is ground into the particle diameter powder less than 500 microns, then mix homogeneously by the weight ratio of 3:100 with the ammonia that concentration is 3 weight %, then in microwave dissolver, at 135 DEG C, carry out micro-wave digestion 10 minutes. Wherein, the microwave frequency used by micro-wave digestion is 2.45GHz, and pressure used is 0.3MPa. The micro-wave digestion product obtained is transferred in hydrolysis vessels, and with the hydrochloric acid that concentration is 8 weight %, its pH value is adjusted to 4.2, it is subsequently adding cellulase (the purchased from American Sigma-Aldrich company of the 5 weight % that weight is cellulose containing raw material dry weight used, model is C1794), it is hydrolyzed 84 hours at 38 DEG C. After hydrolysis terminates, solids removed by filtration residue, obtain the solution containing reducing sugar. After measured, the productivity of reducing sugar is 92.0%.
Embodiment 4
This embodiment is for illustrating the method that employing cellulose containing raw material provided by the invention prepares reducing sugar.
Wheat stalk is dried at 90 DEG C so that it is in water content be 1.7 weight %. And the wheat stalk obtained is ground into the particle diameter powder less than 250 microns, then mix homogeneously by the weight ratio of 5:100 with the sodium hydroxide solution that concentration is 2.5 weight %, then in microwave dissolver, at 130 DEG C, carry out micro-wave digestion 25 minutes. Wherein, the microwave frequency used by micro-wave digestion is 2.45GHz, and pressure used is 0.3MPa. The micro-wave digestion product obtained is transferred in hydrolysis vessels, and with the hydrochloric acid that concentration is 5 weight %, its pH value is adjusted to 4.5, it is subsequently adding the cellulase of the 5 weight % that weight is cellulose containing raw material dry weight used (purchased from Chemical Reagent Co., Ltd., Sinopharm Group, model is the examination of BR(Shanghai)), it is hydrolyzed 96 hours at 40 DEG C. After hydrolysis terminates, solids removed by filtration residue, obtain the solution containing reducing sugar. After measured, the productivity of reducing sugar is 96.0%.
Embodiment 5
This embodiment is for illustrating the method that employing cellulose containing raw material provided by the invention prepares reducing sugar.
Rice straw is dried at 105 DEG C so that it is in water content be 1.4 weight %. And the rice straw obtained is ground into the particle diameter powder less than 220 microns, then mix homogeneously by the weight ratio of 6:100 with the ammonia that concentration is 4.0 weight %, then in microwave dissolver, at 140 DEG C, carry out micro-wave digestion 10 minutes. Wherein, the microwave frequency used by micro-wave digestion is 2.45GHz, and pressure used is 0.5MPa. The micro-wave digestion product obtained is transferred in hydrolysis vessels, and with the sulfuric acid solution that concentration is 5 weight %, its pH value is adjusted to 4.2, it is subsequently adding the cellulase of the 3.5 weight % that weight is cellulose containing raw material dry weight used (purchased from Chemical Reagent Co., Ltd., Sinopharm Group, model is the examination of BR(Shanghai)), it is hydrolyzed 78 hours at 45 DEG C. After hydrolysis terminates, solids removed by filtration residue, obtain the solution containing reducing sugar. After measured, the productivity of reducing sugar is 91.8%.
Embodiment 6
This embodiment is for illustrating the method that employing cellulose containing raw material provided by the invention prepares reducing sugar.
Prepare reducing sugar according to the method for embodiment 1, be 80 DEG C the difference is that, the condition of described micro-wave digestion includes temperature, pressure is 0.06MPa, microwave frequency be 2.45GHz, time is 10 minutes. Obtain the solution containing reducing sugar. After measured, reducing sugar yield is 78.5%.
Embodiment 7
This embodiment is for illustrating the method that employing cellulose containing raw material provided by the invention prepares reducing sugar.
Prepare reducing sugar according to the method for embodiment 1, the difference is that, rice straw is dried at 90 DEG C so that it is in water content be 10 weight %. Obtain the solution containing reducing sugar. After measured, reducing sugar yield is 84.2%.
Comparative example 1
This comparative example is for illustrating the method adopting cellulose containing raw material to prepare reducing sugar of reference.
Reducing sugar is prepared according to the method for embodiment 7, the difference is that, in cellulose containing raw material preprocessing process, the mixture obtained after not mixed with sodium hydroxide solution by cellulose containing raw material carries out micro-wave digestion process, specifically comprises the following steps that
Rice straw is dried at 90 DEG C so that it is in water content be 10 weight %. And the rice straw obtained is ground into the particle diameter powder less than 212 microns, mix homogeneously by the weight ratio of 2:100 with the sodium hydroxide solution that concentration is 1.0 weight % again, then at 100 DEG C, continue stirring mixing 5 minutes, again the micro-wave digestion product obtained is transferred in hydrolysis vessels, with the sulfuric acid solution that concentration is 5 weight %, its pH value is adjusted to 4.5, it is subsequently adding the cellulase of the 4 weight % that weight is cellulose containing raw material dry weight used (purchased from Chemical Reagent Co., Ltd., Sinopharm Group, model is the examination of BR(Shanghai)), it is hydrolyzed 84 hours at 45 DEG C.After hydrolysis terminates, sedimentation filtration removes solid residue, obtains the solution containing reducing sugar. After measured, reducing sugar yield is 58.6%.
Comparative example 2
This comparative example is for illustrating the method adopting cellulose containing raw material to prepare reducing sugar of reference.
Reducing sugar is prepared according to the method for embodiment 7, the difference is that, do not include the step processed by crushed products sodium hydroxide solution, but directly crushed products micro-wave digestion is processed. Obtain the solution containing reducing sugar. After measured, reducing sugar yield is 16.8%.
From the result of above example and comparative example it can be seen that adopt method provided by the invention to prepare reducing sugar, it is possible to significantly improve the productivity of reducing sugar. From contrast with embodiment 6 and 7 of embodiment 1 it can be seen that when the optimal way adopting the present invention prepares reducing sugar, it is possible to improve the productivity of reducing sugar, more prospects for commercial application further. Additionally, the present invention adopts microwave heating to substitute conventional vapor and heating in water bath, reaction carries out in hermetic container, and not only energy consumption is low, condition is relatively mild, but also it is short to shorten the process time, reduces production cost.
The preferred embodiment of the present invention described in detail above; but, the present invention is not limited to the detail in above-mentioned embodiment, in the technology concept of the present invention; technical scheme can being carried out multiple simple variant, these simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, it is possible to be combined by any suitable mode. In order to avoid unnecessary repetition, various possible compound modes are no longer illustrated by the present invention separately.
Additionally, can also carry out combination in any between the various different embodiment of the present invention, as long as it is without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (5)
1. one kind adopts the method that cellulose containing raw material prepares reducing sugar, the method is hydrolyzed after including mixing pretreated cellulose containing raw material with cellulase, it is characterized in that, the method of described pretreatment carries out micro-wave digestion after including mixing described cellulose containing raw material with alkaline solution, the condition of described micro-wave digestion include temperature be 100-150 DEG C, pressure is 0.1-0.8MPa, microwave frequency be 2-3GHz, time is 5-30 minute; The method of described pretreatment is additionally included in before being mixed with alkaline solution by described cellulose containing raw material, is pulverized by described cellulose containing raw material; The water content of described cellulose containing raw material is less than 2 weight %; Described cellulose containing raw material is pulverized the particle diameter of the crushed products obtained less than 550 microns; The concentration of described alkaline solution is 0.1-5 weight %; The weight ratio of described crushed products and alkaline solution is 1-10:100.
2. method according to claim 1, wherein, the alkali in described alkaline solution is selected from one or more in sodium hydroxide, potassium hydroxide, Lithium hydrate, barium hydroxide, manganous hydroxide, zinc hydroxide, sodium carbonate, potassium carbonate, lithium carbonate and ammonia.
3. method according to claim 1 and 2, wherein, with the dry weight basis of every gram of cellulose containing raw material, the consumption of described cellulase is 1-5 weight %.
4. method according to claim 1 and 2, wherein, the condition of described hydrolysis include temperature be 35-45 DEG C, pH value be 4-5, time be 60-100 hour.
5. method according to claim 1, wherein, described cellulose containing raw material is selected from one or more in corn straw, wheat stalk, rice straw, Caulis Sacchari sinensis straw, Sorghum vulgare Pers. straw, cotton stalk, beanstalk and Herba Eichhorniae.
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