CN102690897B - Two-step hydrolysis method for preparing reducing sugars with cellulose - Google Patents
Two-step hydrolysis method for preparing reducing sugars with cellulose Download PDFInfo
- Publication number
- CN102690897B CN102690897B CN201210163175.5A CN201210163175A CN102690897B CN 102690897 B CN102690897 B CN 102690897B CN 201210163175 A CN201210163175 A CN 201210163175A CN 102690897 B CN102690897 B CN 102690897B
- Authority
- CN
- China
- Prior art keywords
- mierocrystalline cellulose
- cellulose
- add
- catalyst
- step hydrolysis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Abstract
The invention discloses a two-step hydrolysis method for preparing reducing sugars with cellulose, comprising the following steps: step (1) of dissolving the cellulose into a solvent to obtain a cellulose solution; in the cellulose solution, enabling the cellulose to contact water by the action of a first catalyst to perform a first-step hydrolysis and obtain hydrolysate; adding a precipitator into the hydrolysate, and separating after precipitating to obtain precipitate; step (2) of adding a second catalyst in the precipitate obtained in the step (1) by utilizing water as a medium to perform a second-step hydrolysis and obtain the reducing sugars, wherein productivity of the reducing sugars reaches 40-85%. The invention further discloses application of the two-step hydrolysis method for preparing reducing sugars with cellulose in fermentation and preparation for compounds such as ethanol, lactic acid and so on in the carbohydrate industry. Cellulose solvent, catalyst and precipitator utilized by the invention can effectively separated and used repeatedly; hydrolysis condition is relatively mild; dosage of acid catalysts is less; and the method is featured with simple operation, low energy consumption, fast reaction and high productivity.
Description
Technical field
The present invention relates to cellulose hydrolysis method, be specifically related to the two one-step hydrolysis methods that a kind of Mierocrystalline cellulose is prepared reducing sugar.
Background technology
Along with energy and environment problem becomes increasingly conspicuous, effectively utilize biological material to become one of hot fields of current research.At present, raw materials such as W-Gum, sugarcane and beet for the production of alcohol fuel.But, due to be applicable to the farmlands of these farm crop limited and with the competition of humans and animals food chain, to the utilization of these biological materials, are unsustainable generations.And Mierocrystalline cellulose is natural reproducible resource the abundantest on the earth, annual output exceedes 1,000 hundred million tons, exceedes existing oil reserves, and realizing the alternative petrochemical industry resource acquisition Chemicals of Mierocrystalline cellulose and fuel is the strategic requirement that guarantees national resources and energy security.
Mierocrystalline cellulose is linked the linear natural polymer forming by β-Isosorbide-5-Nitrae glycosidic link by glucose unit.Hydroxyl in Mierocrystalline cellulose easily with molecule in or oxy radical formation hydrogen bond on the plain molecule of adjacent fiber, these hydrogen bonds make Mierocrystalline cellulose easily form the highly stable crystalline texture of configuration, thereby make cellulosic orientation transform into technological difficulties.Therefore, find a kind of economy, effectively cellulose hydrolysis method is to realize the key point of cellulose conversion.
Conventional cellulolytic method is acid hydrolyzation, supercritical water hydrolysis and enzymolysis process at present.Wherein, mineral acid and hydrolysis technology are the traditional methods of cellulose hydrolysis, but acid hydrolyzation exists the problems such as the large and environmental pollution of sour consumption is serious; Enzymolysis process exists speed slow, the problem such as the separation of enzyme, activity control difficulty.Therefore, increasing scholar adopts quick, efficient, green technology for hydrolyzing to carry out cellulosic Study on Transformation, and the multiple green technology for hydrolyzing such as such as supercritical water, ionic liquid, solid acid are applied to cellulosic hydrolysis.
Ehara and Saka adopt the technology for hydrolyzing of combining of supercritical water and subcritical water first, obtain the productive rate (K.Ehara and S.Saka, J.Wood.Sci, 2005,51,148-153.) of 35.6% hexose.Supercritical water have speed of reaction fast, without features such as catalyzer, but this technology is in High Temperature High Pressure severe condition, and cellulosic hydrolysis is difficult to control, the poor selectivity of reducing sugar, productive rate is low, and by product is many, thereby has increased complicacy and the cost of subsequent processes.
Ionic liquid is cellulosic green solvent, Binder and Raines(J.B.Binder and R.T.Raines, PNAS, 2010,107,4516-4521.) adopt ionic liquid hydrocellulose to obtain 90% above glucose productive rate, but ionic liquid and glucose separation difficulty, the deficiency such as expensive have hindered its extensive development.
Solid acid is for cellulosic hydrolysis, efficiently solve the recovery problem of catalyzer, Fukuoka and Dhepe(Fukuoka and Dhepe.Angew.Chem.Int.Ed., 2006,45 (31), 5161-5163.) reported that Mierocrystalline cellulose shortening in water medium prepares the research of polyvalent alcohol, but the noble metal catalyst adopting is at present expensive.(the Hara et al.J.Am.Chem.Soc.2008 such as Hara, 130,12787-12793.) and (the Onda et al.Green Chemistry 2008 such as Onda, 10,1033.) adopt sulfonated solid acid, under no hydrogen effect, glucose is prepared in hydrolysis, but the deficiency such as the preparation process complexity of these catalyzer, solid acid catalyst consumption be large is unfavorable for the scale operation of cellulose hydrolysis.
Summary of the invention
For liquid mineral acid consumption in prior art is large, enzymic hydrolysis cost is high, solid acid catalyst preparation is complicated, supercritical water is hydrolyzed the problems such as poor selectivity and hydrolysate separation difficulty, the invention provides the two one-step hydrolysis methods that a kind of Mierocrystalline cellulose is prepared reducing sugar.
Mierocrystalline cellulose is prepared two one-step hydrolysis methods of reducing sugar, comprises the steps:
(1) cellulose dissolution is obtained to cellulose solution in solvent, in described cellulose solution, Mierocrystalline cellulose contacts and carries out the first step hydrolysis with water under the first catalyst action, obtains hydrolyzed solution, in described hydrolyzed solution, add precipitation agent, after precipitation, separate and be precipitated thing;
(2) throw out obtaining in step (1) is added to the second catalyzer take water as medium, carry out second step hydrolysis and obtain reducing sugar.
Described Mierocrystalline cellulose derives from paper pulp, Microcrystalline Cellulose, absorbent cotton, bagasse, agricultural crop straw etc., and wherein agricultural crop straw occupies larger proportion.
In step (1), for realizing hydrolysis reaction, in cellulose solution, add the first catalyzer and water, as preferably, in described step (1), Mierocrystalline cellulose is 2 ~ 8:1 with quality ratio; The solvent of dissolving cellulos is phosphate aqueous solution, ionic liquid, the ZnCl that N,N-DIMETHYLACETAMIDE/LiCl, NaOH/ urea, mass percent concentration are 81 ~ 85%
2at least one in the aqueous solution.
If contain metal chloride in the solvent of dissolving cellulos, can significantly improve cellulosic percent hydrolysis, this be because: 1) hydrolysis of metal ion has reduced the pH value of system, has promoted cellulosic hydrolysis; 2) metal ion easily exists with hydrated ion in water, and what this hydrated ion can accelerating fibers element is swelling, destroys cellulosic crystalline structure, thereby accelerates cellulosic hydrolysis reaction; 3) Cl
-there is very strong hydrogen bond ability to accept, can with Mierocrystalline cellulose hydroxyl on hydrogen evolution hydrogen bond, promote cellulosic dissolving.
Ionic liquid is in the test of dissolving cellulos, embodied that solvent temperature is low, dissolution process is easy, dissolution time is short, dissolve the good characteristics such as recyclable, and ionic liquid is Mierocrystalline cellulose non-derivative solvent, Mierocrystalline cellulose just can mix directly and dissolve with it without activation.
Also direct dissolving cellulos of certain density mineral acid, sodium hydroxide/thiocarbamide and sodium hydroxide/urea.
The first catalyzer in described step (1) is liquid acid, solid acid, alkali or metal chloride;
Described liquid acid is at least one in sulfuric acid, phosphoric acid, hydrochloric acid, nitric acid, acetic acid, formic acid;
Described solid acid is Amberlyst, acid zeolite, modified clay or ion exchange resin;
Described alkali is at least one in sodium hydroxide, potassium hydroxide;
In mass, described solid acid consumption is 10% ~ 50% of Mierocrystalline cellulose quality; Described liquid acid consumption is 10% ~ 30% of Mierocrystalline cellulose quality; Described metal chloride is 10% ~ 50% of Mierocrystalline cellulose quality.
Described the first step hydrolysis temperature is 40 ~ 100 ℃, and the first step hydrolysis time is 5 ~ 180min.
In the situation that acidity is certain, cellulosic hydrolysis conversion and hydrolysising reacting temperature and hydrolysis time about: at hydrolysis time and catalyzer, certain in the situation that, hydrolysis reaction has its best temperature range; In the situation that other conditions are certain, Reducing sugar raises with the increase of hydrolysis time, but this relation is not unlimited, along with the growth of hydrolysis time, Mierocrystalline cellulose is constantly converted into reducing sugar, but a large amount of reducing sugars is converted into by product simultaneously, and Reducing sugar is constantly declined.
One or more in the aliphatic ether of the alcohol that precipitation agent in described step (1) is C1 ~ C8, the ketone of C2 ~ C8, C2 ~ C8, the cyclic ethers of C4 ~ C8; Described precipitation agent and the volume ratio of described solvent are 2 ~ 5:1.
As preferably, described precipitation agent is methyl alcohol, ethanol, propyl alcohol, propyl carbinol, isopropylcarbinol, acetone, butanone, ether or tetrahydrofuran (THF).
Mierocrystalline cellulose, after described dissolution with solvents, under the first catalyst action, carries out the first step hydrolysis and obtains Mierocrystalline cellulose oligopolymer, and this Mierocrystalline cellulose oligomer structure is similar to cellulosic structure, also has similar solvability.Therefore,, in described solvent, by hydrogen bond Competition between solvent and Mierocrystalline cellulose oligomer molecules chain, break this oligopolymer crystalline texture and dissolve.After adding precipitation agent as ethanol, acetone isopolarity material, between former solvent and this oligopolymer, hydrogen bond action is destroyed and precipitate.In the process sinking to the bottom, be subject to the effect of extraneous power and the rearrangement of Inhibitory molecules chain, thereby obtain amorphous structure.
Hydrolyzed solution in described step (1) after the first step hydrolysis, after precipitating containing the solvent of alcohol, ketone, ether structure, obtains intermediate product Mierocrystalline cellulose oligose (i.e. described throw out) through common filtering separation method, is metamict.
Cellosolve, precipitation agent and the first catalyzer using in described step (1) can by common distillation or underpressure distillation carry out separate, recycle.
Described the second catalyzer is at least one in liquid acid and solid acid; Described liquid acid is sulfuric acid, hydrochloric acid, phosphoric acid, formic acid, acetic acid or nitric acid; Described solid acid is Amberlyst, acid zeolite, modified clay or ion exchange resin;
In mass, described liquid acid consumption is 1.5% ~ 12% of Mierocrystalline cellulose quality; Described solid acid consumption is 10 ~ 50% of Mierocrystalline cellulose quality; In the hydrolysis of described second step, as the water consumption of medium, be 15 ~ 20 times of Mierocrystalline cellulose quality.Wherein, described liquid acid can with water medium be mixed with after the liquid acid aqueous solution with step (1) in the throw out that obtains carry out second step hydrolysis and obtain reducing sugar.
The liquid acid of using in described step (2) can adopt in alkali and be rear as fermentation culture or by chromatographic column Separation and Recovery, solid acid is by common filtering separation.
Second step hydrolysis temperature in described step (2) is 100 ~ 160 ℃, and second step hydrolysis time is 30 ~ 120min.
As preferably, described second step hydrolysis temperature is 160 ℃, and second step hydrolysis time is 120min.
The present invention has the following advantages: cellulose solution, the first catalyzer and the precipitation agent using in the first step hydrolytic process can effectively separate recycling; Second step hydrolysising condition is relatively gentle, hydrolysis time is short, acid catalyst consumption is few; Can prepare high-concentration reduced sugar solution, subsequent disposal is simple etc.
Accompanying drawing explanation
Fig. 1 is the two one-step hydrolysis method route schematic diagram that a kind of Mierocrystalline cellulose of the present invention is prepared reducing sugar;
Fig. 2 is the XRD figure that in embodiment 14, Mierocrystalline cellulose and the first step are hydrolyzed the Mierocrystalline cellulose oligose obtaining.
Embodiment
Adopt DNS method to determine that Mierocrystalline cellulose of the present invention prepares reducing sugar content in two one-step hydrolysis methods of reducing sugar, the concrete principle of DNS method is as follows:
The reducing sugars such as the cellobiose, glucose that cellulose hydrolysis produces can be by 3 under alkaline condition, 5-dinitrosalicylic acid (DNS) reduction, generate 3-amino-5-NITROSALICYLIC ACID, this product is aobvious red-brown under the condition of boiling, with its characteristic photoabsorption of spectrophotometry, at 540nm place, have maximum absorption, the amount of reducing sugar and the colour intensity of reaction solution relation in direct ratio, utilize colorimetric method for determining reducing sugar content within the specific limits.
Embodiment 1
12.5g ionic liquid (1-ethyl-3-methylimidazole villaumite) is heated to 90 ℃, stir 15min melting, add subsequently 2.5g Mierocrystalline cellulose, after stirring 30min, obtain cellulose solution, under stirring, add 0.5g the first catalyst A mberlyst A-15, 0.75g water, at 90 ℃, carry out the first step hydrolysis 15min, obtain hydrolyzed solution, in hydrolyzed solution, add precipitation agent isopropylcarbinol 200mL to separate out Mierocrystalline cellulose oligopolymer, the Mierocrystalline cellulose oligopolymer that filtration washing obtains is placed in 40mL water, add 1g the second catalyst A mberlyst A-15, under 160 ℃ of conditions, carry out second step hydrolysis reaction 2h.DNS method is measured reducing sugar yield and is reached 70.4%.
Embodiment 2
12.5g ionic liquid (1-ethyl-3-methylimidazole villaumite) is heated to 90 ℃, stir 15min melting, add subsequently 2.5g Mierocrystalline cellulose, after stirring 30min, obtain cellulose solution, under stirring, add 0.5g the first catalyst A mberlyst A-15, 0.75g water, at 90 ℃, carry out the first step hydrolysis 25min, obtain hydrolyzed solution, in hydrolyzed solution, add precipitation agent isopropylcarbinol 200mL to separate out Mierocrystalline cellulose oligopolymer, the Mierocrystalline cellulose oligopolymer that filtration washing obtains is placed in 40mL water, add 1g the second catalyst A mberlyst A-15, under 160 ℃ of conditions, carry out second step hydrolysis reaction 2h.DNS method is measured reducing sugar yield and is reached 76.8%.
Embodiment 3
12.5g ionic liquid (1-ethyl-3-methylimidazole villaumite) is heated to 90 ℃, stir 15min melting, add subsequently 2.5g Mierocrystalline cellulose, after stirring 30min, obtain cellulose solution, under stirring, add 0.5g the first catalyst A mberlyst A-15, 0.75g water, at 90 ℃, carry out the first step hydrolysis 35min, obtain hydrolyzed solution, in hydrolyzed solution, add precipitation agent isopropylcarbinol 200mL to separate out Mierocrystalline cellulose oligopolymer, the Mierocrystalline cellulose oligopolymer that filtration washing obtains is placed in 40mL water, add 1g the second catalyst A mberlyst A-15, under 160 ℃ of conditions, carry out second step hydrolysis reaction 2h.DNS method is measured reducing sugar yield and is reached 81.4%.
Embodiment 4
12.5g ionic liquid (1-ethyl-3-methylimidazole villaumite) is heated to 90 ℃, stir 15min melting, add subsequently 2.5g Mierocrystalline cellulose, after stirring 30min, obtain cellulose solution, under stirring, add 0.5g the first catalyst A mberlyst A-15, 0.75g water, at 90 ℃, carry out the first step hydrolysis 45min, obtain hydrolyzed solution, in hydrolyzed solution, add precipitation agent isopropylcarbinol 200mL to separate out Mierocrystalline cellulose oligopolymer, the Mierocrystalline cellulose oligopolymer that filtration washing obtains is placed in 40mL water, add 1g the second catalyst A mberlyst A-15, under 160 ℃ of conditions, carry out second step hydrolysis reaction 2h.DNS method is measured reducing sugar yield and is reached 75.7%.
Embodiment 5
12.5g ionic liquid (1-ethyl-3-methylimidazole villaumite) is heated to 90 ℃, stir 15min melting, add subsequently 2.5g Mierocrystalline cellulose, after stirring 30min, obtain cellulose solution, under stirring, add 0.5g the first catalyst A mberlyst A-15, 0.75g water, at 90 ℃, carry out the first step hydrolysis 35min, obtain hydrolyzed solution, in hydrolyzed solution, add precipitation agent isopropylcarbinol 200mL to separate out Mierocrystalline cellulose oligopolymer, the Mierocrystalline cellulose oligopolymer that filtration washing obtains is placed in 40mL water, add 1g the second catalyst A mberlyst A-15, under 160 ℃ of conditions, carry out second step hydrolysis reaction 1h.DNS method is measured reducing sugar yield and is reached 76.1%.
Embodiment 6
12.5g ionic liquid (1-ethyl-3-methylimidazole villaumite) is heated to 90 ℃, stir 15min melting, add subsequently 2.5g Mierocrystalline cellulose, after stirring 30min, obtain cellulose solution, under stirring, add 0.5g the first catalyst A mberlyst A-15, 0.75g water, at 90 ℃, carry out the first step hydrolysis 35min, obtain hydrolyzed solution, in hydrolyzed solution, add precipitation agent isopropylcarbinol 200mL to separate out Mierocrystalline cellulose oligopolymer, the Mierocrystalline cellulose oligopolymer that filtration washing obtains is placed in 40mL water, add 1g the second catalyst A mberlyst A-15, under 140 ℃ of conditions, carry out second step hydrolysis reaction 2h.DNS method is measured reducing sugar yield and is reached 46%.
Embodiment 7
12.5g ionic liquid (1-ethyl-3-methylimidazole villaumite) is heated to 90 ℃, stirs 15min melting, adds subsequently 2.5g Mierocrystalline cellulose, after stirring 30min, obtains cellulose solution, and under stirring, slowly adding 1g the first catalyst quality percentage concentration is 50%H
2sO
4(the first catalyst levels is with H for the aqueous solution
2sO
4meter, water in this dilute sulphuric acid can be thought to add for hydrolysis reaction), at 90 ℃, be hydrolyzed 35min, obtain hydrolyzed solution, in hydrolyzed solution, add precipitation agent isopropylcarbinol 200mL to separate out Mierocrystalline cellulose oligopolymer, the Mierocrystalline cellulose oligopolymer that filtration washing obtains is placed in 40mL water, adds 1g the second catalyst A mberlyst A-15, carries out second step hydrolysis reaction 2h under 160 ℃ of conditions.DNS method is measured reducing sugar yield and is reached 43.2%.
Embodiment 8
12.5g ionic liquid (1-ethyl-3-methylimidazole villaumite) is heated to 90 ℃, stirs 15min melting, adds subsequently 2.5g Mierocrystalline cellulose, after stirring 30min, obtains cellulose solution, and under stirring, slowly adding 1g the first catalyst quality percentage concentration is 50%H
2sO
4the aqueous solution, at 90 ℃, carry out the first step hydrolysis 15min, obtain hydrolyzed solution, in hydrolyzed solution, add precipitation agent isopropylcarbinol 200mL to separate out Mierocrystalline cellulose oligopolymer, the Mierocrystalline cellulose oligopolymer that filtration washing obtains is placed in 40mL water, add 1g the second catalyst A mberlyst A-15, under 160 ℃ of conditions, carry out second step hydrolysis reaction 2h.DNS method is measured reducing sugar yield and is reached 58.7%.
Embodiment 9
12.5g ionic liquid (1-ethyl-3-methylimidazole villaumite) is heated to 90 ℃, stirs 15min melting, adds subsequently 2.5g Mierocrystalline cellulose, after stirring 30min, obtains cellulose solution, and under stirring, slowly adding 1g the first catalyst quality percentage concentration is 50%H
2sO
4the aqueous solution, at 90 ℃, carry out the first step hydrolysis 15min, obtain hydrolyzed solution, in hydrolyzed solution, add precipitation agent isopropylcarbinol 200mL to separate out Mierocrystalline cellulose oligopolymer, the Mierocrystalline cellulose oligopolymer that filtration washing obtains is placed in 40mL water, add 1.5g the second catalyst A mberlyst A-15, under 160 ℃ of conditions, carry out second step hydrolysis reaction 2h.DNS method is measured reducing sugar yield and is reached 70.4%.
12.5g reclaims ionic liquid (1-ethyl-3-methylimidazole villaumite) and is heated to 90 ℃, stirs 15min melting, adds subsequently 2.5g Mierocrystalline cellulose, after stirring 30min, obtains cellulose solution, and under stirring, slowly adding 1g the first catalyst quality percentage concentration is 50%H
2sO
4the aqueous solution, carry out the first step hydrolysis 15min, obtain hydrolyzed solution, in hydrolyzed solution, add precipitation agent isopropylcarbinol 200mL to separate out Mierocrystalline cellulose oligopolymer, the Mierocrystalline cellulose oligopolymer that filtration washing obtains is placed in 40mL water, add 1.5g the second catalyst A mberlyst A-15, under 160 ℃ of conditions, carry out second step hydrolysis reaction 2h.DNS method is measured reducing sugar yield and is reached 56.7%.
Embodiment 11
40g ionic liquid (1-ethyl-3-methylimidazole villaumite) is heated to 90 ℃, stir 15min melting, add subsequently 10g Mierocrystalline cellulose, after stirring 30min, obtain cellulose solution, under stirring, slowly add 150g N,N-DIMETHYLACETAMIDE, 10gLiCl, 1g the first catalyst A mberlyst A-15, 1.8g water, carry out the first step hydrolysis 60min, obtain hydrolyzed solution, in hydrolyzed solution, add precipitation agent isopropylcarbinol 400mL to separate out Mierocrystalline cellulose oligopolymer, the Mierocrystalline cellulose oligopolymer that filtration washing obtains is placed in 40mL water, add 1g the second catalyst A mberlyst A-15, under 160 ℃ of conditions, carry out second step hydrolysis reaction 2h.DNS method is measured reducing sugar yield and is reached 62.0%.
Embodiment 12
100g 65% solder(ing)acid is heated to 70 ℃, under stirring, add 2.5g Mierocrystalline cellulose, 60min dissolves left and right, under stirring, slowly add 1g the first catalyst A mberlyst A-15, be warming up to 100 ℃, carry out the first step hydrolysis 60min and obtain hydrolyzed solution, in hydrolyzed solution, add 200mL precipitation agent ethanol to separate out precipitation, the solid that filtration washing obtains is placed in 40mL water, adds 1g the second catalyst A mberlyst A-15, carries out second step hydrolysis reaction 2h under 160 ℃ of conditions.DNS method is measured reducing sugar yield and is reached 43.2%.
Embodiment 13
100g65% solder(ing)acid is heated to 70 ℃, under stirring, add 2.5g Mierocrystalline cellulose, 60min dissolves left and right, slowly adds 1g the first catalyst A mberlyst A-15 under stirring, is warming up to 85 ℃, carry out the first step hydrolysis 60min, obtain hydrolyzed solution, in hydrolyzed solution, add 200mL precipitation agent ethanol to separate out precipitation, the solid that filtration washing obtains is placed in 40mL water, add 1g the second catalyst A mberlyst A-15, under 160 ℃ of conditions, carry out second step hydrolysis reaction 2h.DNS method is measured reducing sugar yield and is reached 52.9%.
Embodiment 14
In 100mL85% phosphoric acid ice-water bath, under stirring action, add 10g Mierocrystalline cellulose, stir 60min and obtain viscous solution, add subsequently 1.0g the first catalyzer 98% sulfuric acid, at 40 ℃, carry out the first step hydrolysis 60min, obtain hydrolyzed solution, in hydrolyzed solution, add 400mL precipitation agent acetone precipitation to separate out Mierocrystalline cellulose oligopolymer, the Mierocrystalline cellulose oligopolymer that filtration washing obtains is placed in 100mL water, add 4g the second catalyst A mberlyst A-15, under 160 ℃ of conditions, carry out second step hydrolysis reaction 2h.DNS method is measured reducing sugar yield and is reached 45.2%.
Embodiment 15
In 100mL85% phosphoric acid ice-water bath, under stirring action, add 10g Mierocrystalline cellulose, stir 60min and obtain viscous solution, add subsequently 1.0g the first catalyzer 98% sulfuric acid, at 80 ℃, carry out the first step hydrolysis 30min, obtain hydrolyzed solution, in hydrolyzed solution, add 400mL precipitation agent acetone precipitation to separate out Mierocrystalline cellulose oligopolymer, it is 0.6%H that the Mierocrystalline cellulose oligopolymer that filtration washing obtains is placed in 200g mass percentage concentration
2sO
4the aqueous solution, carries out second step hydrolysis reaction 2h under 160 ℃ of conditions.DNS method is measured reducing sugar yield and is reached 47.6%.
Embodiment 16
In 100mL85% phosphoric acid ice-water bath, under stirring action, add 10g Mierocrystalline cellulose, stir 60min and obtain viscous solution, add subsequently 1.0g the first catalyzer 98% sulfuric acid, at 65 ℃, carry out the first step hydrolysis 30min, obtain hydrolyzed solution, in hydrolyzed solution, add 400mL precipitation agent acetone precipitation to separate out Mierocrystalline cellulose oligopolymer, it is 0.6%H that the Mierocrystalline cellulose oligopolymer that filtration washing obtains is placed in 200g mass percentage concentration
2sO
4the aqueous solution, reacts 2h under 160 ℃ of conditions.DNS method is measured reducing sugar yield and is reached 52.6%.
Claims (4)
1. Mierocrystalline cellulose is prepared two one-step hydrolysis methods of reducing sugar, it is characterized in that, comprises the steps:
12.5g ionic liquid 1-ethyl-3-methylimidazole villaumite is heated to 90 ℃, stir 15min melting, add subsequently 2.5g Mierocrystalline cellulose, after stirring 30min, obtain cellulose solution, under stirring, add 0.5g the first catalyst A mberlyst A-15, 0.75g water, at 90 ℃, carry out the first step hydrolysis 25min, obtain hydrolyzed solution, in hydrolyzed solution, add precipitation agent isopropylcarbinol 200mL to separate out Mierocrystalline cellulose oligopolymer, the Mierocrystalline cellulose oligopolymer that filtration washing obtains is placed in 40mL water, add 1g the second catalyst A mberlyst A-15, under 160 ℃ of conditions, carry out second step hydrolysis reaction 2h, obtain reducing sugar.
2. Mierocrystalline cellulose is prepared two one-step hydrolysis methods of reducing sugar, it is characterized in that, comprises the steps:
12.5g ionic liquid 1-ethyl-3-methylimidazole villaumite is heated to 90 ℃, stir 15min melting, add subsequently 2.5g Mierocrystalline cellulose, after stirring 30min, obtain cellulose solution, under stirring, add 0.5g the first catalyst A mberlyst A-15, 0.75g water, at 90 ℃, carry out the first step hydrolysis 35min, obtain hydrolyzed solution, in hydrolyzed solution, add precipitation agent isopropylcarbinol 200mL to separate out Mierocrystalline cellulose oligopolymer, the Mierocrystalline cellulose oligopolymer that filtration washing obtains is placed in 40mL water, add 1g the second catalyst A mberlyst A-15, under 160 ℃ of conditions, carry out second step hydrolysis reaction 2h, obtain reducing sugar.
3. Mierocrystalline cellulose is prepared two one-step hydrolysis methods of reducing sugar, it is characterized in that, comprises the steps:
12.5g ionic liquid 1-ethyl-3-methylimidazole villaumite is heated to 90 ℃, stir 15min melting, add subsequently 2.5g Mierocrystalline cellulose, after stirring 30min, obtain cellulose solution, under stirring, add 0.5g the first catalyst A mberlyst A-15, 0.75g water, at 90 ℃, carry out the first step hydrolysis 45min, obtain hydrolyzed solution, in hydrolyzed solution, add precipitation agent isopropylcarbinol 200mL to separate out Mierocrystalline cellulose oligopolymer, the Mierocrystalline cellulose oligopolymer that filtration washing obtains is placed in 40mL water, add 1g the second catalyst A mberlyst A-15, under 160 ℃ of conditions, carry out second step hydrolysis reaction 2h, obtain reducing sugar.
4. Mierocrystalline cellulose is prepared two one-step hydrolysis methods of reducing sugar, it is characterized in that, comprises the steps:
12.5g ionic liquid 1-ethyl-3-methylimidazole villaumite is heated to 90 ℃, stir 15min melting, add subsequently 2.5g Mierocrystalline cellulose, after stirring 30min, obtain cellulose solution, under stirring, add 0.5g the first catalyst A mberlyst A-15, 0.75g water, at 90 ℃, carry out the first step hydrolysis 35min, obtain hydrolyzed solution, in hydrolyzed solution, add precipitation agent isopropylcarbinol 200mL to separate out Mierocrystalline cellulose oligopolymer, the Mierocrystalline cellulose oligopolymer that filtration washing obtains is placed in 40mL water, add 1g the second catalyst A mberlyst A-15, under 160 ℃ of conditions, carry out second step hydrolysis reaction 1h, obtain reducing sugar.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210163175.5A CN102690897B (en) | 2012-05-22 | 2012-05-22 | Two-step hydrolysis method for preparing reducing sugars with cellulose |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210163175.5A CN102690897B (en) | 2012-05-22 | 2012-05-22 | Two-step hydrolysis method for preparing reducing sugars with cellulose |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102690897A CN102690897A (en) | 2012-09-26 |
| CN102690897B true CN102690897B (en) | 2014-04-23 |
Family
ID=46856634
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210163175.5A Active CN102690897B (en) | 2012-05-22 | 2012-05-22 | Two-step hydrolysis method for preparing reducing sugars with cellulose |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102690897B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9695484B2 (en) | 2012-09-28 | 2017-07-04 | Industrial Technology Research Institute | Sugar products and fabrication method thereof |
| CN103710472B (en) * | 2012-09-28 | 2016-07-06 | 财团法人工业技术研究院 | Sugar products and methods of making the same |
| CN103966367B (en) | 2013-02-01 | 2016-01-20 | 财团法人工业技术研究院 | Process for the preparation of saccharides |
| CN103382512B (en) * | 2013-07-16 | 2014-09-17 | 中国科学院宁波材料技术与工程研究所 | Glucose preparation method by hydrolyzing cellulose through microwave heating |
| CN105755883B (en) * | 2016-02-22 | 2017-11-10 | 北京林业大学 | A kind of method for improving lignocellulosic material enzymolysis efficiency and lignin recovery rate |
| CN106222314B (en) * | 2016-08-31 | 2020-04-03 | 中国科学院广州能源研究所 | Method for hydrolyzing biomass in two steps by using carbon-based solid acid catalyst |
| CN106755612A (en) * | 2017-03-16 | 2017-05-31 | 南开大学 | A kind of technique by lignocellulose biomass by hydrolyzation saccharogenesis |
| CN107501357A (en) * | 2017-08-01 | 2017-12-22 | 华南理工大学 | A kind of cellulose fermentable sugars and preparation method and application |
| CN108285475A (en) * | 2017-09-29 | 2018-07-17 | 华东理工大学 | A kind of method of pure cellulose degradation |
| CN108251568A (en) * | 2018-01-10 | 2018-07-06 | 中国科学院宁波材料技术与工程研究所 | A kind of method of the microwave-driven effectively hydrolyzing cellulose with synchronous cooling |
| CN112961126A (en) * | 2021-03-01 | 2021-06-15 | 安徽金轩科技有限公司 | Method for synthesizing furfural |
| CN113637037A (en) * | 2021-08-18 | 2021-11-12 | 华南农业大学 | Oligo-glucose and preparation method thereof |
| WO2024060407A1 (en) * | 2022-09-23 | 2024-03-28 | 浙江大学杭州国际科创中心 | Method for processing lignocelluloses to produce d-glucaric acid |
| CN116813806A (en) * | 2023-07-14 | 2023-09-29 | 北京理工大学 | Preparation method of monodisperse cellooligosaccharide |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157445A (en) * | 2007-09-18 | 2008-04-09 | 陈培豪 | Method for reclaiming sulphuric acid from plant cellulose material concentrated acid hydrolysate |
| CN101289817A (en) * | 2007-04-20 | 2008-10-22 | 中国科学院大连化学物理研究所 | Process for effectively hydrolyzing cellulose in ion liquid |
| CN101495658A (en) * | 2006-05-25 | 2009-07-29 | 贝尔法斯特女王大学 | Conversion method |
| CN101514375A (en) * | 2008-02-20 | 2009-08-26 | 青岛生物能源与过程研究所 | Method for preparing reducing sugar by catalyzing hydrocellulose |
| CN101597654A (en) * | 2009-06-23 | 2009-12-09 | 云天化集团有限责任公司 | A kind of method of utilizing protoplasm material to prepare reducing sugar |
| CN101675172A (en) * | 2007-04-25 | 2010-03-17 | 丰田自动车株式会社 | Plant-fiber-material transformation method |
-
2012
- 2012-05-22 CN CN201210163175.5A patent/CN102690897B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101495658A (en) * | 2006-05-25 | 2009-07-29 | 贝尔法斯特女王大学 | Conversion method |
| CN101289817A (en) * | 2007-04-20 | 2008-10-22 | 中国科学院大连化学物理研究所 | Process for effectively hydrolyzing cellulose in ion liquid |
| CN101675172A (en) * | 2007-04-25 | 2010-03-17 | 丰田自动车株式会社 | Plant-fiber-material transformation method |
| CN101157445A (en) * | 2007-09-18 | 2008-04-09 | 陈培豪 | Method for reclaiming sulphuric acid from plant cellulose material concentrated acid hydrolysate |
| CN101514375A (en) * | 2008-02-20 | 2009-08-26 | 青岛生物能源与过程研究所 | Method for preparing reducing sugar by catalyzing hydrocellulose |
| CN101597654A (en) * | 2009-06-23 | 2009-12-09 | 云天化集团有限责任公司 | A kind of method of utilizing protoplasm material to prepare reducing sugar |
Non-Patent Citations (4)
| Title |
|---|
| Anantharam P. Dadi et al..Enhancement of Cellulose Saccharification Kinetics Using an Ionic Liquid Pretreatment Step.《Biotechnology and Bioengineering》.2006,第95卷(第5期),904-910. |
| Enhancement of Cellulose Saccharification Kinetics Using an Ionic Liquid Pretreatment Step;Anantharam P. Dadi et al.;《Biotechnology and Bioengineering》;20060817;第95卷(第5期);904-910 * |
| 刘振 等.离子液体预处理的纤维素酶解糖化.《应用化学》.2009,第26卷(第9期),1111-1113. |
| 离子液体预处理的纤维素酶解糖化;刘振 等;《应用化学》;20090930;第26卷(第9期);1111-1113 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102690897A (en) | 2012-09-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102690897B (en) | Two-step hydrolysis method for preparing reducing sugars with cellulose | |
| Chen et al. | Co-production of oligosaccharides and fermentable sugar from wheat straw by hydrothermal pretreatment combined with alkaline ethanol extraction | |
| Han et al. | An integrated biorefinery process for adding values to corncob in co-production of xylooligosaccharides and glucose starting from pretreatment with gluconic acid | |
| CN101855368B (en) | Process for preparing a sugar product | |
| Guo et al. | Heteropoly acids enhanced neutral deep eutectic solvent pretreatment for enzymatic hydrolysis and ethanol fermentation of Miscanthus x giganteus under mild conditions | |
| EP2582820B1 (en) | Enzymatic hydrolysis of cellulose | |
| CN101525355B (en) | Method for preparing xylose and arabinose by hydrolyzing lignocellulose | |
| CN107164424A (en) | It is a kind of to aoxidize the lignocellulose pretreatment method that delignification improves enzyme hydrolysis rate | |
| CN103237896A (en) | Enzymatic hydrolysis of lignocellulosic material in the presence of sulfite, dithionite and/or dithiothreitol | |
| CN102517403B (en) | Method for preparing hemicellulose oligosaccharide by high-temperature liquid water | |
| CN104894188B (en) | A kind of preprocess method of enzymatic saccharification bagasse | |
| CN104498562A (en) | Method for pretreating agricultural waste biomass by adopting sodium hydroxide/urea/water system | |
| Yang et al. | Delignification of poplar for xylo-oligosaccharides production using lactic acid catalysis | |
| CN101161666B (en) | Method for preparing main hydrolysate by hydrolyzing plant fiber material with concentrated sulfuric acid | |
| CN105603021B (en) | A method of cigarette stalk hydrolysis result is improved using surfactant | |
| CN103382512B (en) | Glucose preparation method by hydrolyzing cellulose through microwave heating | |
| Ying et al. | Lignin removal improves xylooligosaccharides production from poplar by acetic acid hydrolysis | |
| CN104888655B (en) | Wood fibre glycosyl surfactant active and preparation method thereof | |
| CN103146781B (en) | A kind of Cotton stalk hydrolysate and preparation method thereof | |
| CN105385722B (en) | A method of pretreatment wood fiber biomass improves its sugar yield | |
| CN102613581A (en) | Method for extracting dietary cellulose from manioc slag | |
| CN106755198B (en) | Method for producing sugar by hydrolyzing agricultural and forestry biomass raw material thick mash | |
| CN103881115B (en) | A kind of method strengthening enzymolysis process extraction tobacco leaf xylogen | |
| CN101565468B (en) | Method for producing xylo-oligosaccharide by utilizing cotton seed hulls | |
| CN106191168B (en) | Method for preparing high-concentration fermentation sugar solution by using lignocellulose as raw material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |