CN102690897A - Two-step hydrolysis method for preparing reducing sugars with cellulose - Google Patents
Two-step hydrolysis method for preparing reducing sugars with cellulose Download PDFInfo
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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 the cellulose hydrolysis method, be specifically related to a kind of two one-step hydrolysis methods of preparation of cellulose reducing sugar.
Background technology
Along with the energy and environment problem becomes increasingly conspicuous, effectively utilize biological material to become one of hot fields of current research.At present, be used to produce alcohol fuel such as raw materials such as W-Gum, sugarcane and beets.But, since be applicable to the farmlands of these farm crop limited and with the competition of humans and animals food chain, are unsustainable generations to the utilization of these biological materials.And Mierocrystalline cellulose is a natural reproducible resource the abundantest on the earth, and annual output surpasses 1,000 hundred million tons, surpasses existing oil reserves, realizes that Mierocrystalline cellulose substitutes petrochemical industry resource acquisition Chemicals and fuel is the strategic requirement that guarantees national resources and energy security.
Mierocrystalline cellulose is the linear natural polymer of being made up of through the link of β-1,4 glycosidic link glucose unit.Hydroxyl in the Mierocrystalline cellulose be prone to intramolecularly or the plain molecule of adjacent fiber on oxy radical form hydrogen bond, these hydrogen bonds make Mierocrystalline cellulose form the highly stable crystalline texture of configuration easily, thereby make cellulosic orientation transform into technological difficulties.Therefore, seek a kind of economy, effectively the cellulose hydrolysis method is to realize the key point of cellulose conversion.
Cellulolytic method commonly used at present is acid hydrolyzation, supercritical water hydrolysis and enzymolysis process.Wherein, mineral acid and enzymic hydrolysis technology are the traditional methods of cellulose hydrolysis, reach problems such as environmental pollution is serious greatly but acid hydrolyzation exists sour consumption; Enzymolysis process exists speed slow, problems such as the separation of enzyme, activity control difficulty.Therefore, more and more scholars adopts quick, efficient, green technology for hydrolyzing to carry out cellulosic Study on Transformation, and for example multiple green technology for hydrolyzing such as supercritical water, ionic liquid, solid acid are applied to cellulosic hydrolysis conversion.
Ehara and Saka adopt the associating technology for hydrolyzing of supercritical water and subcritical water first, obtain 35.6% hexose productive rate (K.Ehara and S.Saka, J.Wood.Sci, 2005,51,148-153.).Supercritical water have speed of reaction fast, need not characteristics such as catalyzer, but should technology in the HTHP severe condition, cellulosic hydrolysis is difficult to control; The poor selectivity of reducing sugar; Productive rate is low, and by product is many, thereby has increased the 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 the ionic liquid hydrocellulose to obtain 90% above glucose productive rate, but ionic liquid and glucose separation difficulty, deficiency such as cost an arm and a leg have hindered its extensive development.
Solid acid is used 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 the research that Mierocrystalline cellulose shortening in water medium prepares polyvalent alcohol, but the noble metal catalyst that adopts at present costs an arm and a leg.(Hara et al.J.Am.Chem.Soc.2008 such as Hara; 130,12787-12793.) with (Onda et al.Green Chemistry 2008,10 such as Onda; 1033.) adopt sulfonated solid acid; Hydrolysis prepares glucose under the no hydrogen effect, but deficiency such as these Preparation of catalysts processes are complicated, the solid acid catalyst consumption is big is unfavorable for the scale operation of cellulose hydrolysis.
Summary of the invention
, problems such as enzymic hydrolysis cost high, solid acid catalyst preparation complicated, supercritical water hydrolysis poor selectivity and hydrolysate separation difficulty big to liquid mineral acid consumption in the prior art the invention provides a kind of two one-step hydrolysis methods of preparation of cellulose reducing sugar.
A kind of two one-step hydrolysis methods of preparation of cellulose reducing sugar comprise the steps:
(1) cellulose dissolution is obtained cellulose solution in solvent; In said cellulose solution, Mierocrystalline cellulose contacts with water under first catalyst action and carries out the first step hydrolysis, hydrolyzed solution; In said hydrolyzed solution, add precipitation agent, the post precipitation separation obtains throw out;
(2) be that medium adds second catalyzer with water with the throw out that obtains in the step (1), carry out second one-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.
For realizing hydrolysis reaction, in cellulose solution, add first catalyzer and water in the step (1), as preferably, the middle Mierocrystalline cellulose of said step (1) is 2 ~ 8:1 with the quality ratio; The solvent of dissolving cellulos is that N,N-DIMETHYLACETAMIDE/LiCl, NaOH/ urea, mass percent concentration are 81 ~ 85% phosphate aqueous solution, ionic liquid, ZnCl
2At least a in the aqueous solution.
In the solvent of dissolving cellulos if contain metal chloride and can significantly improve cellulosic percent hydrolysis, this be because: 1) hydrolysis of metals ion has reduced the pH value of system, has promoted cellulosic hydrolysis; 2) metals ion is prone to exists with hydrated ion in water, and this hydrated ion can the plain swelling of accelerating fibers, destroys cellulosic crystalline structure, thereby accelerates cellulosic hydrolysis reaction; 3) Cl
-Have very strong hydrogen bond ability to accept, can with the hydrogen evolution hydrogen bond on the Mierocrystalline cellulose hydroxyl, promote cellulosic dissolving.
Ionic liquid is in the test of dissolving cellulos; Good characteristics such as solvent temperature is low, dissolution process is easy, dissolution time is short, dissolving is recyclable have been embodied; And ionic liquid is a Mierocrystalline cellulose non-derivative solvent, and Mierocrystalline cellulose need not activation just can be mixed directly with it and dissolve.
Certain density mineral acid, sodium hydroxide/thiocarbamide and sodium hydroxide/urea is direct dissolving cellulos also.
First catalyzer in the said step (1) is liquid acid, solid acid, alkali or metal chloride;
Said liquid acid is at least a in sulfuric acid, phosphoric acid, hydrochloric acid, nitric acid, acetic acid, the formic acid;
Said solid acid is Amberlyst, acid zeolite, modified clay or ion exchange resin;
Said alkali is at least a in sodium hydroxide, the Pottasium Hydroxide;
In mass, described solid acid consumption is 10% ~ 50% of a Mierocrystalline cellulose quality; Described liquid acid consumption is 10% ~ 30% of a Mierocrystalline cellulose quality; Described metal chloride is 10% ~ 50% of a Mierocrystalline cellulose quality.
Said the first step hydrolysis temperature is 40 ~ 100 ℃, and the first step hydrolysis time is 5 ~ 180min.
Under the certain situation of acidity, cellulosic hydrolysis conversion is relevant with hydrolysising reacting temperature and hydrolysis time: under the certain situation of hydrolysis time and catalyzer, hydrolysis reaction has its best temperature scope; Under the certain situation of other conditions; The reducing sugar yield raises with the increase of hydrolysis time; But this relation is not unlimited, and along with the growth of hydrolysis time, Mierocrystalline cellulose constantly is converted into reducing sugar; But a large amount of reducing sugars is converted into by product simultaneously, and the reducing sugar yield is constantly descended.
Precipitation agent in the said step (1) is one or more in the cyclic ethers of aliphatic ether, C4 ~ C8 of ketone, the C2 ~ C8 of alcohol, the C2 ~ C8 of C1 ~ C8; The volume ratio of described precipitation agent and said solvent is 2 ~ 5:1.
As preferably, described precipitation agent is methyl alcohol, ethanol, propyl alcohol, propyl carbinol, isopropylcarbinol, acetone, butanone, ether or THF.
Mierocrystalline cellulose under first catalyst action, carries out the first step hydrolysis and obtains the Mierocrystalline cellulose oligopolymer after said dissolution with solvents, and this Mierocrystalline cellulose oligomer structure is similar with cellulosic structure, also has similar solvability.Therefore, in said solvent, break this oligopolymer crystalline texture through hydrogen bond competition effect between solvent and the Mierocrystalline cellulose oligomer molecules chain and dissolve.After adding precipitation agent such as ethanol, acetone isopolarity material, hydrogen bond action is destroyed and precipitates between former solvent and this oligopolymer.Receive the effect of extraneous power in the process that sinks to the bottom and suppress the rearrangement of molecular chain, thereby obtain amorphous structure.
Hydrolyzed solution in the said step (1) after the first step hydrolysis carries out post precipitation through the solvent that contains alcohol, ketone, ether structure, promptly gets intermediate product Mierocrystalline cellulose oligose (being described throw out) through common filtering separation method, is metamict.
The cellosolve, precipitation agent and first catalyzer that use in the said step (1) can separate, recycle through common distillation or underpressure distillation.
Said second catalyzer is at least a in liquid acid and the solid acid; Said liquid acid is sulfuric acid, hydrochloric acid, phosphoric acid, formic acid, acetic acid or nitric acid; Said solid acid is Amberlyst, acid zeolite, modified clay or ion exchange resin;
In mass, said liquid acid consumption is 1.5% ~ 12% of a Mierocrystalline cellulose quality; Said solid acid consumption is 10 ~ 50% of a Mierocrystalline cellulose quality; Be 15 ~ 20 times of Mierocrystalline cellulose quality as the water consumption of medium in said second one-step hydrolysis.Wherein, described liquid acid can with water medium be mixed with behind the liquid acid aqueous solution with step (1) in the throw out that obtains carry out second one-step hydrolysis and obtain reducing sugar.
The middle liquid acid of using of said step (2) can adopt in the alkali perhaps passes through the chromatographic column Separation and Recovery with the back as fermentation culture, and solid acid is through common filtering separation.
The second one-step hydrolysis temperature in the said step (2) is 100 ~ 160 ℃, and the second one-step hydrolysis time was 30 ~ 120min.
As preferably, the said second one-step hydrolysis temperature is 160 ℃, and the second one-step hydrolysis time was 120min.
The present invention has the following advantages: the cellulose solution that uses in the first step hydrolytic process, first catalyzer and precipitation agent can effectively separate recycling; The second one-step hydrolysis condition is gentle relatively, hydrolysis time is short, the acid catalyst consumption is few; Can prepare high-concentration reduced sugar solution, subsequent disposal is simple etc.
Description of drawings
Fig. 1 is two one-step hydrolysis method route synoptic diagram of a kind of preparation of cellulose reducing sugar of the present invention;
The XRD figure of the Mierocrystalline cellulose oligose that Fig. 2 obtains for Mierocrystalline cellulose among the embodiment 14 and the first step hydrolysis.
Embodiment
Adopt the DNS method to confirm reducing sugar content in the two one-step hydrolysis methods of preparation of cellulose reducing sugar of the present invention, the concrete principle of DNS method is following:
Reducing sugars such as the cellobiose that cellulose hydrolysis produces, glucose can be with 3 under alkaline condition; 5-dinitrosalicylic acid (DNS) reduction generates 3-amino-5-nitrosalicylic acid, and this product shows red-brown under the condition of boiling; With its characteristic photoabsorption of spectrophotometry; Have maximum absorption at the 540nm place, the colour intensity of the amount of reducing sugar and reaction solution relation in direct ratio is utilized the 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 ℃, stirs the 15min fusion, adds the 2.5g Mierocrystalline cellulose subsequently; Obtain cellulose solution after stirring 30min, stir the adding 0.5g first catalyst A mberlyst A-15 down, 0.75g water; Under 90 ℃, carry out the first step hydrolysis 15min; Get hydrolyzed solution, in hydrolyzed solution, add precipitation agent isopropylcarbinol 200mL and separate out the Mierocrystalline cellulose oligopolymer, the Mierocrystalline cellulose oligopolymer that filtration washing obtains places 40mL water; Add the 1g second catalyst A mberlyst A-15, carry out second one-step hydrolysis reaction 2h under 160 ℃ of conditions.The 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 ℃, stirs the 15min fusion, adds the 2.5g Mierocrystalline cellulose subsequently; Obtain cellulose solution after stirring 30min, stir the adding 0.5g first catalyst A mberlyst A-15 down, 0.75g water; Under 90 ℃, carry out the first step hydrolysis 25min; Get hydrolyzed solution, in hydrolyzed solution, add precipitation agent isopropylcarbinol 200mL and separate out the Mierocrystalline cellulose oligopolymer, the Mierocrystalline cellulose oligopolymer that filtration washing obtains places 40mL water; Add the 1g second catalyst A mberlyst A-15, carry out second one-step hydrolysis reaction 2h under 160 ℃ of conditions.The 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 ℃, stirs the 15min fusion, adds the 2.5g Mierocrystalline cellulose subsequently; Obtain cellulose solution after stirring 30min, stir the adding 0.5g first catalyst A mberlyst A-15 down, 0.75g water; Under 90 ℃, carry out the first step hydrolysis 35min; Get hydrolyzed solution, in hydrolyzed solution, add precipitation agent isopropylcarbinol 200mL and separate out the Mierocrystalline cellulose oligopolymer, the Mierocrystalline cellulose oligopolymer that filtration washing obtains places 40mL water; Add the 1g second catalyst A mberlyst A-15, carry out second one-step hydrolysis reaction 2h under 160 ℃ of conditions.The 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 ℃, stirs the 15min fusion, adds the 2.5g Mierocrystalline cellulose subsequently; Obtain cellulose solution after stirring 30min, stir the adding 0.5g first catalyst A mberlyst A-15 down, 0.75g water; Under 90 ℃, carry out the first step hydrolysis 45min; Get hydrolyzed solution, in hydrolyzed solution, add precipitation agent isopropylcarbinol 200mL and separate out the Mierocrystalline cellulose oligopolymer, the Mierocrystalline cellulose oligopolymer that filtration washing obtains places 40mL water; Add the 1g second catalyst A mberlyst A-15, carry out second one-step hydrolysis reaction 2h under 160 ℃ of conditions.The 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 ℃, stirs the 15min fusion, adds the 2.5g Mierocrystalline cellulose subsequently; Obtain cellulose solution after stirring 30min, stir the adding 0.5g first catalyst A mberlyst A-15 down, 0.75g water; Under 90 ℃, carry out the first step hydrolysis 35min; Get hydrolyzed solution, in hydrolyzed solution, add precipitation agent isopropylcarbinol 200mL and separate out the Mierocrystalline cellulose oligopolymer, the Mierocrystalline cellulose oligopolymer that filtration washing obtains places 40mL water; Add the 1g second catalyst A mberlyst A-15, carry out second one-step hydrolysis reaction 1h under 160 ℃ of conditions.The 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 ℃, stirs the 15min fusion, adds the 2.5g Mierocrystalline cellulose subsequently; Obtain cellulose solution after stirring 30min, stir the adding 0.5g first catalyst A mberlyst A-15 down, 0.75g water; Under 90 ℃, carry out the first step hydrolysis 35min; Get hydrolyzed solution, in hydrolyzed solution, add precipitation agent isopropylcarbinol 200mL and separate out the Mierocrystalline cellulose oligopolymer, the Mierocrystalline cellulose oligopolymer that filtration washing obtains places 40mL water; Add the 1g second catalyst A mberlyst A-15, carry out second one-step hydrolysis reaction 2h under 140 ℃ of conditions.The 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 the 15min fusion, adds the 2.5g Mierocrystalline cellulose subsequently, obtains cellulose solution behind the stirring 30min, stirring the slow down 1g of the adding first catalyst quality percentage concentration is 50%H
2SO
4(first catalyst levels is with H for the aqueous solution
2SO
4Meter; Water in this dilute sulphuric acid then can be thought to supply water and separates reaction and add), at 90 ℃ of following hydrolysis 35min, hydrolyzed solution; In hydrolyzed solution, add precipitation agent isopropylcarbinol 200mL and separate out the Mierocrystalline cellulose oligopolymer; The Mierocrystalline cellulose oligopolymer that filtration washing obtains places 40mL water, adds the 1g second catalyst A mberlyst A-15, carries out second one-step hydrolysis reaction 2h under 160 ℃ of conditions.The 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 the 15min fusion, adds the 2.5g Mierocrystalline cellulose subsequently, obtains cellulose solution behind the stirring 30min, stirring the slow down 1g of the adding first catalyst quality percentage concentration is 50%H
2SO
4The aqueous solution; Under 90 ℃, carry out the first step hydrolysis 15min; Get hydrolyzed solution, in hydrolyzed solution, add precipitation agent isopropylcarbinol 200mL and separate out the Mierocrystalline cellulose oligopolymer, the Mierocrystalline cellulose oligopolymer that filtration washing obtains places 40mL water; Add the 1g second catalyst A mberlyst A-15, carry out second one-step hydrolysis reaction 2h under 160 ℃ of conditions.The 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 the 15min fusion, adds the 2.5g Mierocrystalline cellulose subsequently, obtains cellulose solution behind the stirring 30min, stirring the slow down 1g of the adding first catalyst quality percentage concentration is 50%H
2SO
4The aqueous solution; Under 90 ℃, carry out the first step hydrolysis 15min; Get hydrolyzed solution, in hydrolyzed solution, add precipitation agent isopropylcarbinol 200mL and separate out the Mierocrystalline cellulose oligopolymer, the Mierocrystalline cellulose oligopolymer that filtration washing obtains places 40mL water; Add the 1.5g second catalyst A mberlyst A-15, carry out second one-step hydrolysis reaction 2h under 160 ℃ of conditions.The DNS method is measured reducing sugar yield and is reached 70.4%.
Be heated to 90 ℃ 12.5g reclaim ionic liquid (1-ethyl-3-Methylimidazole villaumite), stir the 15min fusion, add the 2.5g Mierocrystalline cellulose subsequently, obtain cellulose solution behind the stirring 30min, slowly adding the 1g first catalyst quality percentage concentration under stirring is 50%H
2SO
4The aqueous solution; Carry out the first step hydrolysis 15min; Get hydrolyzed solution, in hydrolyzed solution, add precipitation agent isopropylcarbinol 200mL and separate out the Mierocrystalline cellulose oligopolymer, the Mierocrystalline cellulose oligopolymer that filtration washing obtains places 40mL water; Add the 1.5g second catalyst A mberlyst A-15, carry out second one-step hydrolysis reaction 2h under 160 ℃ of conditions.The 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 ℃, stirs the 15min fusion, adds the 10g Mierocrystalline cellulose subsequently; Obtain cellulose solution after stirring 30min; Stir the slow down 150g of adding N,N-DIMETHYLACETAMIDE, 10gLiCl, the 1g first catalyst A mberlyst A-15,1.8g water, carry out the first step hydrolysis 60min, get hydrolyzed solution; In hydrolyzed solution, add precipitation agent isopropylcarbinol 400mL and separate out the Mierocrystalline cellulose oligopolymer; The Mierocrystalline cellulose oligopolymer that filtration washing obtains places 40mL water, adds the 1g second catalyst A mberlyst A-15, carries out second one-step hydrolysis reaction 2h under 160 ℃ of conditions.The DNS method is measured reducing sugar yield and is reached 62.0%.
Embodiment 12
100g 65% solder(ing)acid is heated to 70 ℃, stirs down to add the 2.5g Mierocrystalline cellulose, dissolves about 60min; Stir the slow down 1g of the adding first catalyst A mberlyst A-15, be warming up to 100 ℃, carry out the first step hydrolysis 60min to get hydrolyzed solution; In hydrolyzed solution, add 200mL precipitation agent ethanol and separate out deposition; The solid that filtration washing obtains places 40mL water, adds the 1g second catalyst A mberlyst A-15, carries out second one-step hydrolysis reaction 2h under 160 ℃ of conditions.The DNS method is measured reducing sugar yield and is reached 43.2%.
Embodiment 13
The 100g65% solder(ing)acid is heated to 70 ℃, stirs down to add the 2.5g Mierocrystalline cellulose, dissolves about 60min; Stir the slow down 1g of the adding first catalyst A mberlyst A-15, be warming up to 85 ℃, carry out the first step hydrolysis 60min; Get hydrolyzed solution, in hydrolyzed solution, add 200mL precipitation agent ethanol and separate out deposition, the solid that filtration washing obtains places 40mL water; Add the 1g second catalyst A mberlyst A-15, carry out second one-step hydrolysis reaction 2h under 160 ℃ of conditions.The DNS method is measured reducing sugar yield and is reached 52.9%.
Embodiment 14
Stirring action adds the 10g Mierocrystalline cellulose down in the 100mL85% phosphoric acid ice-water bath, stirs 60min and obtains viscous solution, adds 1.0g first catalyzer 98% sulfuric acid subsequently; Carry out the first step hydrolysis 60min under 40 ℃; Get hydrolyzed solution, in hydrolyzed solution, add 400mL precipitation agent acetone precipitation and separate out the Mierocrystalline cellulose oligopolymer, the Mierocrystalline cellulose oligopolymer that filtration washing obtains places 100mL water; Add the 4g second catalyst A mberlyst A-15, carry out second one-step hydrolysis reaction 2h under 160 ℃ of conditions.The DNS method is measured reducing sugar yield and is reached 45.2%.
Embodiment 15
Stirring action adds the 10g Mierocrystalline cellulose down in the 100mL85% phosphoric acid ice-water bath; Stir 60min and obtain viscous solution; Add 1.0g first catalyzer 98% sulfuric acid subsequently, carry out the first step hydrolysis 30min under 80 ℃, hydrolyzed solution; In hydrolyzed solution, add 400mL precipitation agent acetone precipitation and separate out the Mierocrystalline cellulose oligopolymer, it is 0.6%H that the Mierocrystalline cellulose oligopolymer that filtration washing obtains places the 200g mass percentage concentration
2SO
4The aqueous solution carries out second one-step hydrolysis reaction 2h under 160 ℃ of conditions.The DNS method is measured reducing sugar yield and is reached 47.6%.
Embodiment 16
Stirring action adds the 10g Mierocrystalline cellulose down in the 100mL85% phosphoric acid ice-water bath; Stir 60min and obtain viscous solution; Add 1.0g first catalyzer 98% sulfuric acid subsequently, carry out the first step hydrolysis 30min under 65 ℃, hydrolyzed solution; In hydrolyzed solution, add 400mL precipitation agent acetone precipitation and separate out the Mierocrystalline cellulose oligopolymer, it is 0.6%H that the Mierocrystalline cellulose oligopolymer that filtration washing obtains places the 200g mass percentage concentration
2SO
4The aqueous solution reacts 2h under 160 ℃ of conditions.The DNS method is measured reducing sugar yield and is reached 52.6%.
Claims (10)
1. two one-step hydrolysis methods of a preparation of cellulose reducing sugar is characterized in that, comprise the steps:
(1) cellulose dissolution is obtained cellulose solution in solvent; In said cellulose solution, Mierocrystalline cellulose contacts with water under first catalyst action and carries out the first step hydrolysis, hydrolyzed solution; In said hydrolyzed solution, add precipitation agent, the post precipitation separation obtains throw out;
(2) be that medium adds second catalyzer with water with the throw out that obtains in the step (1), carry out second one-step hydrolysis and obtain reducing sugar.
2. two one-step hydrolysis methods of preparation of cellulose reducing sugar as claimed in claim 1 is characterized in that, Mierocrystalline cellulose is 2 ~ 8:1 with the quality ratio in the said step (1); The solvent of dissolving cellulos is that N,N-DIMETHYLACETAMIDE/LiCl, NaOH/ urea, mass percent concentration are at least a in 81 ~ 85% phosphate aqueous solution, ionic liquid, the ZnCl2 aqueous solution.
3. two one-step hydrolysis methods of preparation of cellulose reducing sugar as claimed in claim 2 is characterized in that, among said N,N-DIMETHYLACETAMIDE/LiCl, the mass ratio of N,N-DIMETHYLACETAMIDE and LiCl is 15:1; In the NaOH/ urea, the mass ratio of NaOH and urea is 7:12.
4. two one-step hydrolysis methods of preparation of cellulose reducing sugar as claimed in claim 1 is characterized in that first catalyzer in the said step (1) is liquid acid, solid acid, alkali or metal chloride;
Said liquid acid is at least a in sulfuric acid, phosphoric acid, hydrochloric acid, nitric acid, acetic acid, the formic acid;
Said solid acid is Amberlyst, acid zeolite, modified clay or ion exchange resin;
Said alkali is at least a in sodium hydroxide, the Pottasium Hydroxide.
5. two one-step hydrolysis methods of preparation of cellulose reducing sugar as claimed in claim 4 is characterized in that, in mass, described solid acid consumption is 10 ~ 50% of a Mierocrystalline cellulose quality; The consumption of described liquid acid or alkali is 10 ~ 30% of a Mierocrystalline cellulose quality; The metal chloride consumption is 10 ~ 50% of a Mierocrystalline cellulose quality.
6. two one-step hydrolysis methods of preparation of cellulose reducing sugar as claimed in claim 1 is characterized in that said the first step hydrolysis temperature is 40 ~ 100 ℃, and the first step hydrolysis time is 5 ~ 180min.
7. two one-step hydrolysis methods of preparation of cellulose reducing sugar as claimed in claim 1 is characterized in that, the precipitation agent in the said step (1) is one or more in the cyclic ethers of aliphatic ether, C4 ~ C8 of ketone, the C2 ~ C8 of alcohol, the C2 ~ C8 of C1 ~ C8; The volume ratio of described precipitation agent and said solvent is 2 ~ 5:1.
8. two one-step hydrolysis methods of preparation of cellulose reducing sugar as claimed in claim 7 is characterized in that described precipitation agent is methyl alcohol, ethanol, propyl alcohol, propyl carbinol, isopropylcarbinol, acetone, butanone, ether or THF.
9. two one-step hydrolysis methods of preparation of cellulose reducing sugar as claimed in claim 1 is characterized in that said second catalyzer is at least a in liquid acid and the solid acid; Said liquid acid is sulfuric acid, hydrochloric acid, phosphoric acid, formic acid, acetic acid or nitric acid; Said solid acid is Amberlyst, acid zeolite, modified clay or ion exchange resin;
Said liquid acid consumption is 1.5% ~ 12% of a Mierocrystalline cellulose quality; Said solid acid consumption is 10 ~ 50% of a Mierocrystalline cellulose quality; Be 15 ~ 20 times of Mierocrystalline cellulose quality as the water consumption of medium in said second one-step hydrolysis.
10. two one-step hydrolysis methods of preparation of cellulose reducing sugar as claimed in claim 1 is characterized in that, the second one-step hydrolysis temperature in the said step (2) is 100 ~ 160 ℃, and the second one-step hydrolysis time was 30 ~ 120min.
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| CN106755612A (en) * | 2017-03-16 | 2017-05-31 | 南开大学 | A kind of technique by lignocellulose biomass by hydrolyzation saccharogenesis |
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| CN116813806A (en) * | 2023-07-14 | 2023-09-29 | 北京理工大学 | Preparation method of monodisperse cellooligosaccharide |
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