CN102617287A - Method for preparing hexitol or hydroxy-acetone - Google Patents
Method for preparing hexitol or hydroxy-acetone Download PDFInfo
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- CN102617287A CN102617287A CN2012100413433A CN201210041343A CN102617287A CN 102617287 A CN102617287 A CN 102617287A CN 2012100413433 A CN2012100413433 A CN 2012100413433A CN 201210041343 A CN201210041343 A CN 201210041343A CN 102617287 A CN102617287 A CN 102617287A
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- pyruvic alcohol
- alcohol
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Abstract
The invention discloses a method for preparing hexitol or hydroxy-acetone, which comprises the steps as follows: cellulose reacts with glucose or fructose in water under the action of hydrogen atmosphere and catalytic agents, so as to obtain hexitol or hydroxy-acetone; the catalytic agents are supported metal catalysts; active constituents of the supported metal catalysts are metal modified by modifiers; the metal is any one of Pt, Ru, Ni and Cu; and a carrier of the supported metal catalysts is any one of Al2O3, TiO2, ZrO2, SiO2 and activated charcoal. The provided method selectively obtains hexitol or hydroxy-acetone through a one-pot reaction based on cellulose and glucose or fructose, achieves simple process, rapid reaction, high efficiency and energy conservation, and is easy to industrialize; the catalytic agents can be recovered and recycled, so that the cost is saved, and environmental protection can be achieved; in addition, the method has low requirements on equipment, cannot corrode equipment, and achieves low investment.
Description
Technical field
The present invention relates to a kind of method for preparing hexitol or pyruvic alcohol.
Background technology
The biomass source is abundant, renewable, and contains carbon and hydroxy functional group, is the fossil resource substitute that has potentiality.Mierocrystalline cellulose is one of topmost composition of biomass, and its effective conversion is the important content that biomass are utilized.Mierocrystalline cellulose is that glucose monomer passes through 1,4-β-glycosidic link polymerization chaining, and interchain connects into the crystalline structure with high-polymerization degree and high-crystallinity through abundant hydrogen bond.With the Mierocrystalline cellulose depolymerization is glucose monomer, is that polyvalent alcohol is one of effective feasible way that transforms of Mierocrystalline cellulose with their hydrocrackings again.
Polyvalent alcohol is widely used in food, solvent, antifreezing agent, medicine and the makeup.Less from the method for Mierocrystalline cellulose and the efficiently synthetic polyvalent alcohol of verivate thereof at present, it is significant therefore to develop effective conversion pathway.Existent method concentrates in the production of hexitols such as sorbyl alcohol and N.F,USP MANNITOL in a large number; As utilize loading type Pt and Ru hydrogenation catalyst in high-temperature water, can cellulose conversion be hexitol, and handle the Mierocrystalline cellulose hydrogenation catalysts such as Ru, Pt or Ni that are coupled again through the chemical process that physical method such as ball milling or phosphoric acid are handled and to improve the yield of hexitol.Yet from Mierocrystalline cellulose and verivate preparation terepthaloyl moietie, 1 thereof, the method for 2-Ucar 35 and pyruvic alcohol is few.Two examples are only arranged, the Ni-W catalyzer that promptly utilizes load efficiently the catalyzed conversion Mierocrystalline cellulose for terepthaloyl moietie and utilize Ru/C and WO
3Alternative conversion Mierocrystalline cellulose is terepthaloyl moietie and 1, the 2-Ucar 35.But the method that so far, Mierocrystalline cellulose and verivate thereof is converted into pyruvic alcohol does not efficiently have report as yet.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing hexitol or pyruvic alcohol, optionally prepare the target polyvalent alcohol.
For this reason, a kind of method for preparing hexitol or pyruvic alcohol provided by the present invention comprises the steps:
Under the effect of hydrogen atmosphere and catalyzer, Mierocrystalline cellulose, glucose or fructose react in water, promptly get hexitol or pyruvic alcohol;
Said catalyzer is a load type metal catalyst, and the active ingredient of said load type metal catalyst is the metal of being modified by modifier, said metal be among Pt, Ru, Ni and the Cu any; The carrier of said load type metal catalyst is Al
2O
3, TiO
2, ZrO
2, SiO
2With in the gac any.
In the above-mentioned method, the temperature of said reaction can be 200 ℃～250 ℃, specifically can be 200 ℃ or 240 ℃, and the time can be 0.5 hour～and 5 hours, specifically can be 0.5 hour or 5 hours, pressure can be 2MPa～8Mpa, specifically can be 2MPa, 6Mpa or 8Mpa.
In the above-mentioned method, said hexitol can be sorbyl alcohol and/or N.F,USP MANNITOL.
In the above-mentioned method, said Mierocrystalline cellulose can be Microcrystalline Cellulose, cotton, paper pulp, balloonflower root or timber etc.
In the above-mentioned method, in the said load type metal catalyst, the quality percentage composition of the metal in the said active ingredient is 0.5%～50%, as 2%, 5% or 50%.
In the above-mentioned method, in the said active ingredient, said modifier can be SnO
x, CeO
x, Al
2O
x, ZnO
xAnd MgO
xIn any, wherein x is the number between 0～4, but non-vanishing.
In the above-mentioned method, in the said active ingredient, said modifier can be (0～10) with the molfraction ratio of said metal: 1, but the amount of said oxide compound is non-vanishing, specifically can be 0.3: 1,0.5: 1,4.0: 1 or 10.0: 1.
In the above-mentioned method; Said load type metal catalyst can be according to comprising the preparation of following method: in the mixture of the precursor compound of the precursor compound of said modifier and said metal, add aqueous hydrochloric acid; Add said carrier then, promptly get said catalyzer through drying, roasting and reduction; The precursor compound of said modifier is the muriate of respective metal in the said modifier; The precursor compound of said metal is the muriate of said metal.
In the above-mentioned method, the ratio of quality and the number of copies of said catalyzer and said Mierocrystalline cellulose, glucose or fructose can be (0.1～10): 1, specifically can be 0.4: 1,0.5: 1 or 2: 1.
Preparing method provided by the invention transforms Mierocrystalline cellulose, glucose or fructose under the high-temperature water condition; Through introducing Pt, Ru, Ni and the Cu even load type catalyzer that modifier is modified; Optionally be converted into hexitol or pyruvic alcohol; Can know that through embodiment low Sn/M ratio (M=Pt, Ru, Ni and Cu etc.) catalyzer can promote the glucose midbody hydrogenation that cellulose hydrolysis obtains, thereby improve the selectivity of hexitol; The glucose midbody that high Sn/M ratio catalyzer can promote cellulose hydrolysis to obtain tautomerizes to fructose, and the anti-aldol condensation of fructose generates midbodys such as Glycerose then, and these midbodys can obtain pyruvic alcohol through dehydration and hydrogenation reaction; Method provided by the invention optionally obtains hexitol or pyruvic alcohol from Mierocrystalline cellulose, glucose or fructose through one pot reaction, and process is simple, is swift in response, and is energy-efficient, is easy to industriallization; Catalyzer is recyclable, practices thrift cost, environmental protection; And this method is low for equipment requirements, and equipment is not had corrosion, invests little; Through the ratio of binary composition in the regulating catalyst, can be selectively converted to hexitol or pyruvic alcohol, as being 20% in the cellulose conversion rate, the ratio through the modulation binary composition can obtain 82.8% hexitol and 49.7% pyruvic alcohol (C respectively
3The polyvalent alcohol selectivity can reach 75%).
Embodiment
Employed experimental technique is ordinary method like no specified otherwise among the following embodiment.
Used material, reagent etc. like no specified otherwise, all can obtain from commercial sources among the following embodiment.
Method among the following embodiment is with SnO
xThe load type metal catalyst of modifying is an example, and if no special instructions, this method is equally applicable to CeO
x, Al
2O
x, ZnO
xAnd MgO
xDeng the catalyzer of modifying.
Embodiment 1, hydrocellulose prepare hexitol
Load type metal catalyst Pt-SnO
x/ Al
2O
3Preparation: with SnCl
22H
2O and H
2PtCl
66H
2O is 0.3 to mix with the molfraction ratio, drips 1 37% hydrochloric acid soln then and adds entry, adds Al behind the homogeneous solution to be formed
2O
3Be placed in 110 ℃ of baking ovens through drying at room temperature and carry out dried overnight, then successively through roasting (400 ℃ with air atmosphere in roasting 4 hours) with reduce (at 400 ℃ and 20%H
2/ N
2Atmosphere under the reduction 4 hours) promptly get.
1g Microcrystalline Cellulose (microcrystalline is available from Alfa Aesar) is placed the 100ml reaction kettle of the water (50ml) that capacity is housed, add 2% (the quality percentage composition of the metal Pt in the active ingredient) Pt-SnO of the above-mentioned preparation of 0.4g
x/ Al
2O
3(Sn/Pt=0.3, x are 0～4) charges into H
2, making the pressure in the reaction kettle is 60atm, is heated to 200 ℃, reacts 30 minutes.
According to following method, the transformation efficiency that detection fibers is plain and the selectivity of hexitol:
With not reacted Mierocrystalline cellulose weighing quality on balance, be 0.8g; Reaction product is carried out high-efficient liquid phase analysis and quantitative (Shimadazu LC-20A HPLC; Separator column: BioRad Aminex HPX-87H; Analysis condition: moving phase is 0.01M H
2SO
4, 40 ℃, 0.6ml/min); Analytical results shows that reaction product is mainly sorbyl alcohol and N.F,USP MANNITOL (hexitol), quantitatively is 0.184g, and other low amounts of product are C
2-C
5Polyvalent alcohol.
Calculate the cellulose conversion rate according to the following equation, the selectivity of reaction product and productive rate:
The result shows that the cellulose conversion rate is 19.8%, and Mierocrystalline cellulose mainly is converted into hexitol, and selectivity reaches 82.8%, and yield is 16.4%.
The cellulose conversion rate is calculated:
Wherein, the Mierocrystalline cellulose quality=Mierocrystalline cellulose of the conversion quality-Mierocrystalline cellulose residual mass that feeds intake
The selectivity of hexitol calculate (the selectivity definition by the carbon mole number of product with the ratio of carbon mole number of conversion raw material):
The calculation of yield of hexitol:
Embodiment 2, hydrocellulose prepare hexitol
Load type metal catalyst Pt-SnO
x/ Al
2O
3Preparation: concrete preparation method is with embodiment 1, and difference is: SnCl
22H
2O and H
2PtCl
66H
2The molfraction ratio of O is 0.5.
1g Microcrystalline Cellulose (microcrystalline is available from Alfa Aesar) is placed the 100ml reaction kettle of the water (50ml) that capacity is housed, add 0.4g 2%Pt-SnO
x/ Al
2O
3(Sn/Pt=0.5, x are 0～4) charges into H
2, making the pressure in the reaction kettle is 20atm, is heated to 240 ℃, reacts 30 minutes.
According to following method, the transformation efficiency that detection fibers is plain and the selectivity of hexitol:
With not reacted Mierocrystalline cellulose weighing quality on balance, be 0g; Reaction product is carried out high-efficient liquid phase analysis and quantitative (Shimadazu LC-20A HPLC; Separator column: BioRad Aminex HPX-87H; Analysis condition: moving phase is 0.01M H
2SO
4, 40 ℃, 0.6ml/min), analytical results shows that reaction product is mainly hexitol, quantitatively is 0.366g, other low amounts of product are C
2-C
5Polyvalent alcohol.
Calculate cellulose conversion rate, the selectivity of reaction product and productive rate according to embodiment 1 described formula.
The result shows that the cellulose conversion rate is 100%, and Mierocrystalline cellulose mainly is converted into hexitol, and selectivity reaches 32.6%, and yield is 32.6%.
Embodiment 3, hydrocellulose prepare pyruvic alcohol
Load type metal catalyst Pt-SnO
x/ Al
2O
3Preparation: concrete preparation method is with embodiment 1, and difference is: SnCl
22H
2O and H
2PtCl
66H
2The molfraction ratio of O is 4.0.
1g Microcrystalline Cellulose (microcrystalline is available from Alfa Aesar) is placed the 100ml reaction kettle of the water (50ml) that capacity is housed, add 0.4g 2%Pt-SnO
x/ Al
2O
3(Sn/Pt=4.0, x are 0～4) charges into H
2, making the pressure in the reaction kettle is 80atm, is heated to 200 ℃, reacts 30 minutes.
According to following method, the transformation efficiency that detection fibers is plain and the selectivity of pyruvic alcohol:
With not reacted Mierocrystalline cellulose weighing quality on balance, be 0.779g; Reaction product is carried out high-efficient liquid phase analysis and quantitative (Shimadazu LC-20A HPLC; Separator column: BioRad Aminex HPX-87H; Analysis condition: moving phase is 0.01M H
2SO
4, 40 ℃, 0.6ml/min), analytical results shows that reaction product is mainly pyruvic alcohol, quantitatively is 0.052g, other low amounts of product are C
2-C
6Polyvalent alcohol.
Calculate the cellulose conversion rate according to the following equation, the selectivity of reaction product and productive rate:
The result shows that the cellulose conversion rate is 22.1%.Mierocrystalline cellulose mainly is converted into pyruvic alcohol, and selectivity reaches 25.6%, and yield is 5.7%.
The cellulose conversion rate is calculated:
Wherein, the Mierocrystalline cellulose quality=Mierocrystalline cellulose of the conversion quality-Mierocrystalline cellulose residual mass that feeds intake
The selectivity of pyruvic alcohol calculate (the selectivity definition by the carbon mole number of product with the ratio of carbon mole number of conversion raw material):
The calculation of yield of pyruvic alcohol:
Embodiment 4, hydrocellulose prepare pyruvic alcohol
1g Microcrystalline Cellulose (microcrystalline is available from Alfa Aesar) is placed the 100ml reaction kettle of the water (50ml) that capacity is housed, add 0.4g 2%Pt-SnO
x/ Al
2O
3(Sn/Pt=4.0), charge into H
2, making the pressure in the reaction kettle is 60atm, is heated to 240 ℃, reacts 30 minutes.
According to following method, the transformation efficiency that detection fibers is plain and the selectivity of pyruvic alcohol:
With not reacted Mierocrystalline cellulose weighing quality on balance, be 0g; Reaction product is carried out high-efficient liquid phase analysis and quantitative (Shimadazu LC-20AHPLC; Separator column: BioRad Aminex HPX-87H; Analysis condition: moving phase is 0.01M H
2SO
4, 40 ℃, 0.6ml/min), analytical results shows that reaction product is mainly pyruvic alcohol, quantitatively is 0.117g, other low amounts of product are C
2-C
6Polyvalent alcohol.
Calculate cellulose conversion rate, the selectivity of reaction product and productive rate according to embodiment 3 described formula.
The result shows that the cellulose conversion rate is 100%, and Mierocrystalline cellulose mainly is converted into pyruvic alcohol, and selectivity reaches 12.8%, and yield is 12.8%.
Embodiment 5, hydrocellulose prepare pyruvic alcohol
Load type metal catalyst Pt-SnO
x/ Al
2O
3Preparation: concrete preparation method is with embodiment 1, and difference is: SnCl
22H
2O and H
2PtCl
66H
2The molfraction ratio of O is 10.0.
1g Microcrystalline Cellulose (microcrystalline is available from Alfa Aesar) is placed the 100ml reaction kettle of the water (50ml) that capacity is housed, add 0.4g 2%Pt-SnO
x/ Al
2O
3(Sn/Pt=10.0, x are 0～4) charges into H
2, making the pressure in the reaction kettle is 60atm, is heated to 240 ℃, reacts 30 minutes.
According to following method, the transformation efficiency that detection fibers is plain and the selectivity of pyruvic alcohol:
With not reacted Mierocrystalline cellulose weighing quality on balance, be 0g; Reaction product is carried out high-efficient liquid phase analysis and quantitative (Shimadazu LC-20A HPLC; Separator column: BioRad Aminex HPX-87H; Analysis condition: moving phase is 0.01M H
2SO
4, 40 ℃, 0.6ml/min), analytical results shows that reaction product is mainly pyruvic alcohol, quantitatively is 0.148g, other low amounts of product are C
2-C
6Polyvalent alcohol.
Calculate cellulose conversion rate, the selectivity of reaction product and productive rate according to embodiment 3 described formula.
The result shows that the cellulose conversion rate is 100%, and Mierocrystalline cellulose mainly is converted into pyruvic alcohol, and selectivity reaches 16.2%, and yield is 16.2%.
Embodiment 6, hydrocellulose prepare pyruvic alcohol
Load type metal catalyst Ni-SnO
x/ Al
2O
3Preparation: with SnCl
22H
2O and NiCl
26H
2O is 0.5 to mix with the molfraction ratio, drips 2 37% hydrochloric acid soln then and adds entry, adds Al behind the homogeneous solution to be formed
2O
3Be placed in 110 ℃ of baking ovens through drying at room temperature and carry out dried overnight, then successively through roasting (400 ℃ with air atmosphere in roasting 4 hours) with reduce (at 600 ℃ and 20%H
2/ N
2Atmosphere under reduction 3 hours) promptly get with reducing.
1g Microcrystalline Cellulose (microcrystalline is available from Alfa Aesar) is placed the 100ml reaction kettle of the water (50ml) that capacity is housed, add 0.4g 2%Ni-SnO
x/ Al
2O
3(Sn/Ni=0.5, x are 0～4) charges into H
2, making the pressure in the reaction kettle is 60atm, is heated to 200 ℃, reacts 5 hours.
According to following method, the transformation efficiency that detection fibers is plain and the selectivity of pyruvic alcohol:
With not reacted Mierocrystalline cellulose weighing quality on balance, be 0g; Reaction product is carried out high-efficient liquid phase analysis and quantitative (Shimadazu LC-20AHPLC; Separator column: BioRad Aminex HPX-87H; Analysis condition: moving phase is 0.01M H
2SO
4, 40 ℃, 0.6ml/min), analytical results shows that reaction product is mainly pyruvic alcohol, quantitatively is 0.300g, other low amounts of product are C
2-C
6Polyvalent alcohol.
Calculate cellulose conversion rate, the selectivity of reaction product and productive rate according to embodiment 3 described formula.
The result shows that the cellulose conversion rate is 100%, and Mierocrystalline cellulose mainly is converted into pyruvic alcohol, and selectivity reaches 32.8%, and yield is 32.8%.
Embodiment 7, hydrocellulose prepare pyruvic alcohol
1g Microcrystalline Cellulose (microcrystalline is available from Alfa Aesar) is placed the 100ml reaction kettle of the water (50ml) that capacity is housed, add 0.4g 2%Ni-SnO
x/ Al
2O
3(Sn/Ni=0.5, x are 0～4) charges into H
2, making the pressure in the reaction kettle is 60atm, is heated to 240 ℃, reacts 30 minutes.
According to following method, the transformation efficiency that detection fibers is plain and the selectivity of pyruvic alcohol:
With not reacted Mierocrystalline cellulose weighing quality on balance, be 0g; Reaction product is carried out high-efficient liquid phase analysis and quantitative (Shimadazu LC-20A HPLC; Separator column: BioRad Aminex HPX-87H; Analysis condition: moving phase is 0.01M H
2SO
4, 40 ℃, 0.6ml/min), analytical results shows that reaction product is mainly pyruvic alcohol, quantitatively is 0.319g, other low amounts of product are C
2-C
6Polyvalent alcohol.
Calculate cellulose conversion rate, the selectivity of reaction product and productive rate according to embodiment 3 described formula.
The result shows that the cellulose conversion rate is 100%, and Mierocrystalline cellulose mainly is converted into pyruvic alcohol, and selectivity reaches 34.9%, and yield is 34.9%.
Embodiment 8, hydrocellulose prepare pyruvic alcohol
1g Microcrystalline Cellulose (microcrystalline is available from Alfa Aesar) is placed the 100ml reaction kettle of the water (50ml) that capacity is housed, add 0.4g 5%Ni-SnO
x/ Al
2O
3(Sn/Ni=0.5, x are 0～4) charges into H
2, making the pressure in the reaction kettle is 60atm, is heated to 240 ℃, reacts 30 minutes.
According to following method, the transformation efficiency that detection fibers is plain and the selectivity of pyruvic alcohol:
With not reacted Mierocrystalline cellulose weighing quality on balance, be 0g; Reaction product is carried out high-efficient liquid phase analysis and quantitative (Shimadazu LC-20A HPLC; Separator column: BioRad Aminex HPX-87H; Analysis condition: moving phase is 0.01M H
2SO
4, 40 ℃, 0.6ml/min), analytical results shows that reaction product is mainly pyruvic alcohol, quantitatively is 0.332g, other low amounts of product are C
2-C
6Polyvalent alcohol.
Calculate cellulose conversion rate, the selectivity of reaction product and productive rate according to embodiment 3 described formula.
The result shows that the cellulose conversion rate is 100%, and Mierocrystalline cellulose mainly is converted into pyruvic alcohol, and selectivity reaches 36.3%, and yield is 36.3%.
Embodiment 9, hydrocellulose prepare pyruvic alcohol
1g Microcrystalline Cellulose (microcrystalline is available from Alfa Aesar) is placed the 100ml reaction kettle of the water (50ml) that capacity is housed, add 0.4g 50%Ni-SnO
x/ Al
2O
3(Sn/Ni=0.5, x are 0～4) charges into H
2, making the pressure in the reaction kettle is 60atm, is heated to 240 ℃, reacts 30 minutes.
According to following method, the transformation efficiency that detection fibers is plain and the selectivity of pyruvic alcohol:
With not reacted Mierocrystalline cellulose weighing quality on balance, be 0g; Reaction product is carried out high-efficient liquid phase analysis and quantitative (Shimadazu LC-20A HPLC; Separator column: BioRad Aminex HPX-87H; Analysis condition: moving phase is 0.01M H
2SO
4, 40 ℃, 0.6ml/min), analytical results shows that reaction product is mainly pyruvic alcohol, quantitatively is 0.358g, other low amounts of product are C
2-C
6Polyvalent alcohol.
Calculate cellulose conversion rate, the selectivity of reaction product and productive rate according to embodiment 3 described formula.
The result shows that the cellulose conversion rate is 100%, and Mierocrystalline cellulose mainly is converted into pyruvic alcohol, and selectivity reaches 39.2%, and yield is 39.2%.
Embodiment 10, hydrocellulose prepare pyruvic alcohol
Load type metal catalyst Cu-SnO
x/ Al
2O
3Preparation: with SnCl
22H
2O and CuCl
23H
2O is 0.3 to mix with the molfraction ratio, drips 2 37% hydrochloric acid soln then and adds entry, adds Al behind the homogeneous solution to be formed
2O
3Be placed in 110 ℃ of baking ovens through drying at room temperature and carry out dried overnight, then successively through roasting (400 ℃ with air atmosphere in roasting 4 hours) with reduce (at 400 ℃ and 20%H
2/ N
2Atmosphere under the reduction 4 hours) promptly get.
1g Microcrystalline Cellulose (microcrystalline is available from Alfa Aesar) is placed the 100ml reaction kettle of the water (50ml) that capacity is housed, add 0.4g 2%Cu-SnO
x/ Al
2O
3(Sn/Cu=0.3, x are 0～4) charges into H
2, making the pressure in the reaction kettle is 60atm, is heated to 200 ℃, reacts 30 minutes.
According to following method, the transformation efficiency that detection fibers is plain and the selectivity of pyruvic alcohol:
With not reacted Mierocrystalline cellulose weighing quality on balance, be 0.852g; Reaction product is carried out high-efficient liquid phase analysis and quantitative (Shimadazu LC-20A HPLC; Separator column: BioRad Aminex HPX-87H; Analysis condition: moving phase is 0.01M H
2SO
4, 40 ℃, 0.6ml/min), analytical results shows that reaction product is mainly pyruvic alcohol, quantitatively is 0.055g, other low amounts of product are C
2-C
6Polyvalent alcohol.
Calculate cellulose conversion rate, the selectivity of reaction product and productive rate according to embodiment 3 described formula.
The result shows that the cellulose conversion rate is 14.8%, and Mierocrystalline cellulose mainly is converted into pyruvic alcohol, and selectivity reaches 40.8%, and yield is 6.0%.
Embodiment 11, hydrocellulose prepare pyruvic alcohol
Load type metal catalyst Ru-SnO
x/ Al
2O
3Preparation: with SnCl
22H
2O and RuCl
3XH
2O is 0.3 to mix with the molfraction ratio, drips 2 37% hydrochloric acid soln then and adds entry, adds Al behind the homogeneous solution to be formed
2O
3Be placed in 110 ℃ of baking ovens through drying at room temperature and carry out dried overnight, then successively through roasting (400 ℃ with air atmosphere in roasting 4 hours) with reduce (at 400 ℃ and 20%H
2/ N
2Atmosphere under the reduction 4 hours) promptly get.
1g Microcrystalline Cellulose (microcrystalline is available from Alfa Aesar) is placed the 100ml reaction kettle of the water (50ml) that capacity is housed, add 0.4g 2%Ru-SnO
x/ Al
2O
3(Sn/Ru=0.3, x are 0～4) charges into H
2, making the pressure in the reaction kettle is 60atm, is heated to 200 ℃, reacts 30 minutes.
According to following method, the transformation efficiency that detection fibers is plain and the selectivity of pyruvic alcohol:
With not reacted Mierocrystalline cellulose weighing quality on balance, be 0.874g; Reaction product is carried out high-efficient liquid phase analysis and quantitative (Shimadazu LC-20A HPLC; Separator column: BioRad Aminex HPX-87H; Analysis condition: moving phase is 0.01M H
2SO
4, 40 ℃, 0.6ml/min), analytical results shows that reaction product is mainly pyruvic alcohol, quantitatively is 0.056g, other low amounts of product are C
2-C
6Polyvalent alcohol.
Calculate cellulose conversion rate, the selectivity of reaction product and productive rate according to embodiment 3 described formula.
The result shows that the cellulose conversion rate is 12.6%, and Mierocrystalline cellulose mainly is converted into pyruvic alcohol, and selectivity reaches 48.8%, and yield is 6.1%.
Embodiment 12, hydrocellulose prepare pyruvic alcohol
1g Microcrystalline Cellulose (microcrystalline is available from Alfa Aesar) is placed the 100ml reaction kettle of the water (50ml) that capacity is housed, add 0.4g 2%Ru-SnO
x/ Al
2O
3(Sn/Ru=0.3, x are 0～4) charges into H
2, making the pressure in the reaction kettle is 60atm, is heated to 240 ℃, reacts 30 minutes.
According to following method, the transformation efficiency that detection fibers is plain and the selectivity of pyruvic alcohol:
With not reacted Mierocrystalline cellulose weighing quality on balance, be 0g; Reaction product is carried out high-efficient liquid phase analysis and quantitative (Shimadazu LC-20A HPLC; Separator column: BioRad Aminex HPX-87H; Analysis condition: moving phase is 0.01M H
2SO
4, 40 ℃, 0.6ml/min), analytical results shows that reaction product is mainly pyruvic alcohol, quantitatively is 0.283g, other low amounts of product are C
2-C
6Polyvalent alcohol.
Calculate cellulose conversion rate, the selectivity of reaction product and productive rate according to embodiment 3 described formula.
The result shows that the cellulose conversion rate is 100%, and Mierocrystalline cellulose mainly is converted into pyruvic alcohol, and selectivity reaches 31.0%, and yield is 31.0%.
Embodiment 13, glucose prepare pyruvic alcohol
0.2g glucose (available from Alfa Aesar) is placed the 100ml reaction kettle of the water (50ml) that capacity is housed, add 0.4g 2%Ni-SnO
x/ Al
2O
3(Sn/Ni=0.5, x are 0～4) charges into H
2, making the pressure in the reaction kettle is 60atm, is heated to 200 ℃, reacts 30 minutes.
According to following method, detect the transformation efficiency of glucose and the selectivity of pyruvic alcohol:
Reaction product is carried out high-efficient liquid phase analysis and quantitative (Shimadazu LC-20A HPLC; Separator column: BioRad Aminex HPX-87H; Analysis condition: moving phase is 0.01M H
2SO
4, 40 ℃, 0.6ml/min), analytical results shows that glucose is 0g, and reaction product is mainly pyruvic alcohol, quantitatively is 0.087g, and other low amounts of product are C
2-C
6Polyvalent alcohol.
Calculate the selectivity and the productive rate of pyruvic alcohol according to the following equation.
The result shows that inversion rate of glucose is 100%, and glucose mainly is converted into pyruvic alcohol, and selectivity reaches 53.0%, and yield is 53.0%.
The selectivity of pyruvic alcohol is calculated:
The calculation of yield of pyruvic alcohol:
Embodiment 14, glucose prepare pyruvic alcohol
0.2g glucose (available from Alfa Aesar) is placed the 100ml reaction kettle of the water (50ml) that capacity is housed, add 0.4g 2%Ru-SnO
x/ Al
2O
3(Sn/Ru=0.3, x are 0～4) charges into H
2, making the pressure in the reaction kettle is 60atm, is heated to 200 ℃, reacts 30 minutes.
According to following method, detect the transformation efficiency of glucose and the selectivity of pyruvic alcohol:
Reaction product is carried out high-efficient liquid phase analysis and quantitative (Shimadazu LC-20A HPLC; Separator column: BioRad Aminex HPX-87H; Analysis condition: moving phase is 0.01M H
2SO
4, 40 ℃, 0.6ml/min), analytical results shows that glucose is 0g, and reaction product is mainly pyruvic alcohol, quantitatively is 0.077g, and other low amounts of product are C
2-C
6Polyvalent alcohol.
Calculate the selectivity and the productive rate of pyruvic alcohol according to embodiment 13 described formula.
The result shows that inversion rate of glucose is 100%, and glucose mainly is converted into pyruvic alcohol, and selectivity reaches 47.0%, and yield is 47.0%.
Embodiment 15, fructose prepare pyruvic alcohol
0.2g fructose (available from Alfa Aesar) is placed the 100ml reaction kettle of the water (50ml) that capacity is housed, add 0.4g 2%Ni-SnO
x/ Al
2O
3(Sn/Ni=0.5, x are 0～4) charges into H
2, making the pressure in the reaction kettle is 60atm, is heated to 200 ℃, reacts 30 minutes.
According to following method, detect the transformation efficiency of fructose and the selectivity of pyruvic alcohol:
Reaction product is carried out high-efficient liquid phase analysis and quantitative (Shimadazu LC-20A HPLC; Separator column: BioRad Aminex HPX-87H; Analysis condition: moving phase is 0.01M H
2SO
4, 40 ℃, 0.6ml/min), analytical results shows that fructose is 0g, and reaction product is mainly pyruvic alcohol, quantitatively is 0.120g, and other low amounts of product are C
2-C
6Polyvalent alcohol.
Calculate the selectivity and the productive rate of pyruvic alcohol according to the following equation.
The result shows that the fructose transformation efficiency is 100%, and fructose mainly is converted into pyruvic alcohol, and selectivity reaches 72.8%, and yield is 72.8%.
The selectivity of pyruvic alcohol is calculated:
The calculation of yield of pyruvic alcohol:
Embodiment 16, fructose prepare pyruvic alcohol
0.2g fructose (available from Alfa Aesar) is placed the 100ml reaction kettle of the water (50ml) that capacity is housed, add 0.4g 2%Ru-SnO
x/ Al
2O
3(Sn/Ru=0.3, x are 0～4) charges into H
2, making the pressure in the reaction kettle is 60atm, is heated to 200 ℃, reacts 30 minutes.According to following method, detect the transformation efficiency of fructose and the selectivity of pyruvic alcohol:
Reaction product is carried out high-efficient liquid phase analysis and quantitative (Shimadazu LC-20A HPLC; Separator column: BioRad Aminex HPX-87H; Analysis condition: moving phase is 0.01M H
2SO
4, 40 ℃, 0.6ml/min), analytical results shows that fructose is 0g, and reaction product is mainly pyruvic alcohol, quantitatively is 0.113g, and other low amounts of product are C
2-C
6Polyvalent alcohol.
Calculate the selectivity and the productive rate of pyruvic alcohol according to embodiment 15 described formula.
The result shows that the fructose transformation efficiency is 100%.Fructose mainly is converted into pyruvic alcohol, and selectivity reaches 68.8%, and yield is 68.8%.
Claims (9)
1. a method for preparing hexitol or pyruvic alcohol comprises the steps:
Under the effect of hydrogen atmosphere and catalyzer, Mierocrystalline cellulose, glucose or fructose react in water, promptly get hexitol or pyruvic alcohol;
Said catalyzer is a load type metal catalyst, and the active ingredient of said load type metal catalyst is the metal of being modified by modifier, said metal be among Pt, Ru, Ni and the Cu any; The carrier of said load type metal catalyst is Al
2O
3, TiO
2, ZrO
2, SiO
2With in the gac any.
2. method according to claim 1 is characterized in that: the temperature of said reaction is 200 ℃～250 ℃, and the time is 0.5 hour～5 hours, and pressure is 2MPa～8Mpa.
3. method according to claim 1 and 2 is characterized in that: said hexitol is sorbyl alcohol and/or N.F,USP MANNITOL.
4. according to arbitrary described method among the claim 1-3, it is characterized in that: said Mierocrystalline cellulose is Microcrystalline Cellulose, cotton, paper pulp, balloonflower root or timber.
5. according to arbitrary described method among the claim 1-4, it is characterized in that: in the said load type metal catalyst, the quality percentage composition of the metal in the said active ingredient is 0.5%～50%.
6. according to arbitrary described method among the claim 1-5, it is characterized in that: in the said active ingredient, said modifier is SnO
x, CeO
x, Al
2O
x, ZnO
xAnd MgO
xIn any, wherein x is the number between 0～4.
7. according to arbitrary described method among the claim 1-6, it is characterized in that: in the said active ingredient, said modifier is (0～10) with the molfraction ratio of said metal: 1, but the amount of said oxide compound is non-vanishing.
8. according to arbitrary described method among the claim 1-7; It is characterized in that: said load type metal catalyst is according to comprising the preparation of following method: in the mixture of the precursor compound of the precursor compound of said modifier and said metal, add aqueous hydrochloric acid; Add said carrier then, promptly get said catalyzer through drying, roasting and reduction; The precursor compound of said modifier is the muriate of respective metal in the said modifier; The precursor compound of said metal is the muriate of said metal.
9. according to arbitrary described method among the claim 1-8, it is characterized in that: the ratio of quality and the number of copies of said catalyzer and Mierocrystalline cellulose, glucose or fructose is (0.1～10): 1.
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