CN100513371C - Method of producing sorbic alcohol and mannitol by utilizing cellulose - Google Patents
Method of producing sorbic alcohol and mannitol by utilizing cellulose Download PDFInfo
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- CN100513371C CN100513371C CNB2007100996830A CN200710099683A CN100513371C CN 100513371 C CN100513371 C CN 100513371C CN B2007100996830 A CNB2007100996830 A CN B2007100996830A CN 200710099683 A CN200710099683 A CN 200710099683A CN 100513371 C CN100513371 C CN 100513371C
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Abstract
本发明公开了一种利用纤维素生产山梨醇和甘露醇的方法。该方法，是将纤维素置于水中，在催化剂的作用下，于190℃-350℃，反应得到山梨醇和甘露醇。本发明的方法通过水热条件下水自身产生的原位质子酸水解纤维素，同时将水解的中间产物进行耦合加氢，得到山梨醇和甘露醇，反应过程中，不需要加入无机酸，工业零排放，是绿色的过程；该方法对设备要求低，对设备无腐蚀，投资小；水热条件下水自身产生的原位质子酸水解速率快，反应迅速，高效节能，反应体系简单，易于工业化，催化剂寿命长，无流失。The invention discloses a method for producing sorbitol and mannitol from cellulose. In the method, the cellulose is placed in water, and under the action of a catalyst, the sorbitol and mannitol are reacted at 190°C-350°C. The method of the present invention hydrolyzes cellulose by the in-situ proton acid produced by water itself under hydrothermal conditions, and at the same time couples and hydrogenates the hydrolyzed intermediate products to obtain sorbitol and mannitol. During the reaction process, no inorganic acid needs to be added, and the industry has zero emissions , is a green process; this method has low requirements on equipment, no corrosion to equipment, and low investment; under hydrothermal conditions, the in-situ protonic acid generated by water itself has a fast hydrolysis rate, rapid reaction, high efficiency and energy saving, simple reaction system, easy industrialization, catalyst Long life, no loss.
Description
Technical field
The present invention relates to a kind of method of utilizing Mierocrystalline cellulose to produce sorbyl alcohol and N.F,USP MANNITOL.
Background technology
The definition of biomass: under the photosynthetic condition, green plants utilizes sun power, with CO
2, H
2O changes into plant materials; The wood woods, forest industry waste, agricultural wastes, waterplant, oilseed plant, city and industrial organic waste etc. all belong to biomass.Therefore, biomass are renewable resourcess, and wide material sources.The present energy is based on coal, oil, Sweet natural gas, and these fossil resources finally can be exhausted.Based on the definition and the source of biomass, it will be the ideal substitute of fossil resource.60%～80% composition is a Mierocrystalline cellulose in the biomass.Therefore, cellulosic effective conversion is the committed step that biomass substitute fossil energy.Mierocrystalline cellulose is to pass through β-1 with glucose unit, 4-glycosidic link polymeric polymer, and intramolecularly and extramolecular hydrogen bond make the configuration of molecular chain and molecule highly stable.Cellulosic this structure makes cellulosic orientation transform into technical barrier one.
The two kinds of methods that mainly contain of synthesizing sorbyl alcohol and N.F,USP MANNITOL at present from Mierocrystalline cellulose:
1, by the mineral acid hydrolysis Mierocrystalline cellulose, coupling hydro obtains six carbon alcohol polyvalent alcohol simultaneously, as sorbyl alcohol and N.F,USP MANNITOL.The mineral acid that adds is: the H of 0.35-1.5%
3PO
4, temperature of reaction is 160-200 ℃, Ru/C is a catalytic hydrogenation catalyst.Add H
3PO
4Purpose be to make cellulose hydrolysis obtain glucose intermediary product, the glucose that obtains is rapidly by the Ru/C shortening, and is final to six carbon polyols.The problem of this method is: (1) H
3PO
4Adding be not green process, have the discharging of spent acid solution, cause the pollution of environment; (2) H
3PO
4Adding, 160 ℃-200 ℃ temperature of reaction proposes harsh requirement to equipment, unavoidably causes the corrosion of equipment simultaneously, increase equipment drops into expense.
2, by the solid acid hydrolysis Mierocrystalline cellulose, coupling hydro obtains sorbyl alcohol and N.F,USP MANNITOL simultaneously.Catalyzer is a precious metals pt, Ru, and it is loaded on the acid carrier, 190 ℃ of temperature of reaction, in 24 hours reaction times, the productive rate of six carbon polyols is 31%, and wherein sorbyl alcohol is 25%, and N.F,USP MANNITOL is 6%.The problem of this method is: the reaction times is oversize, and reaction efficiency is very low.
Summary of the invention
In order to address the above problem the method that a kind of original position protonic acid hydrocellulose that water self produces under hydrothermal condition production sorbyl alcohol and N.F,USP MANNITOL are provided of the present invention.
The method of production sorbyl alcohol provided by the present invention and N.F,USP MANNITOL is that Mierocrystalline cellulose is placed water, and under the effect of catalyzer, in 190 ℃-350 ℃, reaction obtains sorbyl alcohol and N.F,USP MANNITOL.
Described catalyzer is selected from one or more arbitrary combination among Pd/C, Pt/C, Rh/C, Ru/C, Cu/C and the Au/C.
In the described method, the time of described reaction can be 1-4 hour.
In the described method, the pressure of described reaction is 20atm-80atm (latm=101.325kPa), is preferably 60atm.
In the described method, described water is capacity, and the addition of described catalyzer is 0.1-0.4g/g Mierocrystalline cellulose.
Aforesaid method, described Mierocrystalline cellulose are Microcrystalline Cellulose or natural cellulose.
The original position protonic acid hydrocellulose that method of the present invention produces by water under the hydrothermal condition self, the intermediate product with hydrolysis carries out coupling hydro simultaneously, obtains sorbyl alcohol and N.F,USP MANNITOL.Method of the present invention does not need to add mineral acid, only needs the original position protonic acid hydrocellulose by water under the hydrothermal condition self generation, and industrial zero release is green process; Method of the present invention is low for equipment requirements, and equipment is not had corrosion, invests little; The original position protonic acid hydrolysis rate that water self produces under the hydrothermal condition is fast, is swift in response, and is energy-efficient.Method reaction system of the present invention is simple, is easy to industrialization, and catalyst life is long, does not have to run off.Fiber have very high transformation efficiency and can reach 100% in the method for the present invention, and the productive rate of sorbyl alcohol can reach 48%, and N.F,USP MANNITOL can reach 30%.
Embodiment
Method among the following embodiment if no special instructions, is ordinary method.
Embodiment 1, hydrocellulose are produced sorbyl alcohol and N.F,USP MANNITOL
1g Microcrystalline Cellulose (microcrystalline is available from Alfa Aesar) is placed the 150ml reactor of the water (50ml) that capacity is housed, add 0.4g Pd/C catalyzer, charge into H
2, making the pressure in the reactor is 60atm, is heated to 290 ℃, reacts 1 hour.
According to following method, the productive rate of the transformation efficiency of detection fibers element and sorbyl alcohol and N.F,USP MANNITOL:
Reaction product is carried out mass spectroscopy, and the result shows, mass spectrum is 183 molecular ion peak to mass-to-charge ratio, and the molecular ion peak that provides mass-to-charge ratio 183 molecular weight with the standard of sorbyl alcohol and N.F,USP MANNITOL on mass spectrum coincide; Reaction product is carried out high-efficient liquid phase analysis and quantitative, (Agilent 1100 Series HPLC, Beijing Agilent company limited buys, separator column is: HAMILTON HC-75 Calcium Form Cation Eechange, analysis condition: 30 ℃, 0.6ml/min, ultrapure water is a moving phase) result shows on the high-efficient liquid phase analysis, identical (retention time that sorbyl alcohol goes out the peak is the retention time at two peaks that reaction product provides: 32.4min with the retention time at two peaks that sorbyl alcohol and N.F,USP MANNITOL standard provide on liquid chromatography, the retention time that N.F,USP MANNITOL goes out the peak is: 23.6min), calculate the cellulose conversion rate according to the following equation, the productive rate of reaction product, the result shows, Mierocrystalline cellulose partly is converted into sorbyl alcohol and N.F,USP MANNITOL, obtains 0.34g sorbyl alcohol (concentration in reaction solution is 0.0067g/ml) altogether, 0.22g N.F,USP MANNITOL (concentration in reaction solution is 0.0045g/ml), show that the cellulose conversion rate is 100%, the sorbyl alcohol productive rate is 30%; The N.F,USP MANNITOL productive rate is 20% (feed stock conversion height, at the bottom of the productive rate of product, other product is the small molecular alcohol compounds).
The cellulose conversion rate:
Calculate the selectivity (optionally definition: the growing amount of product and with the ratio of the material quantity that has transformed of same unit representation is a benchmark with the sorbyl alcohol) of sorbyl alcohol and N.F,USP MANNITOL:
The result shows that the selectivity of sorbyl alcohol is 30%, and the selectivity of N.F,USP MANNITOL is 20%.
Embodiment 2, hydrocellulose are produced sorbyl alcohol and N.F,USP MANNITOL
1g natural cellulose (available from Beijing reagent company) is placed the 150ml reactor of the water (50ml) that capacity is housed, add 0.1g Pt/C catalyzer, charge into H
2, making the pressure in the reactor is 60atm, is heated to 220 ℃, reacts 2 hours.
According to following method, the productive rate of the transformation efficiency of detection fibers element and sorbyl alcohol and N.F,USP MANNITOL:
Reaction product is carried out mass spectroscopy, and the result shows, mass spectrum is 183 molecular ion peak to mass-to-charge ratio, and the molecular ion peak that provides mass-to-charge ratio 183 molecular weight with the standard of sorbyl alcohol and N.F,USP MANNITOL on mass spectrum coincide; Reaction product is carried out high-efficient liquid phase analysis and quantitative, (Agilent 1100 Series HPLC, Beijing Agilent company limited buys, separator column is: HAMILTON HC-75 Calcium Form Cation Eechange, analysis condition: 30 ℃, 0.6ml/min, ultrapure water is a moving phase) result shows on the high-efficient liquid phase analysis, identical (retention time that sorbyl alcohol goes out the peak is the retention time at two peaks that reaction product provides: 32.4min with the retention time at two peaks that sorbyl alcohol and N.F,USP MANNITOL standard provide on liquid chromatography, the retention time that N.F,USP MANNITOL goes out the peak is: 23.6min), calculate the cellulose conversion rate according to embodiment 1 described formula, the productive rate of reaction product, the result shows, Mierocrystalline cellulose is converted into sorbyl alcohol and N.F,USP MANNITOL fully, obtains 0.54g sorbyl alcohol (concentration in reaction solution is 0.011g/ml) altogether, 0.34g N.F,USP MANNITOL (concentration in reaction solution is 0.0067), show that the cellulose conversion rate is 100%, the sorbyl alcohol productive rate is 48%; The N.F,USP MANNITOL productive rate is 30%.
According to the selectivity of embodiment 1 described formula calculating sorbyl alcohol and N.F,USP MANNITOL, the result shows that the selectivity of sorbyl alcohol is 48%, and the selectivity of N.F,USP MANNITOL is 30%.
Embodiment 3, hydrocellulose are produced sorbyl alcohol and N.F,USP MANNITOL
1g Microcrystalline Cellulose (microcrystalline is available from Alfa Aesar) is placed the 150ml reactor of the water (50ml) that capacity is housed, add 0.2g Ru/C catalyzer, charge into H
2, making the pressure in the reactor is 20atm, is heated to 240 ℃, reacts 1.5 hours.
According to following method, the productive rate of the transformation efficiency of detection fibers element and sorbyl alcohol and N.F,USP MANNITOL:
Reaction product is carried out mass spectroscopy, and the result shows, mass spectrum is 183 molecular ion peak to mass-to-charge ratio, and the molecular ion peak that provides mass-to-charge ratio 183 molecular weight with the standard of sorbyl alcohol and N.F,USP MANNITOL on mass spectrum coincide; Reaction product is carried out high-efficient liquid phase analysis and quantitative, (Agilent 1100 Series HPLC, Beijing Agilent company limited buys, separator column is: HAMILTON HC-75 Calcium Form Cation Eechange, analysis condition: 30 ℃, 0.6ml/min, ultrapure water is a moving phase) result shows on the high-efficient liquid phase analysis, identical (retention time that sorbyl alcohol goes out the peak is the retention time at two peaks that reaction product provides: 32.4min with the retention time at two peaks that sorbyl alcohol and N.F,USP MANNITOL standard provide on liquid chromatography, the retention time that N.F,USP MANNITOL goes out the peak is: 23.6min), calculate the cellulose conversion rate according to embodiment 1 described formula, the productive rate of reaction product, the result shows, Mierocrystalline cellulose is converted into sorbyl alcohol and N.F,USP MANNITOL fully, obtains 0.43g sorbyl alcohol (concentration in reaction solution is 0.0085g/ml) altogether, 0.17g N.F,USP MANNITOL (concentration in reaction solution is 0.00337g/ml), show that the cellulose conversion rate is 100%, the sorbyl alcohol productive rate is 38%; The N.F,USP MANNITOL productive rate is 15%.
According to the selectivity of embodiment 1 described formula calculating sorbyl alcohol and N.F,USP MANNITOL, the result shows that the selectivity of sorbyl alcohol is 38%, and the selectivity of N.F,USP MANNITOL is 15%.
Embodiment 4, hydrocellulose are produced sorbyl alcohol and N.F,USP MANNITOL
1g natural cellulose (available from Alfa Aesar) is placed the 150ml reactor of the water (50ml) that capacity is housed, add 0.3g Rh/C catalyzer, charge into H
2, making the pressure in the reactor is 60atm, is heated to 190 ℃, reacts 4 hours.
According to following method, the productive rate of the transformation efficiency of detection fibers element and sorbyl alcohol and N.F,USP MANNITOL:
Reaction product is carried out mass spectroscopy, and the result shows, mass spectrum is 183 molecular ion peak to mass-to-charge ratio, and the molecular ion peak that provides mass-to-charge ratio 183 molecular weight with the standard of sorbyl alcohol and N.F,USP MANNITOL on mass spectrum coincide; Reaction product is carried out high-efficient liquid phase analysis and quantitative, (Agilent 1100 Series HPLC, Beijing Agilent company limited buys, separator column is: HAMILTON HC-75 Calcium Form Cation Eechange, analysis condition: 30 ℃, 0.6ml/min, ultrapure water is a moving phase) result shows on the high-efficient liquid phase analysis, identical (retention time that sorbyl alcohol goes out the peak is the retention time at two peaks that reaction product provides: 32.4min with the retention time at two peaks that sorbyl alcohol and N.F,USP MANNITOL standard provide on liquid chromatography, the retention time that N.F,USP MANNITOL goes out the peak is: 23.6min), calculate the cellulose conversion rate according to embodiment 1 described formula, the productive rate of reaction product, the result shows, Mierocrystalline cellulose is converted into sorbyl alcohol and N.F,USP MANNITOL fully, obtains 0.067g sorbyl alcohol (concentration in reaction solution is 0.0013g/ml) altogether, 0.034g N.F,USP MANNITOL (concentration in reaction solution is 0.00067g/ml), show that the cellulose conversion rate is 15%, the sorbyl alcohol productive rate is 6%; The N.F,USP MANNITOL productive rate is 3%.
According to the selectivity of embodiment 1 described formula calculating sorbyl alcohol and N.F,USP MANNITOL, the result shows that the selectivity of sorbyl alcohol is 40%, and the selectivity of N.F,USP MANNITOL is 20%.
Embodiment 5, hydrocellulose are produced sorbyl alcohol and N.F,USP MANNITOL
1g Microcrystalline Cellulose (microcrystalline is available from Alfa Aesar) is placed the 150ml reactor of the water (50ml) that capacity is housed, add 0.1g Cu/C catalyzer, charge into H
2, making the pressure in the reactor is 80atm, is heated to 300 ℃, reacts 1 hour.
According to following method, the productive rate of the transformation efficiency of detection fibers element and sorbyl alcohol and N.F,USP MANNITOL:
Reaction product is carried out mass spectroscopy, and the result shows, mass spectrum is 183 molecular ion peak to mass-to-charge ratio, and the molecular ion peak that provides mass-to-charge ratio 183 molecular weight with the standard of sorbyl alcohol and N.F,USP MANNITOL on mass spectrum coincide; Reaction product is carried out high-efficient liquid phase analysis and quantitative, (Agilent 1100 Series HPLC, Beijing Agilent company limited buys, separator column is: HAMILTON HC-75 Calcium Form Cation Eechange, analysis condition: 30 ℃, 0.6ml/min, ultrapure water is a moving phase) result shows on the high-efficient liquid phase analysis, identical (retention time that sorbyl alcohol goes out the peak is the retention time at two peaks that reaction product provides: 32.4min with the retention time at two peaks that sorbyl alcohol and N.F,USP MANNITOL standard provide on liquid chromatography, the retention time that N.F,USP MANNITOL goes out the peak is: 23.6min), calculate the cellulose conversion rate according to embodiment 1 described formula, the productive rate of reaction product, the result shows, Mierocrystalline cellulose is converted into sorbyl alcohol and N.F,USP MANNITOL fully, obtains 0.24g sorbyl alcohol (concentration in reaction solution is 0.0047g/ml) altogether, 0.11g N.F,USP MANNITOL (concentration in reaction solution is 0.002247g/ml), show that the cellulose conversion rate is 100%, the sorbyl alcohol productive rate is 21%; The N.F,USP MANNITOL productive rate is 10%.
According to the selectivity of embodiment 1 described method calculating sorbyl alcohol and N.F,USP MANNITOL, the result shows that the selectivity of sorbyl alcohol is 21%, and the selectivity of N.F,USP MANNITOL is 10%.
Embodiment 6, hydrocellulose are produced sorbyl alcohol and N.F,USP MANNITOL
1g natural cellulose (available from Beijing reagent company) is placed the 150ml reactor of the water (50ml) that capacity is housed, add 0.1g Au/C catalyzer, charge into H
2, making the pressure in the reactor is 40atm, is heated to 350 ℃, reacts 1 hour.
According to following method, the productive rate of the transformation efficiency of detection fibers element and sorbyl alcohol and N.F,USP MANNITOL:
Reaction product is carried out mass spectroscopy, and the result shows, mass spectrum is 183 molecular ion peak to mass-to-charge ratio, and the molecular ion peak that provides mass-to-charge ratio 183 molecular weight with the standard of sorbyl alcohol and N.F,USP MANNITOL on mass spectrum coincide; Reaction product is carried out high-efficient liquid phase analysis and quantitative, (Agilent 1100 Series HPLC, Beijing Agilent company limited buys, separator column is: HAMILTON HC-75 Calcium Form Cation Eechange, analysis condition: 30 ℃, 0.6ml/min, ultrapure water is a moving phase) result shows on the high-efficient liquid phase analysis, identical (retention time that sorbyl alcohol goes out the peak is the retention time at two peaks that reaction product provides: 32.4min with the retention time at two peaks that sorbyl alcohol and N.F,USP MANNITOL standard provide on liquid chromatography, the retention time that N.F,USP MANNITOL goes out the peak is: 23.6min), calculate the cellulose conversion rate according to embodiment 1 described formula, the productive rate of reaction product, the result shows, Mierocrystalline cellulose is converted into sorbyl alcohol and N.F,USP MANNITOL fully, obtains 0.28g sorbyl alcohol (concentration in reaction solution is 0.0056g/ml) altogether, 0.15g N.F,USP MANNITOL (concentration in reaction solution is 0.0029), show that the cellulose conversion rate is 100%, the sorbyl alcohol productive rate is 25%; The N.F,USP MANNITOL productive rate is 13%.
According to the selectivity of embodiment 1 described method calculating sorbyl alcohol and N.F,USP MANNITOL, the result shows that the selectivity of sorbyl alcohol is 25%, and the selectivity of N.F,USP MANNITOL is 13%.
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| CN102049273B (en) | 2009-10-27 | 2013-05-01 | 中国科学院大连化学物理研究所 | Mesoporous carbon-supported tungsten carbide catalyst and preparation and application thereof |
| CN101768050B (en) * | 2009-12-25 | 2012-12-05 | 北京大学 | Method for preparing ethylene glycol and 1,2-propylene glycol |
| CN103012065B (en) * | 2012-12-27 | 2015-03-18 | 中国科学院广州能源研究所 | Method for preparing high-concentration polyhydric alcohol by circularly hydrolyzing and hydrogenating biomass |
| CN103360212B (en) * | 2013-07-26 | 2016-04-20 | 中国科学院广州能源研究所 | The method of sorbyl alcohol and N.F,USP MANNITOL produced by a kind of concerted catalysis Mierocrystalline cellulose |
| CN108610235A (en) * | 2016-12-09 | 2018-10-02 | 中国科学院大连化学物理研究所 | A kind of steam explosion Hydrogenation for sugar alcohol method |
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- 2007-05-28 CN CNB2007100996830A patent/CN100513371C/en active Active
Non-Patent Citations (2)
| Title |
|---|
| Catalytic Conversion of Cellulose into Sugar Alcohols. Atsushi Fukuoka etal.Angew. Chem. Int. Ed.,Vol.45 . 2006 * |
| 山梨(糖)醇的合成及应用. 熊辉等.湖北化工，第4期. 1999 * |
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