CN103130609A - Cellulose single-step method for preparing sugar alcohol - Google Patents
Cellulose single-step method for preparing sugar alcohol Download PDFInfo
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- CN103130609A CN103130609A CN201110393672XA CN201110393672A CN103130609A CN 103130609 A CN103130609 A CN 103130609A CN 201110393672X A CN201110393672X A CN 201110393672XA CN 201110393672 A CN201110393672 A CN 201110393672A CN 103130609 A CN103130609 A CN 103130609A
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- mierocrystalline cellulose
- cellulose
- sugar alcohol
- catalyzer
- hydrogenation
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Abstract
The invention relates to a method for preparing sugar alcohol through catalytic cracking deoxidization of cellulose, in particular to a single-step method for preparing the sugar alcohol through catalytic hydrogenation of the cellulose. The single-step method is characterized in that a catalyst is loaded on cellulose reactants in the process of preparation, so that the purpose that hydrolyzation and the catalytic hydrogenation of the cellulose are conducted at the same time can be achieved.
Description
Technical field
The present invention relates to the method that cellulosic shortening prepares sugar alcohol, be particularly related to the method by the standby sugar alcohol of Mierocrystalline cellulose one-step catalytic Hydrogenation, refer in particular to when catalytic hydrogenation catalyst is prepared and just support (original position supports) on Mierocrystalline cellulose, then one step of fibrin reaction thing is hydrolyzed the standby sugar alcohol of Hydrogenation.
Background technology
Mierocrystalline cellulose is the maximum natural high polymer of quantity on the earth, belongs to renewable resources.Along with the exhaustion of the fossil type energy and material object resource, cellulosic material has become the important sources of energy, food and the chemical feedstocks of human future.Sorbyl alcohol and maltol etc. as important medicine, food and industrial chemicals, are all to produce by catalytic hydrogenation as raw material with sugared at present, and cost is not low.If can come these sugar alcohols of production of high yield with the cellulose resource of cheapness, will greatly reduce costs, and open up new approach for the utilization of cellulosic material.
The catalytic hydrogenation Mierocrystalline cellulose prepares multi-sugar alcohol etc. has had a lot of people to study and applied for Patents, but in these preparation methods, Mierocrystalline cellulose is all through more or less pre-treatment, waste liquid and chemical cost that pre-treatment produces are many, even its cost compare Mierocrystalline cellulose first is hydrolyzed in sulphuric acid soln, and then carries out hydrogenation (two-step approach) reduction is not arranged; Perhaps catalyzed reaction mostly occurs under the condition of High Temperature High Pressure, and in the product that generates simultaneously, the productive rate of sugar alcohol is relatively low.Therefore, seeking under mild conditions highly selective, to be converted into Mierocrystalline cellulose be the emphasis that sugar alcohol becomes research in recent years.
The present invention is by being supported on catalytic pyrolysis hydrogenation catalyst original position on Mierocrystalline cellulose, and one stepping of hydrolysis/hydrogenation is about to Mierocrystalline cellulose and is converted into sugar alcohol under comparatively gentle condition.The invention has the advantages that: the one, avoided numerous and diverse even expensive pre-treatment step, both reduced chemical cost and pollution, reduced again the corrodibility loss of equipment; The 2nd, efficiently solve solid catalyst and the cellulose crystallite contact area is little, the inefficient problem of catalyzed reaction, and catalyzer is easy to recycling.
Summary of the invention
The invention provides a kind of novel method by the standby sugar alcohol of Mierocrystalline cellulose single stage method hydrolysis Hydrogenation, solvent for use is cheap or can reclaim, and does not pollute etching apparatus, and the sugar alcohol yield is higher.
The present invention is as described below:
1. directly prepared the method for sugar alcohol by the Mierocrystalline cellulose single stage method, it is characterized in that: will be hydrolyzed hydrogenation class catalyzer original position and be supported on Mierocrystalline cellulose, then carry out hydrogenation reaction in certain solvent at the certain temperature of certain hydrogen pressure atmosphere, the reaction certain hour can obtain sugar alcohol.
2.1 in hydrogenation catalyst include but are not limited to transition metal salt or its mixture of 8～11 families such as vitriol, muriate, nitrate of Ni, Pt, Ru etc.
3.1 in original position support, refer to be about to catalyst loading on Mierocrystalline cellulose in catalyzer preparation.
4.1 in hydrogen pressure, its pressure range is at 2～50MPa.
5.1 in certain temperature, refer to 100 ℃～300 ℃, preferred 150 ℃～250 ℃, more preferably 180 ℃～210 ℃.
6.1 in said solvent, include but are not limited to water, dimethyl sulfoxide (DMSO) (DMSO), dimethyl formamide (DMFA) etc. or its mixing solutions.
7. the reaction certain hour refers to 0.5～100h, preferred 2～40h.
8.1 in sugar alcohol refer to Sorbitol Powder and/or mannitol.
9.1～8 any one preparation methods, the consumption of catalyzer with respect to cellulosic mass ratio 0.1～10.
10.1～9 Mierocrystalline cellulose includes but are not limited to naturally occurring alpha-cellulose, β-cellulose or through the Mierocrystalline cellulose of other modifications.
11.1 the Mierocrystalline cellulose form in～10 includes but are not limited to powdery, thread, paper pulp shape etc.
12.1 the Mierocrystalline cellulose in～11 mainly refers to the Mierocrystalline cellulose that exists with crystalline state or the Mierocrystalline cellulose that cellulose crystallity was reduced through certain pre-treatment.
Principal character of the present invention is as follows:
Be supported on Mierocrystalline cellulose with regard to original position in the time of with the preparation of the solid catalyst of catalytic pyrolysis hydrogenation, then carry out one step of catalytic pyrolysis hydrogenation reaction to be converted into sugar alcohol in solution.Its sugar alcohol main component is Sorbitol Powder.
Embodiment
Below enforcement of the present invention is illustrated.
1. the original position of catalyzer supports
Soluble transition metal salt or its mixture of 8～11 families such as Ni, Pt, Ru are added the vessel such as flask, add again certain water or other dispersion medium/solution, the Mierocrystalline cellulose that adds again the states such as a certain amount of powder after stirring and dissolving, stir at a certain temperature certain hour, so that the abundant infiltrated fiber element of dispersion agent and salt; Then add alkali (as ammoniacal liquor, urea etc.) regulator solution to certain pH value, stirring reaction for some time at a certain temperature is so that precipitation of salts and loading on Mierocrystalline cellulose; Then filtration washing, obtain the Mierocrystalline cellulose that original position supported catalyzer.
The Mierocrystalline cellulose that exists with crystalline state that this Mierocrystalline cellulose refers to that powdery, thread, paper pulp shape and natural cellulosic feedstocks state exist or make alpha-cellulose that cellulose crystallity reduced, β-cellulose or through the Mierocrystalline cellulose of other modifications through certain pre-treatment.
2. single stage method prepares the method for sugar alcohol
The Mierocrystalline cellulose that original position was supported catalyzer is hydrolyzed hydrogenating reduction under atmosphere of hydrogen, a step obtains sugar alcohol, is mainly Sorbitol Powder.
3. specific embodiment
[example 1]
1.1 the nickel nitrate aqueous solution 100mL with 0.5mol/L of supporting of catalyzer adds in there-necked flask with mechanical stirring device, temperature measuring equipment profit air set pipe, 80 ℃ were stirred 4 hours; Then add Microcrystalline Cellulose powder 10g, continuing to stir more than 6 hours under 80 ℃; Add in the flask again 10% ammoniacal liquor appropriate, regulate blending dispersion solution PH 〉=11, continue to stir more than 6 hours; Blending dispersion solution/suspension/colloid is filtered, and fully wash with large water gaging.
1.2 the solid substance that a standby sugar alcohol of step catalytic hydrolysis Hydrogenation is crossed solid substance obtained above or drying adds reactor, adds 100ML distilled water, sealed reactor extracts air in still, then fills with hydrogen to 8MPa.Stir rotating speed 200rpm, temperature programming to 185 ℃, reaction 40h.Reaction finishes, and discharges the interior hydrogen of still to normal pressure, extracts product, filters, and calculates transformation efficiency, and product liquid HPLC analyzes quantitative.The sugar alcohol yield is 19.3%.
[example 2]
2.1 the ruthenium chloride aqueous solution 100mL with 0.1mol/L of supporting of catalyzer adds in there-necked flask with mechanical stirring device, temperature measuring equipment profit air set pipe, 80 ℃ of vigorous stirring 4h; Then add Microcrystalline Cellulose powder 10g, continue to stir more than 6 hours at 80 ℃; Then add urea 40g in flask, continue to stir under 80 ℃ to spend the night; Said mixture G5 acid funnel is filtered and uses a large amount of distilled water washs.
2.2 the solid substance that a standby sugar alcohol of step catalytic hydrolysis Hydrogenation is crossed solid substance obtained above or drying adds reactor, adds 100ML distilled water, sealed reactor extracts air in still, then fills with hydrogen to 8MPa.Stir rotating speed 200rpm, temperature programming to 190 ℃, reaction 20h.Reaction finishes, and discharges the interior hydrogen of still to normal pressure, extracts product, filters, and calculates transformation efficiency, and product liquid HPLC analyzes quantitative.The sugar alcohol yield is 43.2%.
[example 3]
3.1 supporting outsourcing pulpboard 50g of catalyzer, the potassium platinichloride aqueous solution 500mL that adds 0.2mol/L, the homogeneous instrument stirs shears 150s, then transfers in the there-necked flask with mechanical stirring device, temperature measuring equipment and air set pipe 80 ℃ of vigorous stirring 6～10h; Then add urea 200g in flask, continue to stir under 80 ℃ to spend the night; Said mixture G5 acid funnel is filtered and uses a large amount of distilled water washs.
3.2 the solid substance that a standby sugar alcohol of step catalytic hydrolysis Hydrogenation is crossed solid substance obtained above or drying adds reactor, adds 100ML distilled water, sealed reactor extracts air in still, then fills with hydrogen to 10MPa.Stir rotating speed 200rpm, temperature programming to 205 ℃, reaction 10h.Reaction finishes, and discharges the interior hydrogen of still to normal pressure, extracts product, filters, and calculates transformation efficiency, and product liquid HPLC analyzes quantitative.The sugar alcohol yield is 36.7%.
[example 4]
4.1 supporting absorbent cotton 20g of catalyzer adds the nickel chloride aqueous solution 150mL of 1mol/L, the homogeneous instrument stirs shears 60s, then transfers in the there-necked flask with mechanical stirring device, temperature measuring equipment and air set pipe 80 ℃ of vigorous stirring 6～10h; Then add urea 120g in flask, continue to stir under 80 ℃ to spend the night; Said mixture G5 acid funnel is filtered and uses a large amount of distilled water washs.
4.2 the solid substance 10g that a standby sugar alcohol of step catalytic hydrolysis Hydrogenation is crossed solid substance obtained above or drying adds reactor, adds 100ML distilled water-dimethyl sulfoxide (DMSO) mixing solutions (V
Water: V
DMSO=4: 1), sealed reactor extracts air in still, then fills with hydrogen to 15MPa.Stir rotating speed 200rpm, temperature programming to 1955 ℃, reaction 48h.Reaction finishes, and discharges the interior hydrogen of still to normal pressure, extracts product, filters, and calculates transformation efficiency, and product liquid HPLC analyzes quantitative.The sugar alcohol yield is 23.5%.
Claims (7)
1. method that is directly prepared sugar alcohol by the Mierocrystalline cellulose single stage method, it is characterized in that: hydrogenation class catalyzer original position is supported on Mierocrystalline cellulose, then carry out hydrogenation reaction in certain solvent at certain temperature under the hydrogen pressure atmosphere of 2～50MPa, reaction 0.5～100h can obtain sugar alcohol, and primary product is Sorbitol Powder.
2. the hydrogenation catalyst in claim 1 includes but are not limited to transition metal salt or its mixture of 8～11 families such as vitriol, muriate, nitrate of Ni, Pt, Ru etc.
3. the original position of claim 1 supports, and refers to be about to catalyst loading on Mierocrystalline cellulose in the catalyzer preparation.
4. the certain temperature of claim 1, refer to 100 ℃～300 ℃, preferred 150 ℃～250 ℃, and more preferably 180 ℃～210 ℃.
5. the said solvent of claim 1, include but are not limited to water, dimethyl sulfoxide (DMSO) (DMSO), dimethyl formamide (DMFA) etc. or its mixing solutions.
6. claim 1～5 any one preparation method, the consumption of catalyzer with respect to cellulosic mass ratio 0.1～10.
7. the Mierocrystalline cellulose of claim 1～6 mainly refers to the Mierocrystalline cellulose that exists with crystalline state or through the Mierocrystalline cellulose that certain pre-treatment reduced cellulose crystallity, includes but are not limited to naturally occurring alpha-cellulose, β-cellulose or through the Mierocrystalline cellulose of other modifications; The Mierocrystalline cellulose form includes but are not limited to powdery, thread, paper pulp shape etc.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106458806A (en) * | 2014-04-10 | 2017-02-22 | 阿彻丹尼尔斯米德兰德公司 | Synthesis of shorter chain polyols |
| US10759727B2 (en) | 2016-02-19 | 2020-09-01 | Intercontinental Great Brands Llc | Processes to create multiple value streams from biomass sources |
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| JP2001079411A (en) * | 1999-09-20 | 2001-03-27 | Asahi Kasei Corp | Method for regenerating catalyst for hydrogenation of reducing sugar |
| AU2003288219A1 (en) * | 2002-12-11 | 2004-06-30 | Basf Aktiengesellschaft | Continuous method for the production of sugar alcohols |
| WO2005021475A1 (en) * | 2003-09-03 | 2005-03-10 | Sk Corporation | Method for preparing sugar alcohols by catalytic hydrogenation of sugars |
| CN101394928A (en) * | 2006-03-01 | 2009-03-25 | 国立大学法人北海道大学 | Catalyst for hydrolysis of cellulose and/or reduction of hydrolysis product thereof, and method for producing sugar alcohol from cellulose |
| CN101428214A (en) * | 2007-11-07 | 2009-05-13 | 中国科学院大连化学物理研究所 | Uses of aluminum oxide supported noble metal catalyst in cellulose hydrogenation hydrolyzation |
| CN102101647A (en) * | 2009-12-16 | 2011-06-22 | 中国科学院大连化学物理研究所 | Method for preparing hydrogen from cellulose |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001079411A (en) * | 1999-09-20 | 2001-03-27 | Asahi Kasei Corp | Method for regenerating catalyst for hydrogenation of reducing sugar |
| AU2003288219A1 (en) * | 2002-12-11 | 2004-06-30 | Basf Aktiengesellschaft | Continuous method for the production of sugar alcohols |
| WO2005021475A1 (en) * | 2003-09-03 | 2005-03-10 | Sk Corporation | Method for preparing sugar alcohols by catalytic hydrogenation of sugars |
| CN101394928A (en) * | 2006-03-01 | 2009-03-25 | 国立大学法人北海道大学 | Catalyst for hydrolysis of cellulose and/or reduction of hydrolysis product thereof, and method for producing sugar alcohol from cellulose |
| CN101428214A (en) * | 2007-11-07 | 2009-05-13 | 中国科学院大连化学物理研究所 | Uses of aluminum oxide supported noble metal catalyst in cellulose hydrogenation hydrolyzation |
| CN102101647A (en) * | 2009-12-16 | 2011-06-22 | 中国科学院大连化学物理研究所 | Method for preparing hydrogen from cellulose |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106458806A (en) * | 2014-04-10 | 2017-02-22 | 阿彻丹尼尔斯米德兰德公司 | Synthesis of shorter chain polyols |
| US10759727B2 (en) | 2016-02-19 | 2020-09-01 | Intercontinental Great Brands Llc | Processes to create multiple value streams from biomass sources |
| US11840500B2 (en) | 2016-02-19 | 2023-12-12 | Intercontinental Great Brands Llc | Processes to create multiple value streams from biomass sources |
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Application publication date: 20130605 |