CN101684069B - Method for enriching acetol from biomass pyrolysis liquid aqueous phase system - Google Patents
Method for enriching acetol from biomass pyrolysis liquid aqueous phase system Download PDFInfo
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- CN101684069B CN101684069B CN200810222756A CN200810222756A CN101684069B CN 101684069 B CN101684069 B CN 101684069B CN 200810222756 A CN200810222756 A CN 200810222756A CN 200810222756 A CN200810222756 A CN 200810222756A CN 101684069 B CN101684069 B CN 101684069B
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- aqueous phase
- pyruvic alcohol
- salt
- alkali
- still liquid
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Abstract
The invention belongs to the technical field of chemical engineering, in particular to a method for enriching acetol from a biomass pyrolysis liquid aqueous phase system. The method adopts basic technical processes of rectification, deacidification, extraction and rectification to enrich the acetol from a raw material, namely the biomass pyrolysis liquid aqueous phase system, to over 50 percent (peak area percentage), and simultaneously reduces water content in the system, and reduces the composition types.
Description
Technical field
The invention belongs to technical field of chemistry and chemical engineering, be specifically related to a kind of from the aqueous phase system of biomass pyrolysis liquid the method for enriching acetol.
Background technology
Pyruvic alcohol is claimed hydroxyacetone again; Can be used for the midbody 4-methylimidazole of synthetic Cimitidine Type A/AB, midbody (s)-(+)-2-aminopropanol of Comprecin RWJ 25213-097, the midbody 4-hydroxy methylimidazole of racemize Histidine; Medicine such as antipyretic and analgesic Frosst) acetone ester and chiral intermediate (1)-(-)-1,2 Ucar 35 synthetic that also can be used for vitamin H (vitamin H) and do not have the ulcer toxic side effect.Pyruvic alcohol still prepares the main raw material of the pyruvic acid with physiologically active, utilizes pyruvic alcohol to prepare the existing abroad industriallization report of technology of pyruvic acid, but does not extensively carry out as yet because of raw material pyruvic alcohol supply deficiency at home.It is raw material with the biomass pyrolysis liquid aqueous phase system of hydroxy acetone that employing is arranged recently; Catalyzed oxidation prepares the technology report of pyruvate salt; In the material system hydroxy acetone content low be the unfavorable factor that this process efficiency of restriction improves, then can significantly improve operation efficiency if can improve the content of pyruvic alcohol in the material system.
Synthetic or the working method of pyruvic alcohol mainly contains two kinds: a martonite (or Mono Chloro acetone) esterification/alcoholysis method and 1, the oxygen of 2-Ucar 35 or K
2Cr
2O
7/ H
2SO
4Oxidation style.The former reaction conditions is gentle, and synthetic simple and production unit requires low, and to cause production cost higher be the shortcoming of this method but the price of raw material one martonite (or Mono Chloro acetone) is higher; Latter's raw materials cost is low and but serialization or semi-continuous production but reaction conditions and equipment requirements are high, it is not high to need with expensive metal catalyst, product yield.In addition, have in recent years and adopt 1,2-Ucar 35 technology of gas-phase dehydrogenation coproduction pyruvic alcohol and pyruvic aldehyde under electrolytic silver catalysis to report, in this technology the catalyzer cost higher be unfavorable factor.
Purpose and meaning
The preparation method of above pyruvic alcohol all is the technological processs that obtain pyruvic alcohol through chemosynthesis and chemical conversion means; Owing to relate to unfavorable factors such as the higher and processing condition harshness of raw materials cost in the reaction process; Therefore the preparation and the production of pyruvic alcohol face many unfavorable factors; Especially in recent years the problems such as the deterioration of the ecological environment that the continuous atrophy of fossil energy, environmental pollution cause become increasingly conspicuous; Human Sustainable development faces a severe challenge, and substituting fossil energy with renewable energy source is the important channel that solves human kind sustainable development, and one of eco-friendly just important renewable energy form of biomass energy; Development and use research to biomass energy has in recent years received worldwide extensive concern, is that the biorefinery industry of raw material is in the ascendant with biomass.Being obtained the hardware and software platform compound of downstream reaction or directly extract the high added value chemical to alleviate human dependence to petrochemical complex greatly by biomass processing, is the important content of biomass resource utilization and development research.Pyruvic alcohol as important chemical feedstocks and midbody is one of important component in the biomass pyrolysis liquid; If can be through the chemical separation method with its enrichment; Then possibly improve the whole utility value of biomass resource, have potential economic worth and far-reaching social benefit.
At the biomass pyrolysis liquid aqueous phase system with hydroxy acetone is raw material; Catalyzed oxidation prepares in the technological process of pyruvate salt; In the system hydroxy acetone content low be the unfavorable factor that this process efficiency of restriction improves, if can improve the operation efficiency that the content of pyruvic alcohol in the material system then can significantly improve technological process.
In addition, the component classification significantly reduces in the system of back owing to handle, and possibly offer an opportunity for further adopting membrane separation technique to obtain the higher pyruvic alcohol of purity.
Summary of the invention
The purpose of this invention is to provide a kind of aqueous phase system of the biomass pyrolysis liquid from wide material sources and reproducible utilization, the chemical separation method of the pyruvic alcohol of added value height and obvious social benefit is obtained in enrichment.
The present invention is a raw material with the aqueous phase system of biomass pyrolysis liquid, at first carries out rectifying, collects still liquid, obtains the significantly reduced aqueous solution of water-content and volatile components; In still liquid, add alkali or basic salt with the acidic substance in the removal system; Filter back adding organic solvent in filtrating and extract, make pyruvic alcohol get into organic phase, obtain the organic solution of pyruvic alcohol by water; Organic phase is carried out normal pressure or rectification under vacuum or distillation remove organic solvent; Last rectification under vacuum makes pyruvic alcohol get into distillate with the light constituent form, is the pyruvic alcohol system of enrichment, and the component classification reduces in the system.
Among the present invention, rectifying for the first time is used for the most of water and the lower boiling volatile components of removal system, and rectifying is carried out under normal pressure, and 95-108 ℃ of still liquid temp, collected still liquid by gas phase temperature 98-104 ℃.
Among the present invention, add alkali or basic salt in the still liquid system behind rectifying and dewatering, with the acidic substance in the removal system, used alkali or weak acid strong alkali salt comprise sodium hydroxide, Pottasium Hydroxide, yellow soda ash, salt of wormwood, sodium hydrogencarbonate, saleratus, lime carbonate.
Among the present invention, the system after alkali or the salt processing is extracted, make pyruvic alcohol get into organic phase by water, used extraction agent comprises chloroform, toluene, ETHYLE ACETATE, methylene dichloride.
Among the present invention, organic extraction is carried out normal pressure or rectification under vacuum or distillation mutually removing most of extraction agent, collect still liquid.
Among the present invention, the system of having removed most of extraction agent is carried out rectification under vacuum, 70-160 ℃ of still liquid temp, gas phase temperature 43-100 ℃, pyruvic alcohol is got into the light constituent form distillate liquid phase, collect distillate, be the pyruvic alcohol system of enrichment.
Practical implementation
Embodiment 1
1. get the wood vinegar 1900ml of hydroxy acetone 4.2% (peak area mark), add in the 5L there-necked flask and carry out atmospheric distillation, 95-107 ℃ of still liquid temp, collected still liquid by gas phase temperature 98-102 ℃;
2. get still liquid after the rectifying, to wherein adding gac 20g, stir, suction filtration after the sedimentation, collect filtrating;
3. in filtrating, add yellow soda ash 100g, suction filtration behind the stirring 2h is collected filtrating;
4. in filtrating, add ETHYLE ACETATE 450ml, leave standstill separating oil/water two-phase system after the stirring; Add the 300ml ethyl acetate extraction to aqueous phase system once more; Separating oil/water two-phase system constantly adds 200ml ETHYLE ACETATE 7 times to aqueous phase, the combined ethyl acetate phase;
5. the organic phase ethyl acetate solution is added atmospheric distillation in the 5L there-necked flask, 85-145 ℃ of still liquid temps, 76-80 ℃ of gas phase temperatures are collected still liquid and filtration.
6. get last time rectifying still liquid rectification under vacuum in the 250ml there-necked flask, 50-123 ℃ of still liquid temp, collected still liquid by gas phase temperature 40-45 ℃;
7. get last time rectifying gained still liquid carries out rectification under vacuum in the 100ml there-necked flask; 72-150 ℃ of still liquid temp, collected distillate 3ml by gas phase temperature 45-85 ℃; Wherein hydroxy acetone content 50.8%; Certain unknown component content 21.4%, oxobutanol content 10.9% (content all refers to the peak area mark here), pyruvic alcohol yield (in the product system in the long-pending and raw material of the area fraction of pyruvic alcohol and products obtained therefrom volume the ratio that amasss of pyruvic alcohol area fraction and raw material volume) is 1.9%.
Embodiment 2
1. get the wood vinegar 1840ml of hydroxy acetone 1.94% (peak area mark), add in the 5L there-necked flask and carry out atmospheric distillation, 95-107 ℃ of still liquid temp, collected still liquid by gas phase temperature 98-102 ℃;
2. in filtrating, add yellow soda ash 310g, stir the 3h after-filtration, collect filtrating;
4. collect the organic phase washing lotion with 210ml ETHYLE ACETATE washing leaching cake after-filtration; In filtrating, add ETHYLE ACETATE 200ml; Stirring is left standstill, and separating oil/water two-phase system adds the 200ml ethyl acetate extraction to aqueous phase system once more; Separating oil/water two-phase system; Continuation adds the 200ml ethyl acetate extraction 4 times to aqueous phase, and combined ethyl acetate extraction liquid and filter cake washing lotion are collected the ETHYLE ACETATE phase;
5. ethyl acetate solution is added atmospheric distillation in the 5L there-necked flask, 75-85 ℃ of still liquid temps, 70-80 ℃ of gas phase temperatures are collected still liquid;
6. rectifying still liquid is last time carried out rectification under vacuum, 50-100 ℃ of still liquid temp, collected still liquid by gas phase temperature 30-55 ℃;
7. get last time that rectifying gained still liquid carries out rectification under vacuum in the 100ml there-necked flask, 85-140 ℃ of still liquid temp, gas phase temperature 50-80 ℃; Collect distillate 2.8ml; Wherein hydroxy acetone content 62.4%, and other main ingredients comprise oxobutanol 19.6%, solvent ethyl acetate 8.1%; Acetate 6.2%, water-content 1.1% (content all refers to the peak area mark here).Pyruvic alcohol yield (in the product system in the long-pending and raw material of the area fraction of pyruvic alcohol and products obtained therefrom volume the ratio that amasss of pyruvic alcohol area fraction and raw material volume) is 4.9%.
Claims (5)
1. the method for an enriching acetol from biomass pyrolysis liquid aqueous phase system; It is characterized in that at first raw material is carried out in system, adding alkali or weak acid strong alkali salt after rectifying and dewatering removes most moisture content, extract with organic solvent afterwards; Obtain the organic solution of pyruvic alcohol; Carry out rectifying again and remove organic solvent and other components, obtain the pyruvic alcohol system of the enrichment of component classification minimizing, said biomass pyrolysis liquid aqueous phase system is a wood vinegar.
2. it is characterized in that according to the said method of claim 1, at first raw material is carried out rectification process, 95-108 ℃ of still liquid temp, gas phase temperature 98-104 ℃.
3. it is characterized in that according to the said method of claim 1 that add alkali or weak acid strong alkali salt in the system after rectifying, used alkali or salt comprise sodium hydroxide, Pottasium Hydroxide, yellow soda ash, salt of wormwood, sodium hydrogencarbonate, saleratus, lime carbonate.
4. it is characterized in that according to the said method of claim 1, the system after alkali or the salt processing extracted that make pyruvic alcohol get into organic phase by water, used extraction agent comprises, chloroform, toluene, ETHYLE ACETATE, methylene dichloride.
5. it is characterized in that according to the said method of claim 1, steaming is carried out rectification under vacuum except that the still liquid behind the extraction agent, 70-160 ℃ of still liquid temp, collected the pyruvic alcohol system that distillate is enrichment by gas phase temperature 43-100 ℃.
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| CN200810222756A CN101684069B (en) | 2008-09-24 | 2008-09-24 | Method for enriching acetol from biomass pyrolysis liquid aqueous phase system |
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| CN200810222756A CN101684069B (en) | 2008-09-24 | 2008-09-24 | Method for enriching acetol from biomass pyrolysis liquid aqueous phase system |
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| CN101684069A CN101684069A (en) | 2010-03-31 |
| CN101684069B true CN101684069B (en) | 2012-09-26 |
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| CN108531204B (en) * | 2018-05-04 | 2019-08-06 | 江苏大学 | Two-stage type biomass directional thermal decomposition prepares the apparatus and method of ketone compounds |
| CN112010824A (en) * | 2020-08-21 | 2020-12-01 | 中国科学院广州能源研究所 | Method for selectively preparing high-value product by fast pyrolysis of cassava residue |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100999676A (en) * | 2006-12-31 | 2007-07-18 | 安徽理工大学 | Process of preparing rich acetone alcohol biological oil by biomass microwave catalytic pyrolysis |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100999676A (en) * | 2006-12-31 | 2007-07-18 | 安徽理工大学 | Process of preparing rich acetone alcohol biological oil by biomass microwave catalytic pyrolysis |
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