CN102703212B - Refining method for separating each component of biological oil - Google Patents
Refining method for separating each component of biological oil Download PDFInfo
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- CN102703212B CN102703212B CN201210201734.7A CN201210201734A CN102703212B CN 102703212 B CN102703212 B CN 102703212B CN 201210201734 A CN201210201734 A CN 201210201734A CN 102703212 B CN102703212 B CN 102703212B
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Abstract
The invention relates to a refining method for separating each component of biological oil. The refining method comprises the following steps of: (1) washing the biological oil to obtain washing liquid and washing residues; (2) distilling the washing liquid under reduced pressure to obtain saccharides and a water phase, drying the washing residues, and extracting by using ethyl acetate to obtain an extract liquor and insoluble residues; and (3) distilling the extract liquor under the reduced pressure to obtain phenols, and drying the insoluble residues. The refining method has the advantages that the biological oil is divided into the water phase, the saccharides, the phenols and the insoluble residues by adopting simple processes of washing, distilling under the reduced pressure, extracting and the like, so that the additional value of the biological oil is improved.
Description
Technical field
The present invention relates to a kind of process for purification for each component separation of bio oil.
Background technology
The present invention relates to a kind of process for purification for each component separation of bio oil.Bio oil is by biomass pyrolysis under 400～700 ℃ of conditions, and pyrolysis gas condensation obtains bio oil.Industrial bio oil is used for burning boiler mainly as low-quality fuel oil.But between bio oil Ph value 2～4, acidity is stronger, and pipeline is had compared with severe corrosive, so producer also will give special boiler when client's bio-oil fuel is provided.Bio-oil composition composition is mainly carbon, hydrogen, oxygen, component has 100～200 kinds, by carbochain acid different in size, aldehyde, ketone, alcohol, ether, phenol, ester and derivative thereof, and some macromolecular substance are as the complex mixture of the multiple organic compound such as carbohydrate, cracking lignan derivatives and water composition.In standing process, can there are various chemical reactions.Each component separation method of bio oil has following several at present: (1) is used glycerine as solvent and heat-transfer medium, in 200～250 ℃ of temperature ranges, under normal pressure, bio oil is distilled, thereby obtains cut; Residual glycerol mixture, by mixing with water, is separated out xylogen precipitation; Add the glycerol mixture of water by being heated to 230 ℃, reclaim raw glycerine and water, recycle.This kind of method adopts temperature higher, and energy consumption is large.(2) utilizing the method for molecular distillation, is-15～5 ℃ in huyashi-chuuka (cold chinese-style noodles) temperature, and hot-face temperature is under the condition of 20～90 ℃, and distillation bio oil, removes huyashi-chuuka (cold chinese-style noodles) overhead product, collects hot side debris.Utilize molecular distillation technique, successfully the water in bio oil and acid constituents are removed.But molecular distillation technique facility investment is larger.(3) first the method for poly-generation of extracting and separating biological oil with two solvents is used ether as solvent, under normal temperature, normal pressure, bio oil is extracted, thereby obtains ether soluble substance (ES); Remaining ether insolubles (EIS) by adding methylene dichloride, obtains methylene dichloride solvend (DCMS) and methylene dichloride insolubles (DCMIS) under normal temperature, normal pressure.These two kinds of products carry out cryodrying again, can obtain lignin component.This kind of method shortcoming is that xylogen value is not high, and biomass pyrolytic after product is used for extracting xylogen, and economic benefit is not high.The several method of the separated upgrading of comprehensive above bio oil, bio oil is just extracted the product that the added values such as xylogen are not high, or removes simply water and acid constituents.The invention provides a kind of new method extract in bio oil carbohydrate and the high value added product such as phenols.
Summary of the invention
The object of the invention is to overcome the defect that prior art exists, a kind of process for purification for each component separation of bio oil is provided, adopt lower temperature, cheap equipment, simple technique is extracted high value added product from bio oil.
Object of the present invention is achieved through the following technical solutions:
A process for purification for each component separation of bio oil, comprises the steps:
(1) bio oil, through washing, obtains water lotion and rinsing residue;
(2) water lotion underpressure distillation obtains carbohydrate and water, after rinsing residue is dry, is extracted with ethyl acetate, and obtains extraction liquid and insoluble sludge;
(3) extraction liquid underpressure distillation obtains phenols, and insoluble sludge is dry.
Preferably, the described washing of step (1) is bio oil and water 1:(0.5～1.5 in mass ratio) mix, 45～55 ℃ of temperature, stir 20～60 minutes.
Preferably, the condition of the described water lotion underpressure distillation of step (2) is: pressure 20～50KPa, 70～80 ℃ of temperature, 40～60 minutes time.
Preferably, the condition of the described extraction liquid underpressure distillation of step (3) is: pressure 10～30KPa, and 55～65 ℃ of temperature, the time is 60～80 minutes.
Carbohydrate yield of the present invention is 30% left and right, and in carbohydrate product, levoglucos(a)e accounts for 13% left and right.The productive rate of phenols is 30% left and right, and insoluble sludge is 8% left and right, 32% remaining water.Wherein in carbohydrate, contain a small amount of phenol derivatives; Phenolic product is mainly methyl catechol, methyl guaiacol and 4; Insoluble sludge ultimate analysis demonstration contains more than 60% C, contains the H below 10%; In water, water-content accounts for major part (more than 80%), contains a small amount of acid, aldehyde, ketone.Ethyl acetate distillate contains a small amount of furfural and methyl catechol.
The present invention utilizes the feature of bio oil, first washes with water, and the carbohydrate in bio oil is dissolved in water, under suitable temperature, pressure, extracts.Phenols in bio oil is water insoluble, but is dissolved in ethyl acetate, can extract by the method for underpressure distillation.Acid, aldehyde, ketone a small amount of in bio oil are dissolved in water, separated with other component.Insoluble sludge after washing, carbon content is high, can be used as solid fuel and uses.Furfural and methyl catechol contained in ethyl acetate distillate can further extract.
The present invention has the following advantages with respect to prior art tool: existing technique is just except disacidify and moisture or extraction xylogen, the primary separation that belongs to bio oil, and the present invention can directly extract the fine chemicals of several high values by several steps, and the rate of recovery is high.
Embodiment
Below in conjunction with specific embodiment, the present invention is more specifically described in detail, but embodiments of the present invention are not limited to this, for not dated especially processing parameter, can carry out with reference to routine techniques.
Embodiment 1
Get bio oil 50.13g, get distilled water 50.27g, at temperature 50 C, mix and blend 30 minutes; Obtain water lotion quality 66.83g and rinsing residue 33.57g, water lotion carries out underpressure distillation, pressure 35KPa, and 75 ℃ of temperature, 50 minutes time, obtain carbohydrate 14.88g, wherein 13% is levoglucos(a)e.Rinsing residue 33.57g is placed in vacuum drying oven dry, and dried quality is 27.26g; In dried residue, add the ethyl acetate of 200g to extract, obtain extraction liquid and insoluble sludge, extraction liquid underpressure distillation, pressure 15KPa, temperature 60 C, the time is 60 minutes, filtering separation, obtain phenols quality 14.84g, in phenol mixture, methyl catechol accounts for 8.93%, the insoluble sludge dry mass 3.91g after filtration; Light constituent is mainly present in water lotion effluent liquid, and in ethyl acetate effluent liquid, its total mass is 16.5g.
Each main ingredient substances content of table 1 phenols
Table 2 water lotion distillate forms
Table 3 ethyl acetate distillate solute chief component
Claims (1)
1. for a process for purification for each component separation of bio oil, it is characterized in that, comprise the steps:
(1) bio oil is through washing, and described washing is bio oil and water 1:(0.5～1.5 in mass ratio) mix, 45～55 ℃ of temperature, stir 20～60 minutes, obtain water lotion and rinsing residue;
(2) water lotion underpressure distillation obtains carbohydrate and water, after rinsing residue is dry, is extracted with ethyl acetate, and obtains extraction liquid and insoluble sludge; The condition of described water lotion underpressure distillation is: pressure 20～50KPa, 70～80 ℃ of temperature, 40～60 minutes time;
(3) extraction liquid underpressure distillation obtains phenols, and insoluble sludge is dry; The condition of described extraction liquid underpressure distillation is: pressure 10～30KPa, and 55～65 ℃ of temperature, the time is 60～80 minutes.
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| CN102703212B true CN102703212B (en) | 2014-07-16 |
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| CN103740461B (en) * | 2014-01-11 | 2018-03-06 | 河南工业大学 | A kind of method of refining for bio oil multi-stage separation |
| CN103755506B (en) * | 2014-01-27 | 2015-10-28 | 复旦大学 | A kind of separation method of biomass water thermally liquefy solid product |
| CN104593157B (en) * | 2014-12-19 | 2018-01-05 | 华南理工大学 | A kind of method of bio oil esterified alkyl simultaneous upgrading oil separation |
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