CN105037111B - A kind of method of separating-purifying 2,6 syringol and acetosyringone from bio oil - Google Patents
A kind of method of separating-purifying 2,6 syringol and acetosyringone from bio oil Download PDFInfo
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- CN105037111B CN105037111B CN201510279412.8A CN201510279412A CN105037111B CN 105037111 B CN105037111 B CN 105037111B CN 201510279412 A CN201510279412 A CN 201510279412A CN 105037111 B CN105037111 B CN 105037111B
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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Abstract
The invention belongs to biological-based chemicals separating-purifying field, the complicated biological oil separating of quantity relating and purifying technique, specifically a kind of separating-purifying 2, method of 6 syringol and acetosyringone from bio oil.Add solid basic oxide or hydroxide to form mixed liquor in water, bio oil is added in the mixed liquor stirring and carries out quaternization, separate and obtain the precipitate that alkalizes, add acid solution to obtain phenol mixture and metal salt solution in alkalization precipitate.Phenol mixture carries out column chromatography for separation using silica gel or aluminium oxide etc. as carrier, by using the organic solvent gradient elution of different ratio, phenols and the different component of organic carboxyl acid class are respectively obtained, after concentrating part component, can get highly purified 2,6 syringol and acetosyringone.The method has isolated high valuable chemicals from complicated bio oil, has certain environmental benefit and economic benefit, is that the recycling of biomass provides good approach.
Description
Technical field
The invention belongs to biological-based chemicals separating-purifying field, the complicated biological oil separating of quantity relating and purification work
Skill, specifically a kind of separating-purifying 2, method of 6- syringol and acetosyringone from bio oil.
Background technology
Growth with population and the raising of living standards of the people, energy demand constantly increases, based on Fossil fuel
Traditional energy is increasingly in short supply, because coal, oil etc. using and the environmental problem such as greenhouse effect of bringing is increasingly serious.Faced by
Energy shortage and the dual-pressure of environmental conservation, the exploitation of biomass castoff equal energy source attract wide attention.Biological
Matter also can be translated into many in addition to the direct method for transformation such as burning, thermal cracking, compost fermentation by Pintsch process, hydrothermal liquefaction
The biological carbon in aperture and the bio oil rich in the high added value chemical productss such as phenols, ketone.From bio oil, separation and Extraction goes out height
The chemicals being worth become a new research direction of biomass application.
Bio oil complicated component, wherein known compound reach kind more than 200, mainly have sugar, organic acid, phenol, aldehyde, alcohol, ketone etc..
The phenols extracting from liquid product can be used as dyestuff, insulation insulant and food additive etc., separately has some phenols to have
The function of diarrhea, sterilizing and weeding；VFA is that important industrial chemicals also can be used for preparing deicer；Separately
Many chemicals are had to be applied to the industries such as chemical industry, food and medicine.Wherein, 2,6- syringol is a kind of important change
Work process intermediates, and be used as spice in industries such as daily use chemicals, medicine, essence synthesis.Acetosyringone be in a kind of structure with
1-Phenylethanone. and the similar phenolic compound of 2,6- syringol, acetosyringone can induce Agrobacterium tumefaciems Ti-plasmids and
The activation of VirA gene and high efficient expression that Agrobacterium rhizogenes carry, are widely used in agriculture bacillus mediated heredity at present
In Study on Transformation.The technology of industrial acquisition 2,6- syringol and acetosyringone was the side by chemical industry synthesis in the past
Method, the step such as after chemical reaction, distillation, concentration and crystallization obtains.How to isolate both compounds from bio oil, be
The target of this research.
At present, domestic and international bio oil isolation technics mainly have extraction, column chromatography for separation, supercritical extraction and membrance separation etc..
Extraction, also known as solvent extraction or liquid-liquid extraction, also known as extracts（It is common to petroleum refining industry）, it is one kind liquid
Extractant process form immiscible bi-component or Multi component therewith, realize the mass transfer separation process of Component seperation, its
Operating condition is gentle, and instrument and equipment is simple, is one of separating bio-oil method the easiest, thus is widely used.
Column chromatography also known as chromatography, be a kind of using components all in mixture in two alternate distribution principle to obtain
Obtain detached method.Column chromatography utilizes different material to distribute in the selectivity of different phase, with mobile phase in fixing phase
Mixture carries out eluting, and in mixture, different materials can move along fixing phase at different rates, is finally reached detached effect
Really.Column chromatography technology both can be used for the Analysis and Identification of a small amount of sample, can be used for isolating and purifying of large sample again.Column chromatography
Separation principle be then to carry out separating according to the difference of molecule absorbability on a silica gel column, the stronger molecule of polarity is easily by silicon
Glue adsorbs, and the weaker molecule of polarity is difficult to be adsorbed.Whole column chromatography procedure is exactly Adsorption and desorption, adsorbs and desorbing more again
Process.The maximum feature of column chromatography is that separation efficiency is high, can isolating construction and the closely similar compound of property.
Membrance separation be according to biomembrane to a kind of designed by the principle of material selective permeation to comprising different component
Biased sample carries out detached method, but be applied to biological separating of oil in also seldom, most of also limitation is in the experimental stage.Its
Reason is probably cost intensive, and fractional dose is few, and technology is not mature enough, is not suitable for commercial applications.In recent years supercritical extraction with
Its extraction effect is good, low-residual, process is simple, with short production cycle, consume energy low advantage rapidly developed, abroad to this
Technical know-how is very ripe with practice, and the domestic research to supercritical extraction process is also weaker.
Due to the complicated component of bio oil, it is difficult to obtain purity from bio oil using the method for single separation and purification
Higher industrial chemical, therefore, it is necessary to develop multiple separation purifying technique combination techniques to carry out separating bio-oil.
Content of the invention
The invention provides from bio oil separating-purifying 2, the method for 6- syringol and acetosyringone, the party
Method process is simple, and it is few to consume reagent, and 2, the 6- syringol obtaining and acetosyringone purity very high.
Technical scheme is as follows：
A kind of separating-purifying 2 from bio oil, the method for 6- syringol and acetosyringone is it is characterised in that have
Body step is as follows：
（1）Add alkaline hydrated oxide to form mixed liquor in water, or add solid basic oxide in water, reaction life
Become the mixed liquor containing alkaline hydrated oxide, described basic anhydride are one of calcium oxide, Barium monoxide, magnesium oxide, institute
The alkaline hydrated oxide stated is one of calcium hydroxide, barium hydroxide, magnesium hydroxide, wherein basic anhydride or hydroxide
Addition is the 5% ~ 20% of water quality；
（2）In step（1）The mixed liquor obtaining is stirring evenly and then adding into bio oil and carries out quaternization, and wherein bio oil adds
Enter amount for the 1% ~ 10% of mixed liquor quality, separate and obtain the precipitate that alkalizes, described is separated into filtration separation, centrifugation, sinks
One of fall separation, described quaternization temperature is 20 ~ 70 DEG C, response time 10 ~ 60 min；
（3）In step（2）Add alcohols to be cleaned by ultrasonic in the alkalization precipitate obtaining and remove the biology being attached in precipitation
Do not carry out the residual organic matter of quaternization in oil, separate and be precipitated and dry, described alcohols is methanol, ethanol, propanol
One of, the described filtration separation, centrifugation, one of settlement separate of being separated into；
（4）In step（3）Acid solution is added, the metal phenolate material in precipitation is acidified again in the drying precipitate obtaining
It is generated to the mixed solution of aldehydes matter and slaine, described acid is one of hydrochloric acid, sulphuric acid, nitric acid, the wherein interpolation of acid
Measure as sour amount of substance：Biological oil quality is 0.5 ~ 5.0 mol/g；
（5）By step（4）Obtained mixed solution is mixed with organic solvent, vibration, standing, layering, obtains organic faciess
And aqueous phase, organic faciess are aldehydes matter, and aqueous phase is metal salt solution, described organic solvent is dichloromethane, ethyl acetate,
One of benzene, toluene；
（6）By step（5）The organic faciess revolving obtaining removes organic solvent as phenol mixture sample, adds chromatographic column
Top layer, carry out eluting using the eluant of different ratio, collect the sample of different time sections.
Wherein,
Chromatographic column fixing phase is silica gel or aluminium oxide；
Chromatographic column operating pressure 1 ~ 15 bar；
Flow rate of mobile phase is 1 ~ 10 cm/min；
Eluant with normal hexane and dichloromethane mixed system or petroleum ether and ethyl acetate mixed system as eluant, when
During with normal hexane and dichloromethane mixed system for eluant, eluant proportioning graded press polarity be from small to large just oneself
Alkane：Dichloromethane 20：1～1：5；When with petroleum ether and ethyl acetate mixed system for eluant, eluant proportioning gradient becomes
Changing by polarity is petroleum ether from small to large：Ethyl acetate 20：1～1：10；By gradient stepwise elution, each gradient elution volume is
50~500 mL；Applied sample amount is respectively phenol mixture sample：Silica gel is 1：20~1：200th, phenol mixture sample：Aluminium oxide is
1：50~1：80；
（7）By step（6）The elution samples detection obtaining, merges the sample containing identical compound and revolving removing is organic
Solvent obtains highly purified 2,6- syringol and acetosyringone.
Described bio oil refers to Entermorpha, microalgae, Caulis et Folium Oryzae, wheat straw, corn straw, corn cob, cigarette straw, sand
The biomass materials such as willow, wood flour, Herba Eichhorniae pass through the oily mater of the Process Production such as hydrothermal liquefaction, Pintsch process.
Compared with prior art, this technology has the advantage that：
（1）The present invention utilizes metal ion and phenols to form the feature that alkalization precipitate separates out, and directly carries from bio oil
Take out phenolic compound, wherein 2- methoxyphenol, 4- ethyl -2- methoxyphenol, 2,6- syringol, acetyl Flos Caryophylli
The overall recovery of ketone can reach more than 80%, and phenols purity can reach more than 90%.And routine extract phenols from bio oil
Method, is typically all made the phenols formation sodium salt in bio oil soluble in water, is extracted by multiple extraction and acidifying, technique
Loaded down with trivial details, garbage is many, and the phenols response rate is relatively low.
（2）The present invention, on the basis of obtaining phenol mixture, is entered to phenol mixture by the eluant of different ratio
Row column chromatography for separation, has obtained highly purified single phenol material 2,6- syringol and acetosyringone, has greatly improved
The value of bio oil.
（3）The present invention, while extracting phenols, obtains metal salt crystals, it can apply to used by refrigeration plant simultaneously
Saline, road ice melting agent and desiccant.
（4）Present invention process is simple, and cost is relatively low, the organic solvent reusable edible after use, bio oil separating phenols
The residue producing in substance process can separate further, or applies on exploitation phenolic resin product.
The present invention obtains high valuable chemicals 2,6- syringol and acetyl by the combination of different separating technologies
Syringone, has huge potentiality in terms of promoting the recycling of biomass.Due to biomass by hydro-thermal liquefaction bio oil
Separating with analysis is a quite arduous job, isolates organising of high added value from biomass by hydro-thermal liquefaction bio oil
Product, accelerate the research steps of the high value added utilization of biomass, and the development to bioenergy and biorefining industry is played
Progradations, can produce huge economic benefit, social benefit and ecological benefits.
Brief description
Fig. 1 is：Present invention process basic flow sheet.
Fig. 2 is：2,6- syringol GC-MS sample analysis result.
Fig. 3 is：Acetosyringone GC-MS sample analysis result.
Specific embodiment
The following examples are used for further illustrating the present invention, are not limitation of the invention.
Embodiment 1
Solid oxidation calcium 1.31 g is added reaction in 10 mL water to generate the mixed liquor of calcium hydroxide, is stirred for uniformly
Bio oil 1.0 g producing after adding Caulis et Folium Oryzae hydrothermal liquefaction afterwards, concussion reaction temperature is 50 DEG C, and the response time is 20 min, instead
After the completion of answering, sucking filtration separates and obtains solid phase precipitation, and solid precipitation, after EtOH Sonicate sucking filtration three times, is put into 105 DEG C of baking oven and dried 4
After h, the solid precipitation obtaining takes 0.05 g to add the hydrochloric ultrasonic wave that 10 mL concentration are 4 mol/L to react 20 min.Take step
Reaction solution dichloromethane extracts in three times, and 1 h is shaken and stands in mixing, forms well-bedded organic faciess and aqueous phase.Take
Upper step organic faciess are evaporated off dichloromethane in 50 DEG C of backspins, after the sample that revolving is obtained is dissolved with 2 mL ethyl acetate, as
Primary sample is added to the top layer of silica gel column chromatography.Using normal hexane and dichloromethane mixed system room temperature Gradient eluting, successively
With 500 mL normal hexane：Dichloromethane is 15：1 eluent, 500 mL normal hexane：Dichloromethane is 5：1 eluant
Eluting, 500 mL normal hexane：Dichloromethane is 1：4 eluent, eluant flow velocity is 8 mL/min.Can obtain respectively
2,6- syringol 3.5 mg of purity 91.4%, acetosyringone 2.5 mg of purity 96.2%, are for primary product.Wash
De- agent is reclaimed after rotary evaporation separates.
Embodiment 2
Solid magnesium hydroxide 1.56 g is added in 10 mL water and forms mixed liquor, be stirred for uniformly adding afterwards Cortex Salicis Cheilophilae water
Bio oil 1.0 g producing after hydrothermal solution, concussion reaction temperature is 70 DEG C, and the response time is 20 min, sucking filtration after the completion of reaction
Separate and obtain solid precipitation, solid precipitation, after EtOH Sonicate sucking filtration three times, after putting into 105 DEG C of baking 4 h of baking oven, obtains
Solid precipitation takes 0.05 g to add the hydrochloric ultrasonic wave that 10 mL concentration are 10 mol/L to react 20 min.Take the reaction solution of step
Extracted in three times with dichloromethane, 1 h is shaken and stands in mixing, form well-bedded organic faciess and aqueous phase.Take step organic
Dichloromethane is evaporated off in 50 DEG C of backspins, after the sample that revolving is obtained is dissolved with 2 mL ethyl acetate, as primary sample
It is added to the top layer of alumina chromatographic column.Using normal hexane and dichloromethane mixed system room temperature Gradient eluting, successively with 500
ML normal hexane：Dichloromethane is 10：1 eluent, 500 mL normal hexane：Dichloromethane is 8：1 eluent,
500 mL normal hexane：Dichloromethane is 1：5 eluent, eluant flow velocity is 8 mL/min.Purity can be obtained respectively
93.7% 2,6- syringol 4.6mg, acetosyringone 3.4 mg of purity 94.6%, are for primary product.
Embodiment 3
Solid oxidation barium 4.62 g is added reaction in 10 mL boiling water to generate the suspension of barium hydroxide, is stirred for all
Bio oil 1.0 g producing after adding Herba Eichhorniae hydrothermal liquefaction after even, concussion reaction temperature is 60 DEG C, and the response time is 20
Min, after the completion of reaction, sucking filtration separates and obtains solid precipitation, and solid precipitation, after EtOH Sonicate sucking filtration three times, puts into baking oven 105
After DEG C drying 4 h, the solid precipitation that obtains takes 0.05 g to add the hydrochloric ultrasonic wave that 10 mL concentration are 8 mol/L to react 20 min.Take
The reaction solution dichloromethane of upper step extracts in three times, and 1 h is shaken and stands in mixing, forms well-bedded organic faciess and water
Phase.Step organic faciess are taken dichloromethane to be evaporated off in 50 DEG C of backspins, the sample that revolving is obtained is dissolved with 2 mL ethyl acetate
Afterwards, it is added to the top layer of silica gel column chromatography as primary sample.Washed with ethyl acetate mixed system room temperature Gradient using petroleum ether
De-, successively with 500 mL petroleum ether：Ethyl acetate is 20：1 eluent, 500 mL normal hexane：Dichloromethane is 8：1
Eluent, 500 mL petroleum ether：Ethyl acetate is 1：10 eluent, eluant flow velocity is 8 mL/min.Respectively
2,6- syringol 4.0 mg of purity 94.3%, acetosyringone 2.8 mg of purity 93.6% can be obtained, be based on
Want product.Eluant reclaims after rotary evaporation separates.The above is only the basic explanation under present inventive concept, and foundation
Any equivalent transformation that technical scheme is made, all should belong to protection scope of the present invention.
Claims (8)
1. one kind separating-purifying 2 from bio oil, the method for 6- syringol and acetosyringone is it is characterised in that the party
Method is passed through step in detail below and is realized：
（1）Add alkaline hydrated oxide to form mixed liquor in water, or add basic anhydride reaction generation to contain alkali in water
The mixed liquor of property hydroxide；
（2）In step（1）Add bio oil to carry out quaternization in the mixed liquor obtaining, separate and obtain the precipitate that alkalizes；
（3）In step（2）Add alcohols to be cleaned by ultrasonic in the alkalization precipitate obtaining, separate and be precipitated and dry；
（4）In step（3）Add acid solution in the drying precipitate obtaining, obtain aldehydes matter and metal mixed salt solution；
（5）By step（4）Obtained mixed solution is mixed with organic solvent, vibration, standing, layering, obtains organic faciess and water
Phase, organic faciess are aldehydes matter, and aqueous phase is metal salt solution；
（6）By step（5）The organic faciess revolving obtaining removes organic solvent as phenol mixture sample, adds the top of chromatographic column
Layer, carries out eluting using the eluant of different ratio, collects the sample of different time sections；
（7）By step（6）The elution samples detection obtaining, merges the sample containing identical compound and revolving removes organic solvent
Obtain highly purified 2,6- syringol and acetosyringone.
2. the side of separating-purifying 2,6- syringol and acetosyringone from bio oil according to claim 1
Method is it is characterised in that step（1）Described basic anhydride are one of calcium oxide, Barium monoxide, magnesium oxide, described alkalescence
Hydroxide is one of calcium hydroxide, barium hydroxide, magnesium hydroxide, the wherein addition of basic anhydride or hydroxide
For water quality 5% ~ 20%.
3. the side of separating-purifying 2,6- syringol and acetosyringone from bio oil according to claim 1
Method is it is characterised in that step（2）In bio oil addition be step（1）The 1% ~ 10% of described mixed liquor quality, alkalization is anti-
Temperature is answered to be 20 ~ 70 DEG C, response time 10 ~ 60 min.
4. the side of separating-purifying 2,6- syringol and acetosyringone from bio oil according to claim 1
Method is it is characterised in that step（3）Described alcohols is one of methanol, ethanol or propanol.
5. the side of separating-purifying 2,6- syringol and acetosyringone from bio oil according to claim 1
Method is it is characterised in that step（4）The acid solution using is one of hydrochloric acid, sulphuric acid or nitric acid, and wherein the addition of acid is acid
Amount of substance/biology oil quality be 0.5 ~ 5.0 mol/g.
6. the side of separating-purifying 2,6- syringol and acetosyringone from bio oil according to claim 1
Method is it is characterised in that step（6）（7）Set revolving temperature is 30-60 DEG C.
7. the side of separating-purifying 2,6- syringol and acetosyringone from bio oil according to claim 1
Method is it is characterised in that step（5）（6）（7）Described in organic solvent be dichloromethane, ethyl acetate, in benzene or toluene one
Kind.
8. the side of separating-purifying 2,6- syringol and acetosyringone from bio oil according to claim 1
Method is it is characterised in that step（6）In,
Chromatographic column fixing phase is silica gel or aluminium oxide；
Chromatographic column operating pressure 1 ~ 15 bar；
Flow rate of mobile phase is 1 ~ 10 cm/min；
Using normal hexane and dichloromethane mixed system or petroleum ether and ethyl acetate mixed system as eluant, when with normal hexane
During with dichloromethane mixed system for eluant, it is normal hexane from small to large that eluant proportioning graded presses polarity：Dichloromethane
Alkane 20：1～1：5；When with petroleum ether and ethyl acetate mixed system for eluant, eluant proportioning graded press polarity from
Little to greatly petroleum ether：Ethyl acetate 20：1～1：10；By gradient stepwise elution, each gradient elution volume is 50 ~ 500 mL；
Applied sample amount is respectively phenol mixture sample：Silica gel is 1：20~1：200, or phenol mixture sample：Aluminium oxide is 1：50
~1：80.
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Citations (4)
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| CN102899069A (en) * | 2012-10-30 | 2013-01-30 | 复旦大学 | Separating and upgrading method of bio-oil by column chromatography |
| CN103159595A (en) * | 2013-03-06 | 2013-06-19 | 复旦大学 | Method for preparing phenolic compound by liquefaction of salix mongolica |
| CN103755506A (en) * | 2014-01-27 | 2014-04-30 | 复旦大学 | Separation method for solid-phase biomass hydrothermal liquefaction products |
| CN104193597A (en) * | 2014-08-06 | 2014-12-10 | 复旦大学 | Method for separating and purifying 2, 6-dimethoxyphenol from biomass hydrothermal liquefaction liquid phase product |
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2015
- 2015-05-28 CN CN201510279412.8A patent/CN105037111B/en active Active
Patent Citations (4)
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|---|---|---|---|---|
| CN102899069A (en) * | 2012-10-30 | 2013-01-30 | 复旦大学 | Separating and upgrading method of bio-oil by column chromatography |
| CN103159595A (en) * | 2013-03-06 | 2013-06-19 | 复旦大学 | Method for preparing phenolic compound by liquefaction of salix mongolica |
| CN103755506A (en) * | 2014-01-27 | 2014-04-30 | 复旦大学 | Separation method for solid-phase biomass hydrothermal liquefaction products |
| CN104193597A (en) * | 2014-08-06 | 2014-12-10 | 复旦大学 | Method for separating and purifying 2, 6-dimethoxyphenol from biomass hydrothermal liquefaction liquid phase product |
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