CN105037111A - Method for separating and purifying 2,6-dimethoxy phenol and acetosyringone from biological oil - Google Patents
Method for separating and purifying 2,6-dimethoxy phenol and acetosyringone from biological oil Download PDFInfo
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- CN105037111A CN105037111A CN201510279412.8A CN201510279412A CN105037111A CN 105037111 A CN105037111 A CN 105037111A CN 201510279412 A CN201510279412 A CN 201510279412A CN 105037111 A CN105037111 A CN 105037111A
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- C07—ORGANIC CHEMISTRY
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- 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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Abstract
The invention belongs to the field of bio-based chemical separation and purification, and relates to a separation and purification process of complex biological oil, particularly to a method for separating and purifying 2,6-dimethoxy phenol and acetosyringone from biological oil. The method comprises: adding a solid alkaline oxide or hydroxide to water so as to form a mixed solution, adding biological oil to the uniformly-stirred mixed solution, carrying out an alkalization reaction, separating to obtain an alkalization precipitate, adding an acid solution to the alkalization precipitate to obtain a phenol mixture and a metal salt solution, carrying out column chromatography separation on the phenol mixture by adopting silica gel or alumina and the like as a carrier, carrying out gradient elution with different proportions of organic solvents so as to respectively obtain different components of phenols and organic carboxylic acids, and concentrating the partial components so as to obtain the high-purity 2,6-dimethoxy phenol and the high-purity acetosyringone. According to the present invention, the high added value chemicals are separated from the complex biological oil through the method, and the method has a certain environmental benefit and a certain economic benefit, and provides the good approach for the resource utilization of the biomass.
Description
Technical field
The invention belongs to bio-based chemical separating-purifying field, relate to the isolation andpurification technique of the bio oil of complicated component, specifically a kind of method of separating-purifying 2,6-syringol and Syringylethanone from bio oil.
Background technology
The environmental problems such as along with the growth of population and the raising of living standards of the people, energy demand constantly increases, and the traditional energy based on fossil oil is increasingly in short supply, the such as Greenhouse effect brought because coal, oil etc. utilize are day by day serious.In the face of the dual-pressure of energy shortage and environment protection, the exploitation of biomass waste equal energy source attract wide attention.Biomass are also translated into the biological carbon of multiple aperture by Pintsch process, hydrothermal liquefaction and are rich in the bio oil of the high added value such as phenols, ketone chemical products except the method for transformation such as direct burning, thermo-cracking, compost fermentation.From bio oil, the outbid chemical of value of separation and Extraction becomes the new research direction of of biomass application.
Bio oil complicated component, wherein known compound reaches kind more than 200, mainly contains sugar, organic acid, phenol, aldehyde, alcohol, ketone etc.The phenols extracted from liquid product can be used as dyestuff, insulation insulating material and foodstuff additive etc., separately has some phenols to have the function of diarrhea, sterilization and disinfection and weeding; VFA is that important industrial chemicals also can be used for preparing deicing agent; Many chemical are separately had to be applied to the industry such as chemical industry, food and medicine.Wherein, 2,6-syringol is a kind of important chemical process intermediate, and is used as spices in industries such as daily use chemicals, medicine, essence synthesis.Syringylethanone be in a kind of structure with methyl phenyl ketone and 2, the phenolic compound that 6-syringol is similar, the activation of the VirA gene that Syringylethanone can induce agrobacterium tumefaciens Ti-plasmids and Agrobacterium rhizogenes to carry and high expression, be widely used in Agrobacterium-mediated genetic transformation research at present.The technology of industrial acquisition 2,6-syringol and Syringylethanone was the method for being synthesized by chemical industry in the past, and the steps such as after chemical reaction, distillation, concentrated and crystallization obtain.From bio oil, how to isolate this two kinds of compounds, be the target of this research.
At present, domestic and international bio oil isolation technique mainly contains extraction, column chromatography for separation, supercritical extraction and membrane sepn etc.
Extraction is also known as solvent extraction or liquid-liquid extraction, also known as extracting (being common to petroleum refining industry), that a kind of liquid extraction agent process forms with it immiscible two-pack or Multi component, realize the mass transfer sepn process of Component seperation, its operational condition is gentle, plant and instrument is simple, is one of the easiest method of separating bio-oil, is thus widely used.
Column chromatography, also known as chromatography, is a kind ofly utilize all components in mixture in two alternate distribution principle to obtain the method be separated.Column chromatography utilizes different substances to distribute in the selectivity of different phase, carries out wash-out with moving phase to the mixture in stationary phase, and materials different in mixture can move along stationary phase with different speed, finally reaches the effect of separation.Column chromatography technology both may be used for the Analysis and Identification of a small amount of sample, may be used for again the separation and purification of large sample.The separation principle of column chromatography is then be separated according to the difference of molecule adsorptive power on a silica gel column, and the stronger molecule of polarity is easily by silica gel adsorption, and the more weak molecule of polarity is not easily adsorbed.Whole column chromatography procedure is exactly the process of Adsorption and desorption, absorption and desorb more again.The maximum feature of column chromatography is that separation efficiency is high, can isolating construction and the closely similar compound of character.
Membrane sepn is according to microbial film to a kind of method be separated the biased sample comprising different components designed by the penetrating principle of matter selective, but be applied to bio oil be separated in also seldom, major part also limitation in the experimental phase.Its reason may be cost intensive, and fractional dose is few, and technology is not mature enough, is not suitable for commercial applications.Supercritical extraction is good with its extraction effect in recent years, low residue, technique are simple, with short production cycle, the advantage such as low that consumes energy is developed rapidly, external to technique theory and practice maturation very, the domestic research to supercritical extraction process is also weaker.
Due to the complicated component of bio oil, utilize the method for single abstraction and purification to be difficult to from bio oil, obtain the higher industrial chemical of purity, therefore, be necessary that developing multiple separation purifying technique combination technique carrys out separating bio-oil.
Summary of the invention
The invention provides the method for separating-purifying 2,6-syringol and Syringylethanone from bio oil, the method process is simple, consumes reagent few, and 2, the 6-syringol obtained and Syringylethanone purity very high.
Technical scheme of the present invention is as follows:
A kind of method of separating-purifying 2,6-syringol and Syringylethanone from bio oil, is characterized in that concrete steps are as follows:
(1) in water, add alkaline hydrated oxide form mixed solution, or solid basic oxide is added in water, reaction generates the mixed solution containing alkaline hydrated oxide, described basic oxide are the one in calcium oxide, barium oxide, magnesium oxide, described alkaline hydrated oxide is the one in calcium hydroxide, hydrated barta, magnesium hydroxide, and wherein basic oxide or oxyhydroxide add-on are 5% ~ 20% of quality;
(2) add bio oil after the mixed solution obtained in step (1) stirs and carry out quaternization, wherein bio oil add-on is 1% ~ 10% of mixed solution quality, separation obtains the throw out that alkalizes, described be separated into filtering separation, centrifugation, settlement separate in one, described quaternization temperature is 20 ~ 70 DEG C, reaction times 10 ~ 60min;
(3) residual organic matter not carrying out quaternization in the bio oil that alcohols ultrasonic cleaning removing is attached in precipitation is added in the alkalization throw out obtained in step (2), separation is precipitated and dries, described alcohols is the one in methyl alcohol, ethanol, propyl alcohol, described be separated into filtering separation, centrifugation, settlement separate in one;
(4) acid solution is added in the oven dry throw out obtained in step (3), metal phenolate material in precipitation is regenerated the mixing solutions of aldehydes matter and metal-salt by acidifying, described acid is the one in hydrochloric acid, sulfuric acid, nitric acid, and the addition of wherein acid is the amount of acid: bio oil quality is 0.5 ~ 5.0mol/g;
(5) mixing solutions that step (4) obtains is mixed with organic solvent, vibration, standing, layering, obtain organic phase and aqueous phase, organic phase is aldehydes matter, aqueous phase is metal salt solution, and described organic solvent is the one in methylene dichloride, ethyl acetate, benzene, toluene;
(6) organic phase that step (5) obtains is revolved steaming removing organic solvent as phenol mixture sample, add the top layer of chromatography column, use the eluent of different ratio to carry out wash-out, collect the sample of different time sections.
Wherein,
Chromatography column stationary phase is silica gel or aluminum oxide;
Chromatography column operating pressure 1 ~ 15bar;
Flow rate of mobile phase is 1 ~ 10cm/min;
Eluent with normal hexane and methylene dichloride mixed system or sherwood oil and ethyl acetate mixed system for eluent, when with normal hexane and methylene dichloride mixed system for eluent time, eluent proportioning graded is normal hexane by polarity from small to large: methylene dichloride 20:1 ~ 1:5; When with sherwood oil and ethyl acetate mixed system for eluent time, eluent proportioning graded is sherwood oil: ethyl acetate 20:1 ~ 1:10 by polarity from small to large; By gradient stepwise elution, each gradient elution volume is 50 ~ 500mL; Applied sample amount is respectively phenol mixture sample: silica gel is 1:20 ~ 1:200, phenol mixture sample: aluminum oxide is 1:50 ~ 1:80;
(7) elution samples step (6) obtained detects, and merges the sample containing same compound and revolve steaming removing organic solvent to obtain highly purified 2,6-syringol and Syringylethanone.
Described bio oil refers to and comprises with the oily mater of the biomass materials such as Enteromorpha, micro-algae, straw, wheat straw, maize straw, corn cob, cigarette stalk, salix monogolica, wood chip, Herba Eichhorniae by the Process Production such as hydrothermal liquefaction, Pintsch process.
Compared with prior art, this technology tool has the following advantages:
(1) the present invention's feature of utilizing metal ion and phenols to form the throw out that alkalizes to separate out, directly from bio oil, extract phenolic compound, wherein 2-methoxyphenol, 4-ethyl-2-methoxyphenol, 2, the total yield of 6-syringol, Syringylethanone can reach more than 80%, and phenols purity can reach more than 90%.And the method extracting phenols from bio oil of routine, be all generally make the phenols in bio oil formed sodium salt soluble in water, by repeatedly extraction and acidifying extract, technique is loaded down with trivial details, and waste is many, and the phenols rate of recovery is also lower.
(2) the present invention is on the basis obtaining phenol mixture, by the eluent of different ratio, column chromatography for separation is carried out to phenol mixture, obtain highly purified single phenol material 2,6-syringol and Syringylethanone, greatly improve the utility value of bio oil.
(3) the present invention is while extraction phenols, and obtain metal salt crystals, it can be applied to refrigeration equipment salt solution used, road ice melting agent and siccative simultaneously.
(4) present invention process is simple, and cost is lower, the organic solvent reusable edible after using, and the resistates produced in bio oil separating phenols material process can be separated further, or is applied on exploitation phenolic resin product.
The present invention obtains high valuable chemicals 2,6-syringol and Syringylethanone by the combination of different separating technology, in the recycling promoting biomass, have huge potentiality.Separation and analysis due to biomass water thermally liquefy bio oil is a quite arduous job, the organic chemicals of high added value is isolated from biomass water thermally liquefy bio oil, accelerate the research steps of the high value added utilization of biomass, prograding is played to the development of bioenergy and biorefining industry, huge economic benefit, social benefit and ecological benefits can be produced.
Accompanying drawing explanation
Fig. 1 is: present invention process basic flow sheet.
Fig. 2 is: 2,6-syringol GC-MS sampling analysis result.
Fig. 3 is: Syringylethanone GC-MS sampling analysis result.
Embodiment
The following examples are used for further illustrating the present invention, are not limitation of the invention.
embodiment 1
Solid oxidation calcium 1.31g is added reaction in 10mL water and generate the mixed solution of calcium hydroxide, the bio oil 1.0g produced after adding straw hydrothermal liquefaction after being stirred, concussion temperature of reaction is 50 DEG C, reaction times is 20min, react the separation of rear suction filtration and obtain solid phase precipitation, solid precipitation is after EtOH Sonicate suction filtration three times, and after putting into 105 DEG C, baking oven baking 4h, the solid precipitation obtained is got 0.05g and added the hydrochloric ultrasonic wave reaction 20min that 10mL concentration is 4mol/L.The reaction soln methylene dichloride getting step divides three extractions, and mixing is shaken and leaves standstill 1h, forms well-bedded organic phase and aqueous phase.Get step organic phase and steam removing methylene dichloride at 50 DEG C of backspins, after revolving the sample 2mL acetic acid ethyl dissolution that steams and obtain, be added to the top layer of silica gel column chromatography as primary sample.Adopt normal hexane and methylene dichloride mixed system normal temperature Gradient wash-out, use 500mL normal hexane successively: methylene dichloride is the eluent of 15:1,500mL normal hexane: methylene dichloride is the eluent of 5:1,500mL normal hexane: methylene dichloride is the eluent of 1:4, eluent flow velocity is 8mL/min.Can obtain 2,6-syringol 3.5mg of purity 91.4%, the Syringylethanone 2.5mg of purity 96.2% respectively, be primary product.Eluent is reclaimed after being separated by rotary evaporation.
embodiment 2
Solid hydrogen magnesium oxide 1.56g is added in 10mL water and forms mixed solution, the bio oil 1.0g produced after adding salix monogolica hydrothermal liquefaction after being stirred, concussion temperature of reaction is 70 DEG C, reaction times is 20min, react the separation of rear suction filtration and obtain solid precipitation, solid precipitation is after EtOH Sonicate suction filtration three times, and after putting into 105 DEG C, baking oven baking 4h, the solid precipitation obtained is got 0.05g and added the hydrochloric ultrasonic wave reaction 20min that 10mL concentration is 10mol/L.The reaction soln methylene dichloride getting step divides three extractions, and mixing is shaken and leaves standstill 1h, forms well-bedded organic phase and aqueous phase.Get step organic phase and steam removing methylene dichloride at 50 DEG C of backspins, after revolving the sample 2mL acetic acid ethyl dissolution that steams and obtain, be added to the top layer of alumina chromatographic column as primary sample.Adopt normal hexane and methylene dichloride mixed system normal temperature Gradient wash-out, use 500mL normal hexane successively: methylene dichloride is the eluent of 10:1,500mL normal hexane: methylene dichloride is the eluent of 8:1,500mL normal hexane: methylene dichloride is the eluent of 1:5, eluent flow velocity is 8mL/min.Can obtain 2,6-syringol 4.6mg of purity 93.7%, the Syringylethanone 3.4mg of purity 94.6% respectively, be primary product.
embodiment 3
Solid oxidation barium 4.62g is added reaction in 10mL boiling water and generate the suspension liquid of hydrated barta, the bio oil 1.0g produced after adding Herba Eichhorniae hydrothermal liquefaction after being stirred, concussion temperature of reaction is 60 DEG C, reaction times is 20min, react the separation of rear suction filtration and obtain solid precipitation, solid precipitation is after EtOH Sonicate suction filtration three times, and after putting into 105 DEG C, baking oven baking 4h, the solid precipitation obtained is got 0.05g and added the hydrochloric ultrasonic wave reaction 20min that 10mL concentration is 8mol/L.The reaction soln methylene dichloride getting step divides three extractions, and mixing is shaken and leaves standstill 1h, forms well-bedded organic phase and aqueous phase.Get step organic phase and steam removing methylene dichloride at 50 DEG C of backspins, after revolving the sample 2mL acetic acid ethyl dissolution that steams and obtain, be added to the top layer of silica gel column chromatography as primary sample.Adopt sherwood oil and ethyl acetate mixed system normal temperature Gradient wash-out, use 500mL sherwood oil successively: ethyl acetate is the eluent of 20:1,500mL normal hexane: methylene dichloride is the eluent of 8:1,500mL sherwood oil: ethyl acetate is the eluent of 1:10, eluent flow velocity is 8mL/min.Can obtain 2,6-syringol 4.0mg of purity 94.3%, the Syringylethanone 2.8mg of purity 93.6% respectively, be primary product.Eluent is reclaimed after being separated by rotary evaporation.Foregoing be only the present invention conceive under basic explanation, and according to any equivalent transformation that technical scheme of the present invention is done, all should protection scope of the present invention be belonged to.
Claims (8)
1. the method for separating-purifying 2,6-syringol and Syringylethanone from a bio oil, is characterized in that the method is realized by following concrete steps:
(1) in water, add alkaline hydrated oxide form mixed solution, or in water, add the mixed solution of basic oxide reaction generation containing alkaline hydrated oxide;
(2) add bio oil in the mixed solution obtained in step (1) and carry out quaternization, be separated and obtain the throw out that alkalizes;
(3) add alcohols ultrasonic cleaning in the alkalization throw out obtained in step (2), be separated and be precipitated and dry;
(4) add acid solution in the oven dry throw out obtained in step (3), obtain aldehydes matter and metal-salt mixing solutions;
(5) mixed with organic solvent by the mixing solutions that step (4) obtains, vibration, standing, layering, obtain organic phase and aqueous phase, organic phase is aldehydes matter, and aqueous phase is metal salt solution;
(6) organic phase that step (5) obtains is revolved steaming removing organic solvent as phenol mixture sample, add the top layer of chromatography column, use the eluent of different ratio to carry out wash-out, collect the sample of different time sections;
(7) elution samples step (6) obtained detects, and merges the sample containing same compound and revolve steaming removing organic solvent to obtain highly purified 2,6-syringol and Syringylethanone.
2. according to claim 1 from bio oil separating-purifying 2, the method of 6-syringol and Syringylethanone, the basic oxide that it is characterized in that described in step (1) are the one in calcium oxide, barium oxide, magnesium oxide, described alkaline hydrated oxide is the one in calcium hydroxide, hydrated barta, magnesium hydroxide, and wherein the add-on of basic oxide or oxyhydroxide is 5% ~ 20% of quality.
3. according to claim 1 from bio oil separating-purifying 2, the method of 6-syringol and Syringylethanone, it is characterized in that the bio oil add-on in step (2) is 1% ~ 10% of the mixed solution quality described in step (1), quaternization temperature is 20 ~ 70 DEG C, reaction times 10 ~ 60min.
4. the method for separating-purifying 2,6-syringol and Syringylethanone from bio oil according to claim 1, the alcohols that it is characterized in that described in step (3) is the one in methyl alcohol, ethanol or propyl alcohol.
5. according to claim 1 from bio oil separating-purifying 2, the method of 6-syringol and Syringylethanone, it is characterized in that the acid solution that step (4) uses is hydrochloric acid, one in sulfuric acid or nitric acid, the addition of wherein acid is the amount/bio oil quality of acid is 0.5 ~ 5.0mol/g.
6. the method for separating-purifying 2,6-syringol and Syringylethanone from bio oil according to claim 1, it is characterized in that revolving set by step (6) (7) steams temperature is 30-60 DEG C.
7. the method for separating-purifying 2,6-syringol and Syringylethanone from bio oil according to claim 1, is characterized in that the organic solvent described in step (5) (6) (7) is the one in methylene dichloride, ethyl acetate, benzene or toluene.
8. the method for separating-purifying 2,6-syringol and Syringylethanone from bio oil according to claim 1, is characterized in that in step (6),
Chromatography column stationary phase is silica gel or aluminum oxide;
Chromatography column operating pressure 1 ~ 15bar;
Flow rate of mobile phase is 1 ~ 10cm/min;
Using normal hexane and methylene dichloride mixed system or sherwood oil and ethyl acetate mixed system as eluent, when with normal hexane and methylene dichloride mixed system for eluent time, eluent proportioning graded is normal hexane by polarity from small to large: methylene dichloride 20:1 ~ 1:5; When with sherwood oil and ethyl acetate mixed system for eluent time, eluent proportioning graded is sherwood oil: ethyl acetate 20:1 ~ 1:10 by polarity from small to large; By gradient stepwise elution, each gradient elution volume is 50 ~ 500mL;
Applied sample amount is respectively phenol mixture sample: silica gel is 1:20 ~ 1:200, or phenol mixture sample: aluminum oxide is 1:50 ~ 1:80.
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| 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 |
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