CN103274904A - Microwave-assisted method for oriented conversion of lignin to phenol - Google Patents
Microwave-assisted method for oriented conversion of lignin to phenol Download PDFInfo
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Abstract
The invention discloses a microwave-assisted double liquid phase system for the oriented conversion of lignin to phenol. A microwave-assisted method for the oriented conversion of lignin to phenol comprises the following steps: adding a certain amount of lignin, a catalyst and a double liquid phase reaction solvent composed of a water phase and an organic phase to a microwave reactor under normal pressure, carrying out constant-speed magnetic stirring, and carrying out a microwave reaction at a constant temperature under a constant pressure in 400-800w for 5-120min; and cooling after reaction ending, allowing the obtained product to stand, separating the upper layer which is the organic phase, concentrating, purifying, and recycling an organic solvent. The method has the advantages of mild processing conditions, simultaneous realization of the reaction and the extraction of the product obtained after the lignin conversion to the organic phase, and increase of the lignin conversion efficiency.
Description
Technical field
The invention belongs to the green directional catalyzing transformation technology of xylogen field, can significantly improve the yield that the industrial lignin orientation is converted into phenolic compound by this method, prepare high value added product thereby be conducive to the xylogen catalyzed conversion.
Background technology
Xylogen is a kind of unformed, three-dimensional high branch polymolecularity natural phenolic polymkeric substance, extensively be present in the plant cell wall, think to be interconnected through carbon-carbon bond and carbon-oxygen bond by phenylpropyl alcohol alkyl unit (guaiacyl propane, Syringa oblata Lindl. base propane and to hydroxyphenyl propane) to be coupled to form more, its depolymerization is converted into small-molecule substance and then production high value fine chemicals is to the most effective application approach of xylogen.
Phenol is mainly used in plastics industry, medicine industry and organic synthesis industry etc. as a kind of widely used Organic Chemicals.In recent years along with the fast development of global electronic communication industry, automotive industry and building trade etc., the demand of resol and dihydroxyphenyl propane significantly improves, driven the strong growth of phenol demand, but the output of domestic phenol can not satisfy the demand in market far away, market has openings increases day by day.
Hanna Pi ń kowska(Pi ń kowska, H., P.Wolak, and A.Zlocinska, Hydrothermal decomposition of alkali lignin in sub-and supercritical water[J] .Chemical Engineering Journal, 2012.187:410-414.) be raw material pyrolysis in half/critical water with the alkali lignin, the yield best result of the phenol in the product is not 4.21%.Kang etc. (Kang, S.M., et al., Characterization of Hydrochars Produced by Hydrothermal Carbonization of Lignin, Cellulose, D-Xylose, and Wood Meal[J] .Industrial﹠amp; Engineering Chemistry Research, 2012.51 (26): 9023-9031.) with the depolymerization of alkali lignin hydro-thermal, product liquid is divided into four classes: dihydroxy-benzene class, single phenols, low-pole material and water soluble oil insoluble substance.Phenolic compound accounts for 50% greatly in the lignin depolymerization product, comprises tens kinds of phenolic compounds, and the gained product liquid comprises more than 100 kind of compound.The Appell(Appell H R at energy research center, Pittsburgh, Fu Y C, Friedman S.Conversion of cellulosic waste to oil[J] .Bureau of mines report of investigation, 1971,7:560), cobalt molybdenum alloy with alumina load is that catalyzer carries out catalyzed conversion with timber, and with respect to pyrolysis, the gentleer and efficiency of pcr product of this reaction conditions obviously improves.Famous PERC method that Here it is.Problems such as but this technology is the existence condition harshness still, and the yield of single phenols is very low.Meier D.(Meier D.Bems J., Faix O.High liquid yields from lignin via catalytic hydropyrolysis[M] .Ed.Rev.Pap.Int.Conf, 1992,2:1016-1031) studied the organic solvent xylogen, intermittently and in the semicontinuous reaction carrying out catalyzed conversion, single phenol content is increased to 8.1% from 4.3%.(Tymchyshyn such as Matthew Tymchyshyn, M.and C.Xu, Liquefaction of bio-mass in hot-compressed water for the production of phenolic compounds[J] .Bioresource Technology, 2010.101 (7): p.2483-2490.), be raw material with the lignocellulose waste, H
2Be reducing medium, Ba (OH)
2And Rb
2CO
3Be catalyzer, carry out catalyzed conversion in hydrothermal reaction kettle, wherein total phenol yield can reach 53%, and single phenols yield is about 10%.Wu Shubin (Sui Xinjin, Wu Shubin. industrial soda xylogen thermochemistry transforms preparation phenol chemical. the chemical industry journal, 2011.62 (6): p.1763-1769.) by more several mineral acids, organic acid catalytic liquefaction effect, adopted pure aluminium silicate catalyzed conversion xylogen, phenol yield is 13.65% in the product.More than the research reaction conditions is comparatively harsh, and products therefrom is multiple phenol mixture, separation purifying technique is not fully studied.This shows that the new technology route of the directed conversion preparation of exploitation xylogen phenol is imperative.
Summary of the invention
It is that product such as is difficult to separate, reaction conditions is not gentle at shortcoming in the phenol process that [goal of the invention] the object of the invention is to overcome existing lignin conversion, develops the plain green phenol process that transforms of a kind of novel wooden.
[design of the present invention] compared to by material thermal conduction with traditional type of heating such as the oil bath of object heating or sand-baths, microwave heating speed is fast, be heated evenly.Compare with traditional single liquid-phase reaction system, biliquid phase reaction system can the realization response process and the product sepn process carry out synchronously, help lend some impetus to reaction forward and carry out.Based on the production technique of present industrial lignin and the structure of itself complexity, industrial lignin is soluble in alkaline aqueous solution, and target product phenol is soluble in organic solvent.Based on this, the present invention has designed organic phase and the immiscible biliquid phase reaction system of water, and industrial lignin is degraded to phenol at aqueous phase, and the latter constantly is extracted in the organic phase in reaction process.The mode that adds inorganic salt by aqueous phase improves phenol at the partition ratio of biliquid in mutually, and then improves the yield of target product.In addition, ionic liquid is applied to chemical reaction process more and more as green solvent, reaction reagent and catalyzer etc.The report of xylogen catalyzed conversion as yet not more to be seen but ionic liquid is directly used in.In view of more than, the present invention is coupled microwave-assisted and ionic liquid-catalyzed biliquid phase reaction system, is the efficient of phenol to improve lignin conversion, is beneficial to the high value trans-utilization of industrial lignin.
[technical solution of the present invention]
1, the directed method that transforms phenol of a kind of biliquid phase system microwave-assisted xylogen is characterized in that the method includes the steps of:
Step 1, industrial lignin are made with extra care: to industrial lignin oven drying at low temperature, sieving for standby;
Step 2, the configuration of biliquid phase system solvent: biliquid middle aqueous phase mutually adds quantitative NaOH raising industrial lignin solvability, adds micro-NaCl and improves the partition ratio of product (phenols) in water and organic phase; Biliquid mutually in organic phase disposed according to the certain proportioning of quality by methyl iso-butyl ketone (MIBK) and propyl carbinol or sec-butyl alcohol;
Step 3, according to a certain percentage with quantitative industrial lignin and ionic-liquid catalyst as: 1-aminoethyl-3 methyl imidazolium tetrafluoroborate etc. is added in the biliquid phase reaction solvent; place microwave reactor; stirring and refluxing reaction under the nitrogen protection; the constant temperature reaction can obtain phenol under certain microwave output power.
Step 4, reaction are cooled off, leave standstill, are separated after finishing, and the gained upper organic phase recycles after underpressure distillation.
Screen cloth is 20 orders～40 orders in the step 1.
Step 2 aqueous phase NaOH strength of solution is that 0.1-2%(is with respect to the aqueous solution); The NaCl strength of solution is that 0.1-0.5%(is with respect to the aqueous solution).Methyl iso-butyl ketone (MIBK) and propyl carbinol or sec-butyl alcohol mass ratio are the 5:5-9:1(mass ratio in the organic phase).Organic phase and water volume ratio are 2:1-1:2.
Ratio according to catalyzer and xylogen in the step 3 is the 0.1-0.5(mass ratio), xylogen and reaction solvent solid-to-liquid ratio be the 0.02-0.1(mass ratio) quantitative industrial lignin and catalyzer are added in the biliquid phase reaction solvent; place microwave reactor; stirring and refluxing reaction under the nitrogen protection; be warming up to 80 ℃; microwave output power is 400～800w, reaction times 5～120min.
In the step 4 organic phase product through centrifugal, filter the mode that back employing gas chromatography mass spectrometry is combined with nucleus magnetic resonance product carried out qualitative analysis.The content of phenol and other by products (pyrocatechol, p-cresol etc.) in the employing Agilent Technologies1200Series HPLC liquid chromatography external standard method xylogen hydrolyzed solution, the UV detector, chromatographic column is C18 post (3.9.mm * 150mm), moving phase is methanol=40:60 (v/v), flow velocity is 0.6ml/min, and detector temperature is 35 ℃.
The present invention has following characteristics and advantage:
1. the present invention is coupled microwave-assisted and biliquid phase reaction system, and having improved lignin conversion is the yield of phenol, the reaction conditions gentleness, and product is easy to separate and purifies.
2. the directed biliquid phase system that transforms of a kind of microwave-assisted xylogen of the present invention, the employing ionic liquid is catalyzer, has realized lignin conversion process green.
Embodiment
The present invention will be further described below by embodiment.
Embodiment 1
60 ℃ of oven dry of industrial lignin powder are spent the night, and it is standby to cross 40 mesh sieves; The aqueous solution of configuration 45ml, wherein NaOH content is 1%, NaCl content is 0.5%; Configuration 90ml organic solvent, wherein the mass ratio of methyl iso-butyl ketone (MIBK) and propyl carbinol is 7:3; Add xylogen 0.5g; 1-aminoethyl-3 methyl imidazolium tetrafluoroborate catalyzer 0.2g is in biliquid phase reaction solvent; place microwave reactor; stirring and refluxing reaction under the nitrogen protection; be warming up to 80 ℃, microwave output power is 400w, reaction times 5～120min; timing sampling is analyzed, and phenol yield is 5.32%.
Embodiment 2
60 ℃ of oven dry of industrial lignin powder are spent the night, and it is standby to cross 20 mesh sieves; The aqueous solution of configuration 45ml, wherein NaOH content is 1%, NaCl content is 0.5%; Configuration 45ml organic solvent, wherein the mass ratio of methyl iso-butyl ketone (MIBK) and propyl carbinol is 7:3; Add xylogen 0.5g; 1-aminoethyl-3 methyl imidazolium tetrafluoroborate catalyzer 0.2g is in biliquid phase reaction solvent; place microwave reactor; stirring and refluxing reaction under the nitrogen protection; be warming up to 80 ℃, microwave output power is 400w, reaction times 5～120min; timing sampling is analyzed, and phenol yield is 7.24%.
Embodiment 3
60 ℃ of oven dry of industrial lignin powder are spent the night, and it is standby to cross 40 mesh sieves; The aqueous solution of configuration 45ml, wherein NaOH content is 1%, NaCl content is 0.5%; Configuration 45ml organic solvent, wherein the mass ratio of methyl iso-butyl ketone (MIBK) and propyl carbinol is 7:3; Add xylogen 0.5g; 1-aminoethyl-3 methyl imidazolium tetrafluoroborate catalyzer 0.2g is in biliquid phase reaction solvent; place microwave reactor; stirring and refluxing reaction under the nitrogen protection; be warming up to 80 ℃, microwave output power is 400w, reaction times 5～120min; timing sampling is analyzed, and phenol yield is 8.12%.
Embodiment 4
60 ℃ of oven dry of industrial lignin powder are spent the night, and it is standby to cross 40 mesh sieves; The aqueous solution of configuration 45ml, wherein NaOH content is 1%, NaCl content is 0.5%; Configuration 45ml organic solvent, wherein the mass ratio of methyl iso-butyl ketone (MIBK) and propyl carbinol is 7:3; Add xylogen 0.5g; 1-aminoethyl-3 methyl imidazolium tetrafluoroborate catalyzer 0.1g is in biliquid phase reaction solvent; place microwave reactor; stirring and refluxing reaction under the nitrogen protection; be warming up to 80 ℃, microwave output power is 400w, reaction times 5～120min; timing sampling is analyzed, and phenol yield is 8.43%.
More than the present invention has been done exemplary description, should be noted that the replacement that is equal to that under the situation that does not break away from core of the present invention any simple distortion, modification or other those skilled in the art can not spend creative work all falls into the scope of protection of the invention.
Claims (6)
1. the directed method that transforms phenol of microwave-assisted xylogen is characterized in that the reaction system that this method adopts is the biliquid phase.
2. the directed method that transforms phenol of a kind of microwave-assisted xylogen according to claim 1 is characterized in that: biliquid mutually in aqueous phase add quantitative NaOH and improve lignin dissolution; Add micro-NaCl and improve the partition ratio of product phenols in water and organic phase.
3. the directed method that transforms phenol of a kind of microwave-assisted xylogen according to claim 1 is characterized in that: biliquid mutually in organic phase be that 7:3～9:1 dispose with propyl carbinol or sec-butyl alcohol according to mass ratio by methyl iso-butyl ketone (MIBK).
4. the directed method that transforms phenol of a kind of microwave-assisted xylogen according to claim 1, it is characterized in that: catalyst system therefor is the amino methyl imidazolium tetrafluoroborate class plasma liquid that replaces, and the ratio of catalyzer and xylogen is 0.1～0.5.
5. the directed method that transforms phenol of a kind of microwave-assisted xylogen according to claim 1, it is characterized in that: xylogen and catalyzer are added in the biliquid phase reaction solvent, place microwave reactor, stirring and refluxing is reacted under the nitrogen protection; Microwave output power is 400～800w; Reaction times 5～120min.
6. the directed method that transforms phenol of a kind of microwave-assisted xylogen according to claim 1, it is characterized in that: reaction is cooled off, leaves standstill, is separated after finishing, and the gained upper organic phase recycles after underpressure distillation.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110229049A (en) * | 2019-07-15 | 2019-09-13 | 中国林业科学研究院林产化学工业研究所 | A kind of method of microwave cooperating double solvents Catalytic lignin hydrogenolysis preparation phenolic substances |
| CN113042061A (en) * | 2021-03-01 | 2021-06-29 | 南京林业大学 | Preparation method of catalyst, bio-based lubricating oil base oil and preparation method thereof |
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| CN101932670A (en) * | 2007-08-14 | 2010-12-29 | 卑尔根技术交易股份公司 | One-step conversion of solid lignin to liquid products |
| CN102924204A (en) * | 2012-11-06 | 2013-02-13 | 浙江大学 | Method for degrading and preparing micromolecule phenolic compound in ionic liquid by using microwave strengthened lignin |
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Patent Citations (2)
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| CN101932670A (en) * | 2007-08-14 | 2010-12-29 | 卑尔根技术交易股份公司 | One-step conversion of solid lignin to liquid products |
| CN102924204A (en) * | 2012-11-06 | 2013-02-13 | 浙江大学 | Method for degrading and preparing micromolecule phenolic compound in ionic liquid by using microwave strengthened lignin |
Non-Patent Citations (2)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110229049A (en) * | 2019-07-15 | 2019-09-13 | 中国林业科学研究院林产化学工业研究所 | A kind of method of microwave cooperating double solvents Catalytic lignin hydrogenolysis preparation phenolic substances |
| CN113042061A (en) * | 2021-03-01 | 2021-06-29 | 南京林业大学 | Preparation method of catalyst, bio-based lubricating oil base oil and preparation method thereof |
| CN113042061B (en) * | 2021-03-01 | 2023-12-22 | 南京林业大学 | Preparation method of catalyst, bio-based lubricating oil base oil and preparation method thereof |
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