CN103274904B - A kind of microwave-assisted xylogen orientation transforms the method for phenol - Google Patents
A kind of microwave-assisted xylogen orientation transforms the method for phenol Download PDFInfo
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- CN103274904B CN103274904B CN201310228376.3A CN201310228376A CN103274904B CN 103274904 B CN103274904 B CN 103274904B CN 201310228376 A CN201310228376 A CN 201310228376A CN 103274904 B CN103274904 B CN 103274904B
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Abstract
The invention discloses the Two Liquid Phases system that a kind of microwave-assisted xylogen orientation transforms phenol.At ambient pressure, quantitative xylogen, catalyzer and the Two Liquid Phases reaction solvent that is made up of aqueous phase and organic phase are joined in microwave reactor, and constant speed magnetic agitation, under constant temperature level pressure, carry out microwave reaction 5 ~ 120min with 400 ~ 800w.Reaction terminates rear cooling, leaves standstill, and is separated upper organic phase, and after concentrated purification, organic solvent recycles.The method treatment condition are gentle, be extracted in organic phase, improve the efficiency of lignin conversion while reaction by lignin conversion products therefrom.
Description
Technical field
The invention belongs to the green directional catalyzing transformation technology field of xylogen, can significantly improve by the method the yield that industrial lignin orientation is converted into phenolic compound, thus be conducive to catalytic lignin conversion and prepare high value added product.
Background technology
Xylogen is a kind of unformed, three-dimensional high branch polymolecularity natural phenolic polymkeric substance, extensively be present in 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) more and be coupled to form, 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, as the widely used Organic Chemicals of one, is mainly used in plastics industry, medicine industry and organic synthesis industry etc.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 meet the demand in market far away, market has openings increases day by day.
HannaPi ń kowska(Pi ń kowska, H., P.Wolak, andA.Zlocinska, Hydrothermaldecompositionofalkalilignininsub-andsupercri ticalwater [J] .ChemicalEngineeringJournal, take 2012.187:410-414.) alkali lignin as raw material pyrolysis in half/critical, the yield best result of the phenol in product is not 4.21%.(the Kang such as Kang, S.M., etal., CharacterizationofHydrocharsProducedbyHydrothermalCarbon izationofLignin, Cellulose, D-Xylose, andWoodMeal [J] .Industrial & EngineeringChemistryResearch, 2012.51 (26): 9023-9031.) by alkali lignin hydrothermal depolymerization, product liquid is divided into four classes: dihydroxy-benzene class, single phenols, low-pole material and water soluble oil insoluble substance.In lignin depolymerization product, phenolic compound accounts for 50% greatly, and comprise tens kinds of phenolic compounds, gained product liquid comprises 100 multiple compounds.The Appell(AppellHR at energy research center, Pittsburgh, FuYC, FriedmanS.Conversionofcellulosicwastetooil [J] .Bureauofminesreportofinvestigation, 1971,7:560), be that timber is carried out catalyzed conversion by catalyzer with the cobalt molybdenum alloy of alumina load, relative to pyrolysis, the gentleer and efficiency of pcr product of this reaction conditions significantly improves.Famous PERC method that Here it is.But this technique still existence condition is harsh, the problems such as the yield of single phenols is very low.MeierD.(MeierD.BemsJ., FaixO.Highliquidyieldsfromligninviacatalytichydropyrolys is [M] .Ed.Rev.Pap.Int.Conf, 1992,2:1016-1031) have studied organic solvent xylogen, in interval and semicontinuous reaction, carry out catalyzed conversion, single phenol content is increased to 8.1% from 4.3%.(the Tymchyshyn such as MatthewTymchyshyn, M.andC.Xu, Liquefactionofbio-massinhot-compressedwaterfortheproduct ionofphenoliccompounds [J] .BioresourceTechnology, 2010.101 (7): p.2483-2490.), with lignocellulose waste for raw material, H
2for reducing medium, Ba (OH)
2and Rb
2cO
3for catalyzer, in hydrothermal reaction kettle, carry out catalyzed conversion, wherein total phenol yield can reach 53%, and single phenols yield is about 10%.Wu Shubin (Sui Xinjin, Wu Shubin. industrial soda xylogen thermochemical study prepares phenol chemical. Journal of Chemical Industry and Engineering, 2011.62 (6): p.1763-1769.) by more several mineral acid, organic acid catalytic liquefaction effect, have employed pure aluminium silicate catalyzed conversion xylogen, in product, phenol yield is 13.65%.More than study reaction conditions comparatively harsh, products therefrom is multiple phenol mixture, does not fully study separation purifying technique.As can be seen here, develop xylogen orientation and transform that to prepare the new technology route of phenol imperative.
Summary of the invention
[goal of the invention] the object of the invention is that overcoming existing lignin conversion is that in phenol process, product is difficult to shortcomings such as being separated, reaction conditions is not gentle, develops a kind of Novel wooden quality green and transforms phenol process.
[design of the present invention] compared to by material thermal conduction by type of heating traditional to the oil bath of heating objects or sand-bath etc., microwave heating speed is fast, be heated evenly.Compared with traditional single liquid-phase reaction system, Two Liquid Phases reaction system can realization response process and product separation course synchronization be carried out, and helps lend some impetus to reaction forward and carries out.Based on the production technique of current 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 devises organic phase and the immiscible Two Liquid Phases reactive system of aqueous phase, and industrial lignin is degraded to phenol in aqueous phase, and the latter is constantly extracted in organic phase in reaction process.Improve the partition ratio of phenol in Two Liquid Phases by the mode adding inorganic salt in aqueous phase, and then improve 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.But the report that ionic liquid is directly used in catalytic lignin conversion is not yet common.In view of more than, microwave-assisted is coupled with ionic liquid-catalyzed Two Liquid Phases reaction system by the present invention, to improve the efficiency that lignin conversion is phenol, is beneficial to the high level trans-utilization of industrial lignin.
[technical solution of the present invention]
1, Two Liquid Phases system microwave-assisted xylogen orientation transforms a method for phenol, it is characterized in that the method includes the steps of:
Step one, industrial lignin are refining: to industrial lignin oven drying at low temperature, sieving for standby;
Step 2, Two Liquid Phases system solvent configure: add quantitative NaOH in Two Liquid Phases in aqueous phase and improve industrial lignin solvability, add micro-NaCl and improve product (phenols) partition ratio in aqueous phase and organic phase; In Two Liquid Phases, organic phase is configured 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 by quantitative industrial lignin and ionic-liquid catalyst as: 1-aminoethyl-3 methyl imidazolium tetrafluoroborate etc. is added in Two Liquid Phases reaction solvent; be placed in microwave reactor; stirred under nitrogen atmosphere back flow reaction; under certain microwave output power, constant temperature reaction, can obtain phenol.
Step 4, reaction terminate rear cooling, leave standstill, are separated, and gained upper organic phase uses through underpressure distillation Posterior circle.
In step one, screen cloth is 20 order ~ 40 orders.
In step 2 aqueous phase, NaOH solution concentration is that 0.1-2%(is relative to the aqueous solution); NaCl solution concentration is that 0.1-0.5%(is relative to the aqueous solution).In organic phase, methyl iso-butyl ketone (MIBK) and propyl carbinol or sec-butyl alcohol mass ratio are 5:5-9:1(mass ratio).Organic phase and aqueous phase volume ratio are 2:1-1:2.
Be 0.1-0.5(mass ratio according to the ratio of catalyzer and xylogen in step 3), xylogen and reaction solvent solid-to-liquid ratio be 0.02-0.1(mass ratio) quantitative industrial lignin and catalyzer are added in Two Liquid Phases reaction solvent; be placed in microwave reactor; stirred under nitrogen atmosphere back flow reaction; be warming up to 80 DEG C; microwave output power is 400 ~ 800w, reaction times 5 ~ 120min.
In step 4 organic phase product through centrifugal, filter after adopt gas chromatography mass spectrometry to be combined with nucleus magnetic resonance mode qualitative analysis is carried out to product.Adopt the content of phenol and other by products (pyrocatechol, p-cresol etc.) in AgilentTechnologies1200SeriesHPLC liquid chromatography external standard method xylogen hydrolyzed solution, UV detector, chromatographic column is C18 post (3.9.mm × 150mm), moving phase is methanol/water=40:60 (v/v), flow velocity is 0.6ml/min, and detector temperature is 35 DEG C.
The present invention has following characteristics and advantage:
1. microwave-assisted is coupled with Two Liquid Phases reaction system by the present invention, improves the yield that lignin conversion is phenol, and reaction conditions is gentle, and product is easy to separating-purifying.
2. the Two Liquid Phases system of a kind of microwave-assisted xylogen orientation of the present invention conversion, employing ionic liquid is catalyzer, achieves lignin conversion process green.
Embodiment
Below by embodiment, the present invention will be further described.
Embodiment 1
The 60 DEG C of oven dry of industrial lignin powder are spent the night, crosses 40 mesh sieves for subsequent use; 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 Two Liquid Phases reaction solvent; be placed in microwave reactor; stirred under nitrogen atmosphere back flow reaction; be warming up to 80 DEG C, microwave output power is 400w, reaction times 5 ~ 120min; timing sampling is analyzed, and phenol yield is 5.32%.
Embodiment 2
The 60 DEG C of oven dry of industrial lignin powder are spent the night, crosses 20 mesh sieves for subsequent use; 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 Two Liquid Phases reaction solvent; be placed in microwave reactor; stirred under nitrogen atmosphere back flow reaction; be warming up to 80 DEG C, microwave output power is 400w, reaction times 5 ~ 120min; timing sampling is analyzed, and phenol yield is 7.24%.
Embodiment 3
The 60 DEG C of oven dry of industrial lignin powder are spent the night, crosses 40 mesh sieves for subsequent use; 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 Two Liquid Phases reaction solvent; be placed in microwave reactor; stirred under nitrogen atmosphere back flow reaction; be warming up to 80 DEG C, microwave output power is 400w, reaction times 5 ~ 120min; timing sampling is analyzed, and phenol yield is 8.12%.
Embodiment 4
The 60 DEG C of oven dry of industrial lignin powder are spent the night, crosses 40 mesh sieves for subsequent use; 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 Two Liquid Phases reaction solvent; be placed in microwave reactor; stirred under nitrogen atmosphere back flow reaction; be warming up to 80 DEG C, microwave output power is 400w, reaction times 5 ~ 120min; timing sampling is analyzed, and phenol yield is 8.43%.
Above to invention has been exemplary description, should be noted that any simple distortion, amendment or other those skilled in the art can not spend the equivalent replacement of creative work all to fall into the scope of protection of the invention when not departing from core of the present invention.
Claims (4)
1. microwave-assisted xylogen orientation transforms a method for phenol, and it is characterized in that the reaction system that the method adopts is Two Liquid Phases, its process mainly comprises following:
1) quantitative xylogen is added in Two Liquid Phases reaction system, wherein: add quantitative NaOH in Two Liquid Phases in aqueous phase and improve lignin dissolution; Add micro-NaCl and improve the partition ratio of product in aqueous phase and organic phase; In Two Liquid Phases, organic phase is prepared according to a certain ratio by methyl iso-butyl ketone (MIBK) and propyl carbinol or sec-butyl alcohol; Added in reaction system by quota ion liquid catalyst, magnetic agitation, reacts for some time under constant temperature;
2) after reaction terminates, get upper organic phase analysis, after extracting product, organic phase recycles.
2. a kind of microwave-assisted xylogen orientation transforms the method for phenol as claimed in claim 1, it is characterized in that: used catalyst is the amino methyl imidazolium tetrafluoroborate class ionic liquid replaced, and the ratio of catalyzer and xylogen is 0.1-0.5.
3. a kind of microwave-assisted xylogen orientation transforms the method for phenol as claimed in claim 1, it is characterized in that: xylogen and catalyzer are added in Two Liquid Phases reaction solvent, be placed in microwave reactor, stirred under nitrogen atmosphere back flow reaction; Microwave output power is 400 ~ 800w; Reaction times 5 ~ 120min.
4. a kind of microwave-assisted xylogen orientation transforms the method for phenol as claimed in claim 1, it is characterized in that: reaction terminates rear cooling, leaves standstill, is separated, and gained upper organic phase uses through underpressure distillation Posterior circle.
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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 |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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)
| Title |
|---|
| Separation and recovery of cellulose and lignin using ionic liquids: a process for recovery from paper-based waste;Huma Lateef et al.;《Journal of Chemical Technology and Biotechnology》;20090814;第84卷(第12期);第1818-1827页 * |
| Solubility and rate of dissolution for Miscanthus in hydrophilic ionic liquids;Sasisanker Padmanabhan et al.;《Fluid Phase Equilibria》;20110705;第309卷(第1期);第89-96页 * |
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