CN109336774A - The synthetic method and application of a kind of functionalization biology base ionic liquid - Google Patents
The synthetic method and application of a kind of functionalization biology base ionic liquid Download PDFInfo
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- CN109336774A CN109336774A CN201811249052.7A CN201811249052A CN109336774A CN 109336774 A CN109336774 A CN 109336774A CN 201811249052 A CN201811249052 A CN 201811249052A CN 109336774 A CN109336774 A CN 109336774A
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0279—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the cationic portion being acyclic or nitrogen being a substituent on a ring
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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Abstract
The invention discloses the synthetic method of a kind of functionalization biology base ionic liquid and its applications in alkali lignin pretreatment reaction, with N, N- dimethylethanolamine (DMEA) is raw material, there is the Br φ nsted biology base ionic liquid of different structure by acid-base neutralization synthesis, and with Nuclear Magnetic Resonance, thermogravimetric analysis, the methods of solvatochromism characterize the structure of ionic liquid, thermal stability, acid-base property.The ionic liquid makes the ehter bond in alkali lignin structure that selectivity occur at a lower temperature and breaks to form oligomer, realize the preliminary depolymerization of alkali lignin complexity macromolecular structure in a mild condition as the pretreated green solvent of alkali lignin and catalyst.Experimental data shows that ionic liquid processing significantly improves the yield of low molecular weight compound in catabolite, and wherein the conversion ratio of vanillic aldehyde and selectivity can reach 40% or more.The synthetic method of such ionic liquid is simple, at low cost, and biodegradable, toxicity are low, stablizes in pretreatment reaction and activity is high.
Description
Technical field
The present invention relates to physical chemistry green energy resource fields, and in particular to a kind of steam forces down, liquid temperature range is wide, molten
The synthesis of the ionic liquid for the advantages that solution property is good, thermal stability is high and its first step converted in biomass efficient pre-process anti-
Application in answering.
Background technique
Fossil energy is the limited and non-renewable resource of deposit, and the fast development of global economy exacerbates fossil energy
Consumption, lack of energy not can avoid.With the continuous protrusion of energy problem, received using biomass as the new energy of raw material more next
More extensive concern.The advantages that biomass energy is renewable because having reserves height, no CO2 emission, by international community's public affairs
It is regarded to the efficient resource of alleviating energy crisis.Alkali lignin as biomass energy important component is with phenylpropyl alcohol alkane
Unit is the unformed three-dimensional network polymer of main structure body, is that a large amount of renewable aromatics, phenol can be uniquely provided in nature
The non-oil resource of class compound, however during the utilization of biomass, alkali lignin is difficult to drop because of the complexity of its structure
Solution, is largely wasted usually as by-product or is burned off with inefficient form of thermal energy.Therefore, biomass energy production is greatly developed
Industry develops efficient alkali lignin biodegrading process, realizes that it is cleanly and efficiently converted into energy chemistry product and has become many countries
Important development strategy.
Pretreatment is the first step of alkali lignin efficient degradation, is the degradation rate for improving alkali lignin, reduces later period hydro-thermal
Reaction temperature required for liquefaction reaction obtains indispensable step during more high valuable chemicals.Pretreatment
The aromatic ring paradigmatic structure of alkali lignin complexity can be not only destroyed, reaction condition more harsh in pyrolytic process is improved, it can also
With preliminary concentration product, the selectivity for obtaining aromatics chemicals is promoted.General preprocess method includes physical method, chemistry
Method and biological method.Physics pretreatment method is such as mechanically pulverized, microwave, acid system, alkaline process, and energy consumption is larger, wants to consersion unit
Ask stringent, post-processing causes secondary pollution to environment；Though bioanalysis pretreatment condition is mild, environmental pollution is small, there is processing
Period length, low efficiency, the activity of enzyme are not easy the disadvantages of keeping.In recent years, ionic liquid is due to its excellent physicochemical properties
Especially its stronger solvability, as environmentally friendly solvent before living beings preprocessing technical field shows to apply well
Scape.
Ionic liquid has many advantages, such as, such as: compared with traditional organic solvent, water, supercritical fluid, vapour pressure compared with
It is low, it is not volatile；Wider with temperature range existing for liquid, temperature is from below or near to room temperature to stabilization within the scope of 300 DEG C
In the presence of；Its property can be adjusted by changing the structure of zwitterion；Ionic liquid substitutes organic solvent as green solvent,
The processing environment of homogeneous is formed, transformation efficiency is improved, reduces alkali lignin molecular weight, pyrolysis reaction temperature and required pressure
By force.Its synthesis step is simple and easy, is easy recycling, using more in biomass pretreatment.But researchers systematically grind
What the ionic liquid for the dissolution alkali lignin studied carefully mostly was made of glyoxaline cation.Glyoxaline ion liquid has certain cell
Toxicity, biological degradability is poor, and synthesis material limits its economy and large-scale use mostly from petroleum.Compared to imidazoles
Class ionic liquid, biology base ionic liquid starting material natural reproducible, cost is relatively low, and biodegradable toxicity is lower, to alkali wood
Quality has good dissolubility, meets the requirement of " Green Chemistry ".
In recent years, biology base ionic liquid is paid close attention to by people due to its many advantage, but in biomass pre-treatment step
It reports fresh few.Current relevant report relates generally to biology base ionic liquid and reaches component point applied to the pretreatment of wood fibre
From purpose.Earlier result of study show in the lignocellulosic material crossed through ionic liquid pretreatment the crystallinity of cellulose and
Hydrolysis efficiency significantly improves, and part alkali lignin and hemicellulose are deviate from, and part alkali lignin occurs in preprocessing process
Certain oxidation reaction, react generation product assay and distribution increasingly by the concern of researchers.
Summary of the invention
The purpose of the present invention is be directed to the deficiency of existing preconditioning technique, provide a kind of synthetic method of ionic liquid and answer
With.The present invention uses N, and N- dimethylethanolamine (DMEA) is raw material, synthesizes functionalization biology base ionic liquid by acid-base neutralization
Body, and be used in alkali lignin preprocessing process, the use generation for simplifying treatment process, reducing a large amount of organic reagents
Pollution and burn into realize the β-O-4 of alkali lignin structure, α-O-4 ehter bond and be selectively broken, form vanillic aldehyde and hydro carbons
Object is closed, wherein for the selectivity of vanillic aldehyde up to 40% or more, the synthetic method of biology base ionic liquid is simple, stability is high, easy
It recycles, is reusable.
In order to realize the above object, it is that the present invention takes the specific technical proposal is:
A kind of synthetic method of functionalization biology base ionic liquid, method includes the following steps:
Step 1: with N, N- dimethylethanolamine (DMEA) is raw material, carries out ion friendship by mixing, stirring with acid, solvent
It changes, removes solvent at reduced pressure conditions using Rotary Evaporators, and is sufficiently dry in vacuum oven, be made [DMEA] [M]
Class functionalization biology base ionic liquid；Wherein, [M] is acid ion；The acid is hydrochloric acid, acetic acid or sulfuric acid；Institute
The solvent stated is deionized water and anhydrous methanol；The raw material: acid: the molar ratio of solvent is 1: 1: 1；The mixing time is
24-48h；The vacuum oven temperature is 55-75 DEG C.
Above-mentioned functionalization biology base ionic liquid is applied in alkali lignin pretreatment reaction, obtains the hydro carbons of high yield
Close object and aldehyde compound.
The application is to mix alkali lignin with 1: 9 mass ratio with functionalization biology base ionic liquid, in 100-
160 DEG C, under conditions of 30-150min, make the ehter bond in alkali lignin structure that the fracture of selectivity occur, alkali lignin degraded
For hydrocarbon compound and aldehyde compound；Wherein, the ehter bond is β-O-4, α-O-4 key；The hydrocarbon compound is dodecane
Hydrocarbon, tetradecane hydrocarbon, hexadecane hydrocarbon, octadecane hydrocarbon etc.；The aldehyde compound is vanillic aldehyde.
The thermal decomposition temperature of ionic liquid of the invention is between 200-300 DEG C, under 80-160 DEG C of pretreatment condition
It is very stable, and can be hydrocarbon compound and aldehyde compound by alkali lignin initial breakdown.
Compared with the prior art, the present invention has the following advantages:
(1) chemical structure characteristic based on alkali lignin complexity, pre-treatment step not only can tentatively destroy its aromatic ring knot
Structure can also promote the selectivity of aromatics chemicals with enriched product.
(2) selection is at low cost, synthesis step is simple, to the functionalization biology base ionic liquid of alkali lignin favorable solubility
Body, biodegradable, toxicity is low, meets environmentally protective.
(3) contain OAc-Ionic liquid show the strong protective effect to phenolic hydroxyl group, the net of alkali lignin after pretreatment
Shape structure division is destroyed, it is easier to be converted into phenol small molecule compound, the selectivity of vanillic aldehyde reaches 40% or more.
Detailed description of the invention
Fig. 1 is the structural formula of three kinds of ionic liquids of the invention；
Fig. 2~4 are respectively the present invention [DMEA] [Cl], [DMEA] [OAc] and [DMEA] [HSO4] ionic liquid nuclear-magnetism
Resonate hydrogen spectrogram；
Fig. 5 is abosrption spectrogram of the 4- nitroaniline of the present invention in ionic liquid；
Fig. 6 is the work flow diagram of ionic liquid pretreatment alkali lignin of the present invention；
Fig. 7 is the present invention through the alkali lignin infrared spectrum before and after ionic liquid pretreatment；
Fig. 8 is the GC-MS spectrogram of [DMEA] [Cl] ionic liquid pretreatment alkali lignin；
Fig. 9 is the GC-MS spectrogram of [DMEA] [OAc] ionic liquid pretreatment alkali lignin；
Figure 10 is [DMEA] [HSO4] ionic liquid pretreatment alkali lignin GC-MS spectrogram；
Specific embodiment
Embodiment 1
0.1mol deionized water is moved into 100ml there-necked flask, then weighs 0.1mol N, N- dimethylethanolamine (DMEA)
It is dissolved in deionized water and at room temperature with magneton and stirring, weigh the hydrochloric acid that the amount of equal substances has diluted, there-necked flask is added dropwise
In.Continue stirring 24 hours at room temperature, then removes aqueous solvent at reduced pressure conditions with Rotary Evaporators, and in vacuum oven
[DMEA] [Cl] ionic liquid is made in interior abundant drying.
Alkali lignin KL is mixed in round-bottomed flask with [DMEA] [Cl] with the mass ratio of 0.5:4.5g, and by the pre- of setting
Treatment conditions (80-160 DEG C of reaction temperature, reaction time 30-150min) heating stirring.Slurries are cooled to room temperature and use a certain amount of
Deionized water (20-30ml DI water) dilution, be put into 4 DEG C with diluted HCl tune pH value of solution to 2-3 and by suspension
Refrigerator overnight is to ensure to precipitate completely.Suspension is transferred in centrifuge tube, separately plus deionized water, put into a centrifuge with
The speed of 8000rpm is centrifuged 15min.Supernatant liquid is pretreated water-phase product, and lower layer's solid is pretreated alkali
Lignin (i.e. regeneration alkali lignin L1).Pretreated alkali lignin is freeze-dried.Into the water-phase product that pretreatment obtains
Ethyl acetate (EA) mixing of 20~30ml is added, separates organic layer, with anhydrous magnesium sulfate drying, filtering, revolving, obtains alkali wood
Quality depolymerization product (L2).Product L1For hydrothermal liquefaction reaction later, L2For a series of detection and analysis.
Embodiment 2
0.1mol deionized water is moved into 100ml there-necked flask, then weighs 0.1mol N, N- dimethylethanolamine (DMEA)
It is dissolved in deionized water and at room temperature with magneton and stirring, weigh the sulfuric acid that the amount of equal substances has diluted, there-necked flask is added dropwise
In.Continue stirring 24 hours at room temperature, then removes aqueous solvent at reduced pressure conditions with Rotary Evaporators, and in vacuum oven
[DMEA] [HSO is made in interior abundant drying4] ionic liquid.
Alkali lignin (KL) and [DMEA] [HSO4] mixed in round-bottomed flask with the mass ratio of 0.5:4.5g, and by setting
Pretreatment condition (80-160 DEG C of reaction temperature, reaction time 30-150min) heating stirring.Slurries are cooled to room temperature and use one
Quantitative deionized water (20-30ml DI water) dilution, is put into diluted HCl tune pH value of solution to 2-3 and by suspension
4 DEG C of refrigerator overnights are to ensure to precipitate completely.Suspension is transferred in centrifuge tube, separately plus deionized water, is put into a centrifuge
15min is centrifuged with the speed of 8000rpm.Supernatant liquid is pretreated water-phase product, and lower layer's solid is pretreated
Alkali lignin (i.e. regeneration alkali lignin L1).Pretreated alkali lignin is freeze-dried.It is produced to the water phase obtained to pretreatment
Ethyl acetate (EA) mixing of 20~30ml is added in object, separates organic layer, and, filtering dry with anhydrous magnesium sulfate, revolving, obtains
Obtain alkali lignin depolymerization product (L2).Product L1For hydrothermal liquefaction reaction later, L2For a series of detection and analysis.
Embodiment 3
0.1mol anhydrous methanol is moved into 100ml there-necked flask, then weighs 0.1mol N, N- dimethylethanolamine (DMEA)
It is dissolved in anhydrous methanol and at room temperature with magneton and stirring, weigh the acetic acid of the amount of equal substances, be added dropwise in there-necked flask.Continue
It is stirred at room temperature 24 hours, then removes solvent anhydrous methanol at reduced pressure conditions with Rotary Evaporators, and in vacuum oven
[DMEA] [OAc] ionic liquid is made in interior abundant drying.
Alkali lignin KL with [DMEA] [OAc] to be mixed in round-bottomed flask with the mass ratio of 0.5:4.5g, and by setting
Pretreatment condition (80-160 DEG C of reaction temperature, reaction time 30-150min) heating stirring.Slurries are cooled to room temperature and use one
Quantitative deionized water (20-30ml DI water) dilution, is put into diluted HCl tune pH value of solution to 2-3 and by suspension
4 DEG C of refrigerator overnights are to ensure to precipitate completely.Suspension is transferred in centrifuge tube, separately plus deionized water, is put into a centrifuge
15min is centrifuged with the speed of 8000rpm.Supernatant liquid is pretreated water-phase product, and lower layer's solid is pretreated
Alkali lignin (i.e. regeneration alkali lignin L1).Pretreated alkali lignin is being freeze-dried.The water phase obtained to pretreatment produces
Ethyl acetate (EA) mixing of 20~30ml is added in object, separates organic layer, with anhydrous magnesium sulfate drying, filtering, revolving, obtains
Alkali lignin depolymerization product (L2).Product L1For hydrothermal liquefaction reaction later, L2For a series of detection and analysis.
1 three kinds of ionic liquid acidity of table (Hammett acid function H0) calculating compared with
The present invention measures the acidity of functionalization biology base ionic liquid with the method for Hammett indicator, selects 4- nitro
Aniline makees indicator, water as solvent (three kinds of ionic liquids are dissolved in water).By Fig. 5 it can be observed that unprotonated 4- nitrobenzene
The maximum absorbance of amine is at 380nm, and after acidic ion liquid is added, the maximum absorbance of unprotonated indicator is reduced.
Therefore in pure water, the maximum absorbance value of unprotonated 4- nitroaniline can be used as decision [B]/[BH+] ratio just
Begin to refer to, to calculate the Hammett acid function H after functionalization biology base ionic liquid is added0, it is shown in Table 1.
Functionalization biology base Ionic Liquids Acidity sequence is [DMEA] [HSO as can be seen from Table 14]>[DMEA][OAc]>
[DMEA][Cl]。
Depolymerization product (the L that ionic liquid is obtained through different time pretreatment alkali lignin under the conditions of 2 160 DEG C of table2) member
Element composition and calorific value (HHV) comparison
Depolymerization product (the L obtained after pretreatment2) elemental analysis the results are shown in Table 2.It is not difficult to find that working as from these data
Pretreated reaction temperature is 160 DEG C, and with the increase of pretreatment reaction time, phosphorus content 55.2-64.21% is higher than original
55.05% in material.It is high through the processed alkali lignin calorific value of three kinds of ionic liquids when the pretreatment reaction time is 60min, it can
It is up to 22.54%, 24.32%, 23.80% respectively.In all experiments, oxygen content highest reduce 10%, O/C ratio also from
0.72 is reduced to 0.47.It can be seen that in preprocessing process deoxidation effect also compare it is obvious.
It is found by the analysis of experimental data, at 160 DEG C, under the conditions of 60min, is handled through [DMEA] [oAc] ionic liquid
The calorific value highest that alkali lignin obtains, thus it is further to present invention work detailed by specific [DMEA] [oAc] embodiment
Explanation.
The reaction time influences [DMEA] [oAc] pretreated alkali lignin under the conditions of 3 160 DEG C of table
By taking [DMEA] [oAc] ionic liquid as an example, the reaction time is studied to vanillic aldehyde in alkali lignin degradation rate and product
The influence of content.By above-mentioned table 3 as can be seen that when one timing of reaction temperature, yield shadow of the reaction time to hydrocarbon compound
Sound is not apparent；But when reaction temperature is certain (160 DEG C), and the reaction time is 60min through at [DMEA] [oAc] ionic liquid
The degradation rate highest for the alkali lignin managed, depolymerization product (L2) yield may be up to 15.66%, wherein target product vanillic aldehyde
Content highest.The selectivity fracture for realizing ehter bond in alkali lignin structure, makes alkali lignin complexity macromolecular structure in temperature
Preliminary depolymerization under the conditions of, improves the content of low molecular weight compound aldehydes.
The FT-IR bands of a spectrum distribution of the pretreatment of table 4 front and back alkali lignin
Infrared spectrum (FT-IR spectrum) be for analyze depolymerization product composition functional group and structure according to pertinent literature
The classification of different absorption bands is carried out, the results are shown in Table 4.
By FT-IR spectral characterization, as a result as shown in Figure 7.Pretreated alkali lignin sample has with initial alkali lignin
Similar spectral signature, showing the general chemical structure of alkali lignin main chain, there is no great changes.However, being seen in Fig. 7
The variation for observing peak relative intensity shows the opposite variation of functional group during ionic liquid pretreatment.Pretreated alkali is wooden
1704cm in plain sample-1、1300cm-1Obtain prominent 1704cm (unobvious in alkali lignin bands of a spectrum)-1Centered on bands of a spectrum can be classified as
It is not coupled ketone, the flexible spectrum of the carbonyl of carbonyl and ester group.By pretreated alkali lignin to 1510cm-1Neighbouring absorption band is virtue
The feature of ring, 1280cm-1And 1080cm-1Bands of a spectrum also show the intensity of enhancing, this is related with C=O stretching, extension.These peak intensities
The oxidation (or forming Xi Baite ketone) of alkali lignin during the increase of degree may be from pretreatment.
As shown in Figure 7, these peaks are for [DMEA] [HSO4] pretreatment be it is most outstanding, for [DMEA] [Cl] in advance locate
Reason is least.Statistics indicate that [DMEA] [HSO4] generate due to the oxidation of alkali lignin and be not coupled and be conjugated in pretreatment
Carbonyl.After ionic liquid pretreatment, observe that intensity is 1510cm-1Intensity increase, belong to aromatic skeleton vibration.This
Kind effect pre-processes [DMEA] [HSO4] and [DMEA] [OAc] more prominent.The enhanced strength for thinking the band is in acidity
Under the conditions of alkali lignin aliphatic lateral chain condensation reaction or division result.
FT-IR and elemental analysis the result shows that, three kinds of ionic liquids are different to the chemical reactivity of alkali lignin, thus by
The chemical change of the alkali lignin skeleton of three kinds of ionic liquids induction is also different.Pervious document report confirms alkali in ionic liquid
Depolymerization that the heat treatment of lignin both can induce and again congealing reaction.But these exact mechanism of reaction are extremely complex, still
It is unclear.
Above-mentioned GC-MS the result shows that, depolymerization product depends on pretreatment temperature, the type of time and ionic liquid.?
Under 160 DEG C of lower pretreatment temperature, [DMEA] [OAc] and [DMEA] [HSO4] pretreated vanillic aldehyde and hydro carbons yield are most
It is high.
Alkali lignin depolymerization product (the L that table 5 obtains after pre-processing2) GC-MS product distribution
To the alkali lignin depolymerization product (L obtained after pretreatment2) carry out the composition analysis of product.And by alkali lignin
Depolymerization product (L2) in the higher compound of content and structural formula be listed in Table 5 below.In conjunction with table 5 and the GC-MS product of Fig. 8~10 point
Cloth situation can illustrate the H in acidic ion liquid+β-O-4 the key capableing of in the fracture alkali lignin structure of selectivity, is conducive to C+
Formation, make Cα-CβBreak to form the small molecules chemical combination such as oligomer and phenols (mainly vanilla aldehyde compound and hydrocarbon product)
Object effectively inhibits radical reaction, to reduce the molecular weight of alkali lignin.
Only the present invention will be further described for the above various embodiments, is not intended to limit the invention patent, all is this hair
Bright equivalence enforcement, is intended to be limited solely by within the scope of the claims of patent of invention.
Claims (3)
1. a kind of synthetic method of functionalization biology base ionic liquid, which is characterized in that this method comprising the following specific steps
Step 1: with N, N- dimethylethanolamine (DMEA) is raw material, carries out ion exchange by mixing, stirring with acid, solvent,
Solvent is removed at reduced pressure conditions using Rotary Evaporators, and sufficiently dry in vacuum oven, [DMEA] [M] class function is made
Biology base ionic liquid can be changed；Wherein, [M] is acid ion；The acid is hydrochloric acid, acetic acid or sulfuric acid；Described
Solvent is deionized water or anhydrous methanol；The raw material: acid: the molar ratio of solvent is 1: 1: 1；The mixing time be 24 ~
48h；The vacuum oven temperature is 55 ~ 75 DEG C.
2. functionalization biology base ionic liquid described in a kind of claim 1 is applied in alkali lignin pretreatment reaction, obtain high
The hydrocarbon compound and aldehyde compound of yield.
3. application according to claim 2, which is characterized in that by alkali lignin and functionalization biology base ionic liquid with 1:
9 mass ratio mixing makes the ehter bond in alkali lignin structure that selectivity occur under conditions of 100-160 DEG C, 30-150 min
Fracture, alkali lignin is degraded to hydrocarbon compound and aldehyde compound；Wherein, the ehter bond is β-O-4 or α-O-4 key；
The hydrocarbon compound is dodecane hydrocarbon, tetradecane hydrocarbon, hexadecane hydrocarbon and octadecane hydrocarbon；The aldehyde compound is vanillic aldehyde.
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