CN106987862A - A kind of method of the electrochemical degradation lignin in eutectic solvent - Google Patents
A kind of method of the electrochemical degradation lignin in eutectic solvent Download PDFInfo
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- CN106987862A CN106987862A CN201710235040.8A CN201710235040A CN106987862A CN 106987862 A CN106987862 A CN 106987862A CN 201710235040 A CN201710235040 A CN 201710235040A CN 106987862 A CN106987862 A CN 106987862A
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Abstract
The invention discloses a kind of method of the electrochemical degradation lignin in eutectic solvent, it is introduced into sulfonic lignin and is dissolved in eutectic solvent, the Electro-catalytic Oxidation Process lignin in the electrolytic cell that three electrodes are constituted, reclaims lignin and eutectic solvent after reaction in electrolyte and is recycled.The invention provides a kind of mild condition, current utilization rate high, conversion ratio and selectivity it is high, can cycle utilize, the method for environment amenable lignin degrading, lignin degradation is allowed to obtain more useful fine chemical products, with good development prospect and industrial application value.
Description
Technical field
Technical field is utilized the invention belongs to Liginon Resource increment conversion, is related to a kind of electrochemical oxidation degraded wooden
Element, the technical method for producing the fine chemicals such as vanillic aldehyde and guaiacol.
Background technology
Lignin is a kind of abundant renewable resource, can be for preparation armaticity structures alone.Traditional industrial mistake
Journey obtains energy by the lignin that burns.The latest developments of bioengineering, on the one hand realize and are converted into cellulose biomass
Liquid fuel, on the other hand generates substantial amounts of lignin.Therefore, in the urgent need to being with fuel by lignin increment conversion, adding
Plus the high value compound that agent and fine chemical product are representative.A variety of value products can be generated by raw material of lignin,
Therefore, the degradation process of lignin receives much concern.The core of lignin degradation is to be converted into lignin natural polymer to enter
Monomer or oligomer small molecule that one step is utilized.
The method of lignin degradation mainly has pyrolysis, enzymatic, homogeneous or heterogeneous catalysis.Pyrolysis lignin can be given birth to
Material oil, then as fuel.Enzymatic can crack lignin model compound, the lignin in removing timber.Homogeneously
Or heterogeneous catalysis also can successfully lignin degrading.But, homogeneous or heterogeneous catalysis process often uses ruthenium, iron, copper and vanadium etc.
Metallic catalyst, catalytic reaction will be carried out under the harsh conditions such as HTHP.The recovery of metallic catalyst and catalyst inactivation
Limit the application of catalytic process.
Electrochemical degradation lignin is as a kind of potential sustainable transform mode, and its advantage is fairly obvious.On the one hand, instead
There was only electro transfer in answering, and catalyst rests on electrode surface all the time;On the other hand, degradation reaction is entered at normal temperatures and pressures
OK, mild condition.Patent of invention " a kind of method of electrochemical means lignin degrading "(CN 102277591 B)Made using water
For electroanalysis solvent, by preferred electrode materials, optimize electrode lay-out, the oxygen that anode is generated is converted in close cathodic reduction
For hydrogen peroxide, so as to realize the appropriate oxidative degradation of lignin." a kind of electrochemical degradation lignin prepares 2,6- to patent of invention
The method of di-tert-butyl-4-methy phenol "(CN201310043286.7)Sodium hydroxide solution is used for electroanalysis solvent, with Pb/
PbO2 electrodes are as working electrode, and Cu plate electrodes are as auxiliary electrode, and standard saturated calomel electrode is electrolysed oxygen as reference electrode
Change lignin degrading, then 2,6- di-tert-butyl-4-methy phenols are made in acidified, separation and purifying.Patent of invention " ferrous sulfate
The method that electrochemical degradation lignin prepares dibutyl phthalate in solution "(CN 201310335441.2)Using sulfuric acid
Ferrous iron solution is electroanalysis solvent, the electrolytic oxidation lignin degrading in the electrolytic cell that three electrodes are constituted, and finally obtains O-phthalic
Dibutyl phthalate.In above-mentioned aqueous phase system, degraded along with the electrochemical oxidation of lignin, oxygen evolution reaction is synchronously carried out, i.e., one
Portion of electrical current is used for the cleavage reaction of carbon-carbon bond and carbon-oxygen bond in lignin, and one part of current is separated out for oxygen, current utilization rate
It is relatively low.
The content of the invention
In order to solve problems of the prior art, lignin degradation is allowed to obtain more useful fine chemical products,
The invention discloses a kind of method of the electrochemical degradation lignin in eutectic solvent, it is desirable to provide a kind of mild condition, electricity
Flow utilization rate high, conversion ratio and selectivity it is high, can cycle utilize, the method for environment amenable lignin degrading.
The technical proposal of the invention is realized in this way:
The invention discloses a kind of method of the electrochemical degradation lignin in eutectic solvent, comprise the following steps:
(1)It will be introduced into sulfonic lignin by sulfonation pretreatment first and be dissolved in eutectic solvent and form homogeneous system;
(2)By the lignin homogeneous system prepared be added to three electrodes composition electrolytic cell in, with working electrode be selected from nickel,
One kind in platinum, gold, copper electrode, auxiliary electrode is platinum electrode or carbon electrode, and reference electrode is selected from silver/silver chloride electrode, saturation
One kind in calomel electrode or hydrogen electrode, constitutes electrolytic cell, the electro-catalysis under the conditions of oxidizing potential is 0.5-1V, reaction 1-24h
Oxidative degradation lignin is to produce vanillic aldehyde and guaiacol;
Wherein, the eutectic solvent salt and hydrogen bond donor by being made up of, and wherein salt is selected from choline hydrochloride, methyl triphenyl
One or more in bromide phosphine, N, N- diethylaluminum ethoxide ammonium chlorides, hydrogen bond donor is in urea, ethylene glycol, glycerine
One or more material mixings.
Preferably, step(1)In, the solubility of lignin is 0.1-100g/L in the homogeneous system.
As a kind of preferred embodiment, the method for described electrochemical degradation lignin also includes:Reclaim electricity after reaction
Lignin and eutectic solvent in solution liquid are recycled.Specifically recovery method can be:After sour diluting reaction
Electrolyte, is collected by filtration the insoluble lignin of precipitation;By the solvable lignin in organic extractant phase supernatant liquor, then methyl is different
The stirring mixed with water of butyl ketone, centrifuges organic phase and aqueous phase;The methyl iso-butyl ketone (MIBK) in organic phase is distilled off, obtains
The arene compound that lignin oxidation's degraded is produced, is distilled off the moisture in aqueous phase, obtains eutectic solvent, circulating is used for
Lignin electrochemical oxidation is degraded.Preferably, the acid of dilute electrolyte is one kind in dilute sulfuric acid, watery hydrochloric acid, dust technology, acid group
Ion concentration is 0.001-0.1 mol/L, and the volume ratio of acid and electrolyte is(1-20):1;The organic phase is ethyl acetate.
Compared with prior art, beneficial effects of the present invention are:
(1)The present invention utilizes three electrolysis devices, the electrochemical oxidation lignin degrading in eutectic solvent system, it is to avoid oxygen
Evolution reaction, improves current utilization rate, environmentally friendly;
(2)The sulfonation pretreating process of lignin uses common process, introduces sulfonic lignin and adds lignin
Hydrophily, make the degradation conditions of lignin gentle, selectivity is high, degraded obtains vanillic aldehyde and guaiacol etc. and become more meticulous
The high conversion rate of product, makes guaiacol yield up to 30-38%, vanillic aldehyde yield is 34-37%, and lignin conversion rate is improved
To 80-95%;
(3)Eutectic solvent system is with low cost, can be recycled by simple distillation.
Embodiment
The technical scheme in the embodiment of the present invention will be clearly and completely described below, it is clear that described implementation
Example only a part of embodiment of the invention, rather than whole embodiments.Based on the embodiment in the present invention, this area is common
The every other embodiment that technical staff is obtained under the premise of creative work is not made, belongs to the model that the present invention is protected
Enclose.
Embodiment 1
A kind of method of the electrochemical degradation lignin in eutectic solvent, through the following steps that realize:
(1)Choline hydrochloride and urea press 1:2 ratio Hybrid Heating, obtains the colourless eutectic solvent of homogeneous transparent, is introduced into
Sulfonic lignin, which is dissolved in eutectic solvent, forms homogeneous system, and the concentration of lignin is 10g/L;
(2)In the electrolytic cell that the lignin homogeneous system prepared is added to three electrodes composition, using nickel electrode as working electrode,
Platinum electrode is auxiliary electrode, and reference electrode is silver/silver chloride electrode, sets oxidizing potential as 0.5V, the reaction time is 5h, electricity is urged
Change oxidative degradation lignin, guaiacol yield is 38%, and vanillic aldehyde yield is 36%, lignin conversion rate 87%;
(3)By VAcid:VElectrolyteFor 1:Electrolyte of 5 ratio after 0.01mol/L dilute sulfuric acid diluting reaction, is collected by filtration precipitation
Insoluble lignin is further degraded as raw material;Ethyl acetate makees the solvable lignin in organic extractant phase supernatant liquor, then will
Methyl iso-butyl ketone (MIBK) stirring mixed with water, centrifuges organic phase and aqueous phase;The methyl-isobutyl in organic phase is distilled off
Ketone, obtains arene compound of lignin oxidation's degraded generation based on vanillic aldehyde and guaiacol, is distilled off in aqueous phase
Moisture, obtain eutectic solvent, circulate for lignin electrochemical oxidation degraded.
Embodiment 2
A kind of method of the electrochemical degradation lignin in eutectic solvent, through the following steps that realize:
(1)Choline hydrochloride and ethylene glycol press 1:2 ratio Hybrid Heating, obtains the colourless eutectic solvent of homogeneous transparent, will draw
Enter sulfonic lignin and be dissolved in eutectic solvent to form homogeneous system, the concentration of lignin is 20g/L;
(2)In the electrolytic cell that the lignin homogeneous system prepared is added to three electrodes composition, using platinum electrode as working electrode,
Carbon electrode is auxiliary electrode, and reference electrode is saturated calomel electrode, sets oxidizing potential as 1V, and the reaction time is 24h, electro-catalysis
Oxidative degradation lignin, guaiacol yield is 38%, and vanillic aldehyde yield is 37%, lignin conversion rate 95%;
(3)By VAcid:VElectrolyteFor 1:Electrolyte of 10 ratio after 0. 1mol/L watery hydrochloric acid diluting reaction, is collected by filtration analysis
Go out insoluble lignin as raw material further to degrade;Ethyl acetate makees the solvable lignin in organic extractant phase supernatant liquor, then
By methyl iso-butyl ketone (MIBK) stirring mixed with water, organic phase and aqueous phase are centrifuged;The methyl tert-butyl in organic phase is distilled off
Base ketone, obtains arene compound of lignin oxidation's degraded generation based on vanillic aldehyde and guaiacol, aqueous phase is distilled off
In moisture, obtain eutectic solvent, circulate for lignin electrochemical oxidation degraded.
Embodiment 3
A kind of method of the electrochemical degradation lignin in eutectic solvent, through the following steps that realize:
(1)N, N- diethylaluminum ethoxide ammonium chloride and glycerine press 1:3 ratio Hybrid Heating, obtains colourless low common of homogeneous transparent
Molten solvent, is introduced into sulfonic lignin and is dissolved in eutectic solvent and form homogeneous system, and the concentration of lignin is 40g/L;
(2)In the electrolytic cell that the lignin homogeneous system prepared is added to three electrodes composition, using gold as working electrode, platinum electricity
Extremely auxiliary electrode, reference electrode is hydrogen electrode, sets oxidizing potential as 1V, and the reaction time is 3h, Electro-catalytic Oxidation Process wood
Quality, guaiacol yield is 36%, and vanillic aldehyde yield is 35%, lignin conversion rate 85%;
(3)By VAcid:VElectrolyteFor 1:Electrolyte of 20 ratio after 0.02mol/L dust technology diluting reaction, is collected by filtration analysis
Go out insoluble lignin as raw material further to degrade;Ethyl acetate makees the solvable lignin in organic extractant phase supernatant liquor, then
By methyl iso-butyl ketone (MIBK) stirring mixed with water, organic phase and aqueous phase are centrifuged;The methyl tert-butyl in organic phase is distilled off
Base ketone, obtains arene compound of lignin oxidation's degraded generation based on vanillic aldehyde and guaiacol, aqueous phase is distilled off
In moisture, obtain eutectic solvent, circulate for lignin electrochemical oxidation degraded.
Embodiment 4
A kind of method of the electrochemical degradation lignin in eutectic solvent, through the following steps that realize:
(1)Methyltriphenylphosphonium bromide and ethylene glycol press 1:3 ratio Hybrid Heating, obtains the colourless eutectic of homogeneous transparent molten
Agent, is introduced into sulfonic lignin and is dissolved in eutectic solvent and form homogeneous system, and the concentration of lignin is 80g/L;
(2)In the electrolytic cell that the lignin homogeneous system prepared is added to three electrodes composition, using copper as working electrode, platinum electricity
Extremely auxiliary electrode, reference electrode is silver/silver chloride electrode, sets oxidizing potential as 0.5V, the reaction time is 10h, electro-catalysis
Oxidative degradation lignin, guaiacol yield is 38%, and vanillic aldehyde yield is 37%, lignin conversion rate 90%;
(3)By VAcid:VElectrolyteFor 1:Electrolyte of 4 ratio after 0.05mol/L dilute sulfuric acid diluting reaction, is collected by filtration precipitation
Insoluble lignin is further degraded as raw material;Ethyl acetate makees the solvable lignin in organic extractant phase supernatant liquor, then will
Methyl iso-butyl ketone (MIBK) stirring mixed with water, centrifuges organic phase and aqueous phase;The methyl-isobutyl in organic phase is distilled off
Ketone, obtains arene compound of lignin oxidation's degraded generation based on vanillic aldehyde and guaiacol, is distilled off in aqueous phase
Moisture, obtain eutectic solvent, circulate for lignin electrochemical oxidation degraded.
Embodiment 5
A kind of method of the electrochemical degradation lignin in eutectic solvent, through the following steps that realize:
(1)N, N- diethylaluminum ethoxide ammonium chloride, methyltriphenylphosphonium bromide and ethylene glycol press 1:3:12 ratio Hybrid Heating, is obtained
To the colourless eutectic solvent of homogeneous transparent, it is introduced into sulfonic lignin and is dissolved in eutectic solvent and form homogeneous system,
The concentration of lignin is 10g/L;
(2)In the electrolytic cell that the lignin homogeneous system prepared is added to three electrodes composition, using nickel as working electrode, platinum electricity
Extremely auxiliary electrode, reference electrode is silver/silver chloride electrode, sets oxidizing potential as 1V, the reaction time is 15h, electrocatalytic oxidation
Change lignin degrading, guaiacol yield is 38%, and vanillic aldehyde yield is 37%, lignin conversion rate 92%;
(3)By VAcid:VElectrolyteFor 1:Electrolyte of 2 ratio after 0.06mol/L dilute sulfuric acid diluting reaction, is collected by filtration precipitation
Insoluble lignin is further degraded as raw material;Ethyl acetate makees the solvable lignin in organic extractant phase supernatant liquor, then will
Methyl iso-butyl ketone (MIBK) stirring mixed with water, centrifuges organic phase and aqueous phase;The methyl-isobutyl in organic phase is distilled off
Ketone, obtains arene compound of lignin oxidation's degraded generation based on vanillic aldehyde and guaiacol, is distilled off in aqueous phase
Moisture, obtain eutectic solvent, circulate for lignin electrochemical oxidation degraded.
Embodiment 6
A kind of method of the electrochemical degradation lignin in eutectic solvent, through the following steps that realize:
(1)N, N- diethylaluminum ethoxide ammonium chloride, ethylene glycol and glycerine press 1:1:3 ratio Hybrid Heating, obtains homogeneous transparent
Colourless eutectic solvent, is introduced into sulfonic lignin and is dissolved in eutectic solvent and form homogeneous system, lignin it is dense
Spend for 5g/L;
(2)In the electrolytic cell that the lignin homogeneous system prepared is added to three electrodes composition, using nickel as working electrode, platinum electricity
Extremely auxiliary electrode, reference electrode is silver/silver chloride electrode, sets oxidizing potential as 1V, the reaction time is 20h, electrocatalytic oxidation
Change lignin degrading, guaiacol yield is 38%, and vanillic aldehyde yield is 37%, lignin conversion rate 94%;
(3)By VAcid:VElectrolyteFor 1:Electrolyte of 4 ratio after 0.01mol/L dust technology diluting reaction, is collected by filtration precipitation
Insoluble lignin is further degraded as raw material;Ethyl acetate makees the solvable lignin in organic extractant phase supernatant liquor, then will
Methyl iso-butyl ketone (MIBK) stirring mixed with water, centrifuges organic phase and aqueous phase;The methyl-isobutyl in organic phase is distilled off
Ketone, obtains arene compound of lignin oxidation's degraded generation based on vanillic aldehyde and guaiacol, is distilled off in aqueous phase
Moisture, obtain eutectic solvent, circulate for lignin electrochemical oxidation degraded.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
God is with principle, and any modification, equivalent substitution and improvements made etc. should be included in the scope of the protection.
Claims (6)
1. a kind of method of the electrochemical degradation lignin in eutectic solvent, it is characterised in that comprise the following steps:
(1)It will be introduced into sulfonic lignin by sulfonation processing first and be dissolved in eutectic solvent and form homogeneous system;
(2)By the lignin homogeneous system prepared be added to three electrodes composition electrolytic cell in, with working electrode be selected from nickel,
One kind in platinum, gold, copper electrode, auxiliary electrode is platinum electrode or carbon electrode, and reference electrode is selected from silver/silver chloride electrode, saturation
One kind in calomel electrode or hydrogen electrode, constitutes electrolytic cell, the electro-catalysis under the conditions of oxidizing potential is 0.5-1V, reaction 1-24h
Oxidative degradation lignin is to produce vanillic aldehyde and guaiacol;
Wherein, the eutectic solvent salt and hydrogen bond donor by being made up of, and wherein salt is selected from choline hydrochloride, methyl triphenyl
One or more in bromide phosphine, N, N- diethylaluminum ethoxide ammonium chlorides, hydrogen bond donor is in urea, ethylene glycol, glycerine
One or more material mixings.
2. the method for electrochemical degradation lignin as claimed in claim 1, it is characterised in that:Step(1)In, the homogeneous body
The solubility of lignin is 0.1-100g/L in system.
3. the method for electrochemical degradation lignin as claimed in claim 1, it is characterised in that also include:Reclaim and be electrolysed after reaction
Lignin and eutectic solvent in liquid are recycled.
4. the method for electrochemical degradation lignin as claimed in claim 3, it is characterised in that:With the electrolysis after sour diluting reaction
Liquid, is collected by filtration the insoluble lignin of precipitation;By the solvable lignin in organic extractant phase supernatant liquor, then by methyl-isobutyl
Ketone stirring mixed with water, centrifuges organic phase and aqueous phase;The methyl iso-butyl ketone (MIBK) in organic phase is distilled off, obtains wooden
The arene compound that plain oxidative degradation is produced, is distilled off the moisture in aqueous phase, obtains eutectic solvent, circulates for wooden
Plain electrochemical oxidation degraded.
5. the method for electrochemical degradation lignin as claimed in claim 4, it is characterised in that:The acid of dilute electrolyte is dilute sulphur
One kind in acid, watery hydrochloric acid, dust technology, acid ion concentration is 0.001-0.1 mol/L, and the volume ratio of acid and electrolyte is
(1-20):1.
6. the method for electrochemical degradation lignin as claimed in claim 4, it is characterised in that:The organic phase is acetic acid second
Ester.
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CN108823595A (en) * | 2018-07-12 | 2018-11-16 | 东北石油大学 | A kind of method of solar energy STEP process high-temperature electrolysis lignin |
CN109518209A (en) * | 2019-01-15 | 2019-03-26 | 河北工业大学 | The method that 4-hydroxyanisol unit and tertiary butyl chloride in electro-catalysis lignin prepare 3- tert-butyl 4-hydroxyanisol |
CN109680296A (en) * | 2018-12-24 | 2019-04-26 | 河北工业大学 | A method of the O-methoxy phenolic group group decomposited with lignin prepares eugenol with additional allyl reaction |
CN113088542A (en) * | 2021-04-23 | 2021-07-09 | 淮阴师范学院 | Biomass pretreatment process and method for recovering solvent used in treatment process |
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Cited By (6)
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CN109518209A (en) * | 2019-01-15 | 2019-03-26 | 河北工业大学 | The method that 4-hydroxyanisol unit and tertiary butyl chloride in electro-catalysis lignin prepare 3- tert-butyl 4-hydroxyanisol |
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CN113088542A (en) * | 2021-04-23 | 2021-07-09 | 淮阴师范学院 | Biomass pretreatment process and method for recovering solvent used in treatment process |
CN113088542B (en) * | 2021-04-23 | 2023-10-24 | 淮阴师范学院 | Biomass pretreatment process and solvent recovery method used in treatment process thereof |
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