CN106676574A - Method for preparing aromatic compounds by conducting hydrogenation and depolymerization on spruce lignin through electro-catalysis technology - Google Patents
Method for preparing aromatic compounds by conducting hydrogenation and depolymerization on spruce lignin through electro-catalysis technology Download PDFInfo
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Abstract
The invention provides a method for preparing aromatic compounds by conducting hydrogenation and depolymerization on spruce lignin through the electro-catalysis technology. According to the method, electrocatalytic oxidation is conducted in a sodium hydroxide solution so that the lignin can be degraded, meanwhile, degradation intermediates in the spruce lignin are subjected to hydrogenation reduction through cooperation of electro-catalysis, that is, an electrolytic reaction tank is composed of a Pb/PbO2 electrode and a Ni electrode, a lignin alkaline solution serves as an electrolyte solution, part of chemical bonds in the lignin are subjected to oxidative cleavage by active substances (hydroxyl radical.OH or peroxy-anion radical O2<->) generated on the surface of the anode (the Pb/PbO2 electrode) through electrolysis alkaline water, the molecular weight of the lignin is effectively reduced, depolymerized compound intermediates are subjected to hydrogenation reduction by adsorption hydrogen atoms (Hads) generated on the surface of the cathode (the Ni electrode) through the electrolysis alkaline water, and finally, aromatic products including methylbenzene, ortho-xylene and m-xylene are obtained.
Description
Technical field
Present invention belongs to biomass energy chemical field, is related to a kind of electricity consumption catalysis technique hydrogenation depolymerization corn straw
The method that lignin prepares aromatic compound, i.e., active specy (the hydrogen-oxygen freedom for being produced in anode surface using electrolysis aqueous alkali
Base OH crosses Atomic oxygen radical anion O2 ·-) part chemical bond key in oxidation scission lignin, make lignin obtain effective depolymerization
And cause its molecular weight to reduce, while cathode surface is because being electrolysed the hydrogen ion adsorption (H that hydrone is producedads) hydro-reduction is wooden
On the intermediate of element cracking, stable valuable arene compounds are finally given.
Technical background
Lignin is a kind of natural reproducible macromolecular material, content and its abundant, accounts for four points of xylophyta
One of.Due to the armaticity and the network structure of high polymerization degree of lignin, lignin is difficult to effectively be degraded.Therefore pulping and paper-making
The by-product lignin produced in industry can not be utilized mostly, and " the lignin night " that about 5000 tons are had every year is directly discharged into
Directly burn in river or after concentration, this not only causes the waste of precious resources, goes back severe contamination natural environment.If can seek
Find efficient, cheap, environmental protection biodegrading process lignin is fractured into into small molecule or valuable chemicals are obtained,
Extremely profound significance will be produced to social development.
In recent years, the exploitation of Renewable resource have caused domestic and international researcher to pay attention to.Wherein, lignin is
The derived energy chemical of raw material is strengthened, and only the biodegrading process of lignin just has many document reports, such as alcoholysis, acidolysis, pyrolysis, electricity
Catalytic degradation and enzymatic degradation method etc..For example：Li Guangxue is with ZnCl2,CoMo/Al2O3For catalyst, lignin hydrogenation has been investigated
The process conditions of liquefaction, product is toluene, guaiacol, methyl phenyl ethers anisole, phenol etc..Imperial Venus etc. adopts solid under the conditions of 250 DEG C
Body alkali MgO is catalyst, and the catalytic degradation characteristic research of Masson Pine lignin has been carried out as solvent with tetrahydrofuran, obtains 97%
Conversion ratio and 13.2% single phenol yield.Zeng etc. enters in Supercritical Ethanol (7MPa, 250 DEG C) Yong Fenton reagent to lignin
Row catalytic degradation, obtains monocyclic compound, oligomer, phenol, carboxylic acid and ester etc..Chang etc. is in TiO2Surface photocatalytic oxidation
Lignin degrading sulfonate, although degradation rate reaches 90%, but photocatalytic degradation method easily causes deep oxidative degradation, and alkali is wooden
Element is finally decomposed to CO2And H2O.Omar Movil-Cabrera etc. use Co/Pt electrodes electrocatalytic oxidation in sodium hydroxide solution
Change lignin degrading, obtain the products such as heptane, heptene, phenol, but Pt's is expensive.
Conclude existing lignin degradation method and to can be seen that also exist at present technique harsh and high to equipment requirements
The supercritical technology of problem, such as High Temperature High Pressure；Hydrogenation depolymerization lignin will use hydrogen addition technology, hydrogen inherently to clean money
Source；Catalyst noble metal causes production cost too high.Although the hydrogen atom content on lignin molecule is very low, corn straw is wooden
The oxygen-containing small molecule chemical combination such as the hydrocarbon oxygen element quantity ratio (C: H: O=1: 1.13: 0.476) of element, organic aldehyde, phenol, carboxylic acid and ester
Thing is the common compounds of lignin degradation, but if is obtained in that hydrocarbons have more can lignin degradation technique
Practical value.Therefore more effective, eco-friendly method lignin degrading is adopted, the molecular weight of lignin is reduced and is had
The micromolecular compound of value, is current main direction of studying.
The content of the invention
The purpose of the present invention is for not enough present in current techniques, there is provided a kind of electricity consumption catalysis technique hydrogenation depolymerization is beautiful
The method that rice straw lignin prepares aromatic compound.The method by sodium hydroxide solution Electro-catalytic Oxidation Process it is wooden
Element, while coordinate electric catalyticing hydro to reduce the degraded intermediate of Spruce lignin, i.e., using Pb/PbO2Electrode and Ni electrodes
, used as electrolyte solution, electrolysis aqueous alkali is in anode (Pb/PbO for composition cell reaction pond and lignin aqueous slkali2Electrode) surface
(hydroxyl free radical OH crosses Atomic oxygen radical anion O to the active specy of generation2 ·-) part chemical bond in oxidation scission lignin
Key, makes lignin molecule amount effectively reduce, and the compound intermediate that depolymerization goes out is electrolysed aqueous alkali and is produced on negative electrode (Ni electrodes) surface
Raw hydrogen ion adsorption (Hads) hydro-reduction, finally give the aromatic products such as toluene, o-Dimethylbenzene, meta-xylene.
The technical scheme is that
A kind of method that electricity consumption catalysis technique hydrogenation depolymerization Spruce lignin prepares aromatic compound, including following step
Suddenly：
The first step：Sodium hydroxide solution is added in reactor, Spruce lignin is added, 30~60min is stirred,
The homogeneous aqueous slkali of lignin is formed after dissolving；
Wherein, 2~10g Spruce lignins are added per 200ml sodium hydroxide solutions；Described sodium hydroxide solution
Dense is 0.5~1mol/L；
Second step：There is parallel fixed Pb/PbO in lignin aqueous slkali reactor in the title of previous step2Electrode is anode, nickel
Electrode is negative electrode, keeps 2~2.5cm of distance between two electrodes, constant-current electrolysis is carried out under at the uniform velocity stirring under room temperature, in two interpolars
It is 10~50mA/cm to apply electric current close2, after electrocatalytic reaction time 1h~5h, stopped reaction；
3rd step：Solution after electrolysis is moved in another reactor, is then added in the reactor isopyknic
Extractant, then Deca dilute sulfuric acid under agitation again, until the pH value of the solution in reactor is 1~2, when there is no longer new wood
Quality residue is separated out, and obtains the solution containing aromatic compound；
Described dilute sulfuric acid concentration is 0.5~0.86mol/L；
Described extractant is specially chloroform.
The biodegrading process is simple to operate and friendly to environment.The electrocatalytic oxidation effect of anode surface can make corn straw wood
The molecular weight of quality constantly reduces, and realizes effective fracture of lignin macromole, in cathode surface electrolysis aqueous alkali preparation
Active hydrogen has been done directly the hydro-reduction to lignin degradation intermediate and has reacted, and the protium content of catabolite has certain journey
Improve, or even the aromatic compound with higher-value such as toluene, meta-xylene, o-Dimethylbenzene can also be obtained.
The invention has the beneficial effects as follows：
(1) the present invention adsorbs the reactive hydrogen atom (MH in electrode surface by being electrolysed the aqueous alkali hydrogen manufacturing containing ligninads)
The intermediate molecule that can be cracked with hydro-reduction lignin, finally gives the hydrogenation products of hydrogen content raising, and corn straw is wooden
The number of elements ratio (carbon C: hydrogen H: oxygen O=1: 1.13: 0.476) of element, the hydrocarbon oxygen element quantity of target product than toluene (C: H:
0), o-Dimethylbenzene (C: H: O=1: 1.25: 0), meta-xylene (C: H: O=1: 1.25: 0) O=1: 1.14:；
(2) the carbon hydrogen element of target product, than improving, is the hydro-reduction reaction for completing at room temperature, at a normal in the present invention,
Hydrogen feed is not only used, it is thus also avoided that hydrogenation reaction needs the complicated technology condition of High Temperature High Pressure；
(3) the aromatic product that obtains in the present invention, toluene (27g/kg- lignins), o-Dimethylbenzene (9g/kg- lignins) and
Meta-xylene (10g/kg- lignins) yield is higher, can partly substitute or supplement the product of fossil feedstock (oil and coal) production
Product, stable in properties, using value is high.
Description of the drawings
Fig. 1 is that embodiment Electrocatalysis Degradation process Spruce lignin residue molecular weight distribution GPC is schemed and aromatic product.
Specific embodiment
Spruce lignin of the present invention be commercially available prod, 60~80 mesh granules.
Embodiment 1
In being furnished with the beaker of agitator, 8g Spruce lignins are added to be dissolved in 200mL sodium hydroxide solution (1mol/
L in), the homogeneous aqueous slkali of lignin is formed, beaker is put in 30 DEG C of thermostat water baths.To wooden under D.C. regulated power supply
Plain aqueous slkali is electrolysed, and anode is Pb/PbO2Electrode, negative electrode is Ni electrodes, and electric current density is 30mA/cm2, the work of electrode
Area is all 24cm2.Stop electrolysis after 2h and obtain lignin degradation mother solution.Add after 200mL chloroform in degraded mother solution,
While stirring Deca dilute sulfuric acid (0.86mol/L) adjusts solution ph to 1~2, and catabolite is extracted to the chloromethane of organic faciess three
In alkane, all precipitations from mother solution in acid condition of residual residue lignin.The residue lignin for filtering to isolate carries out 2~
3 washing desalinations and after being dried 6h in vacuum drying oven, characterize its molecular weight after weighing, 200mL is subsequently redissolved in again
In sodium hydroxide solution and carry out second Electrocatalysis Degradation reaction.
Solidliquid mixture obtained in the previous step is separated with centrifuge, is obtained undegradable lignin residue and liquid is produced
The mean molecule quantity of thing, lignin or lignin residue is determined with gel permeation chromatography；
Previous step is obtained into liquid separatory funnel to separate, organic faciess and water phase is obtained, the lignin hydrogenation in organic faciess
Catabolite is with using gas chromatogram fixative and gas chromatogram and mass spectrograph multiple techniques qualitative and quantitative analysis.
The present invention determines the number-average molecular weight and Weight-average molecular of Spruce lignin raw material using gel permeation chromatography
Molecular weight distribution is measured and calculated, with analytical balance a small amount of lignin is weighed, N,N-dimethylacetamide makees solvent, prepares quality
Fraction is 2% solution, and detection and analysis is carried out on high performance liquid chromatograph (Shimadzu LC-20AD), from differential refraction
Detector (Shimadzu RID-10A), chromatographic column is Waters StyragelHT4, and mobile phase is N,N-dimethylacetamide,
Flow velocity is 0.9uL/min, and run time is 15min.
The present invention still determines the molecular weight distribution of lignin residue using gel permeation chromatography, takes a small amount of electrocatalytic reaction
Residual residue lignin afterwards, is dissolved in N,N-dimethylacetamide, is configured to the solution that mass fraction is 0.2%.Detection side
Method is as above, obtained the weight average molecular weight (Mw) and number-average molecular weight (Mw) of residue lignin, and its molecular weight distribution
(DPI)。
The present invention is to the catabolite in extraction phase using gas chromatogram and mass spectrograph multiple techniques qualitative analyses lignin
Catabolite, gas chromatogram (Agilent 7890B), capillary chromatographic column (Agilent HP-5MS), quadrupole rod flight time
Tandem mass spectrometer (Agilent 7200B).
The present invention is carried out using gas chromatogram (Shimadzu 2010-plus) to the catabolite in extraction phase to sample
Uantitative analytical, chromatographic column (Agilent HP-5MS), injection port temperature is 220 DEG C, and ion flame detector temperature is 280 DEG C,
Sample size is 1 μ L, and split ratio is 1:30, nitrogen is carrier gas and carrier gas speed is 30mL/min, and the temperature programming of column oven is 50
DEG C retain 1min, heating rate is 10 DEG C/min, is warming up to 250 DEG C, and keep 20min.
Aromatic hydrocarbons (toluene, o-Dimethylbenzene, meta-xylene) yield is shown in attached in the molecular weight distribution data measured and catabolite
Shown in table 1.
Fig. 1 gives weight average molecular weight Mw, number-average molecular weight Mn, the molecular weight distributing index DPI of Spruce lignin
Changes in contrast, illustrate electric catalyticing hydro depolymehzation process not only lignin raw material macromolecules degradation be 3 parts of relatively small molecular weight
Compound, while the compound intermediate that depolymerization goes out be hydrogenated be reduced to the aromatic hydrocarbons such as toluene, o-Dimethylbenzene, meta-xylene product
Thing.
Embodiment 2
4g Spruce lignins are dissolved in 200mL sodium hydroxide solutions (1mol/L), and between two electrodes electric current density is applied
10mA/cm2, Electrocatalysis Degradation response time 4h.Other steps are with embodiment 1.Lignin residue molecular weight distribution data and drop
Aromatics yield is seen attached list shown in 1 in solution product.
Embodiment 3
2g Spruce lignins are dissolved in 200mL sodium hydroxide solutions (0.6mol/L), electric current are applied between two electrodes close
Degree 20mA/cm2, Electrocatalysis Degradation response time 6h.Other steps are with embodiment 1.Lignin residue molecular weight distribution data and
Aromatics yield is as shown in appendix 1 in catabolite.
Embodiment 4
8g Spruce lignins are dissolved in 200mL sodium hydroxide solutions (1mol/L), and between two electrodes electric current density is applied
For 30mA/cm2, Electrocatalysis Degradation response time 8h.Other steps are with embodiment 1.Lignin residue molecular weight distribution data and
Aromatics yield is as shown in appendix 1 in catabolite.
Embodiment 5
8g Spruce lignins are dissolved in 200mL sodium hydroxide solutions (0.8mol/L), electric current are applied between two electrodes close
Spend for 40mA/cm2, the Electrocatalysis Degradation response time is 10h.Other steps are with embodiment 1.Lignin residue molecular weight distribution number
According to and catabolite in aromatics yield as shown in appendix 1.
Embodiment 6
10g Spruce lignins are dissolved in 200mL sodium hydroxide solutions (1mol/L), and between two electrodes electric current density is applied
For 50mA/cm2, Electrocatalysis Degradation response time 2h.Other steps are with embodiment 1.Lignin residue molecular weight distribution data and
Aromatics yield is as shown in appendix 1 in catabolite.
Embodiment 7
In being furnished with the beaker of agitator, 8g Spruce lignins are added in 200mL sodium hydroxide solutions (1mol/L)
In, the homogeneous aqueous slkali of lignin is formed, beaker is put in 30 DEG C of thermostat water baths.To lignin under D.C. regulated power supply
Aqueous slkali is electrolysed, and anode is Pb/PbO2Electrode, negative electrode is Ni electrodes, and the work area of electrode is 20cm2, between two electrodes
Applying electric current density is 30mA/cm2, Electrocatalysis Degradation reaction is stopped after 2h.200mL chloroform is added in degraded mother solution
Afterwards, while stirring Deca dilute sulfuric acid (0.86mol/L) adjusts pH to 1~2, and residual residue lignin is all analysed in acid condition
Go out.After 2~3 washings desalination, dryings are carried out to remaining residue lignin, weighing, taking a small amount of sample GPC, to measure residue wooden
The number-average molecular weight and weight average molecular weight of element simultaneously calculate molecular weight distribution, and remaining residue carries out second electrochemical degradation.Extraction
Catabolite in phase chloroform is analyzed using gas chromatogram molecular method quantification.Residual residue lignin is entered under the same conditions
After second Electrocatalysis Degradation reaction 2h of row, catabolite and quantitative analyses are extracted, the residue lignin isolated is identical
Number-average molecular weight, weight average molecular weight and molecular weight distribution are measured under experiment condition, and carries out third time electrolysis, this experimentation is followed
Ring 4 times.Aromatics yield is as shown in subordinate list 2 in lignin residue molecular weight distribution data and catabolite.
Embodiment 8
4g Spruce lignins are dissolved in 200mL sodium hydroxide solutions (0.5mol/L), electric current are applied between two electrodes close
Spend for 40mA/cm2.Other steps are with embodiment 7.Aromatics yield is such as in lignin residue molecular weight distribution data and catabolite
Shown in subordinate list 3.
Embodiment 9
6g Spruce lignins are dissolved in 200mL sodium hydroxide solutions (0.7mol/L), electric current are applied between two electrodes close
Spend for 30mA/cm2.Other steps are with embodiment 7.Aromatics yield is such as in lignin residue molecular weight distribution data and catabolite
Shown in subordinate list 4.
Embodiment 10
6g Spruce lignins are dissolved in 200mL sodium hydroxide solutions (1mol/L), and between two electrodes electric current density is applied
For 20mA/cm2.Other steps are with embodiment 7.Aromatics yield is for example attached in lignin residue molecular weight distribution data and catabolite
Shown in table 5.
Embodiment 11
2g Spruce lignins are dissolved in 200mL sodium hydroxide solutions (1mol/L), and between two electrodes electric current density is applied
For 10mA/cm2.Other steps are with embodiment 7.Aromatics yield is for example attached in lignin residue molecular weight distribution data and catabolite
Shown in table 6.
The summary sheet of the molecular weight distribution of lignin residue and catabolite aromatic compound yield in embodiment 1-6 of table 1
Note "-" does not detect the compound.
The summary sheet of the molecular weight distribution of lignin residue and catabolite aromatic compound yield in the embodiment 7 of table 2
Note："-" is represented and does not detect the compound.
The summary sheet of the molecular weight distribution of lignin residue and catabolite aromatic compound yield in the embodiment 8 of table 3
Note："-" is represented and does not detect the compound.
The summary sheet of the molecular weight distribution of lignin residue and catabolite aromatic compound yield in the embodiment 9 of table 4
Note："-" is represented and does not detect the compound.
The summary sheet of the molecular weight distribution of lignin residue and catabolite aromatic compound yield in the embodiment 10 of table 5
Note："-" is represented and does not detect the compound.
The summary sheet of the molecular weight distribution of lignin residue and catabolite aromatic compound yield in the embodiment 11 of table 6
Note："-" is represented and does not detect the compound.
Unaccomplished matter of the present invention is known technology.
Claims (2)
1. a kind of method that electricity consumption catalysis technique hydrogenation depolymerization Spruce lignin prepares aromatic compound, it is characterized by including
Following steps：
The first step：Sodium hydroxide solution is added in reactor, Spruce lignin is added, 30~60min, dissolving is stirred
The homogeneous aqueous slkali of lignin is formed afterwards；
Wherein, 2~10g Spruce lignins are added per 200ml sodium hydroxide solutions；The dense of described sodium hydroxide solution be
0.5~1mol/L；
Second step：There is parallel fixed Pb/PbO in lignin aqueous slkali reactor in the title of previous step2Electrode is anode, nickel electrode
For negative electrode, 2~2.5cm of distance between two electrodes is kept, under at the uniform velocity stirring under room temperature constant-current electrolysis is carried out, applied in two interpolars
Plus it is 10 ~ 50mA/cm that electric current is close2, after electrocatalytic reaction time 1h ~ 5h, stopped reaction；
3rd step：Solution after electrolysis is moved in another reactor, then isopyknic extraction is added in the reactor
Agent, then Deca dilute sulfuric acid under agitation again, until the pH value of the solution in reactor is 1 ~ 2, when there is no longer new lignin
Residue is separated out, and obtains the solution containing aromatic compound；
Described extractant is specially chloroform.
2. the method that electro-catalysis technology hydrogenation depolymerization Spruce lignin as claimed in claim 1 prepares aromatic compound,
It is characterized by described dilute sulfuric acid concentration is 0.5 ~ 0.86mol/L.
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| CN107890871A (en) * | 2017-12-01 | 2018-04-10 | 东北石油大学 | The method that lignosulfonates catalytic degradation produces compound aromatic base |
| 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 |
| 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 |
| CN111807573A (en) * | 2020-07-16 | 2020-10-23 | 湖南中湘春天环保科技有限公司 | Treatment device and method for thallium-containing wastewater |
| CN112831799A (en) * | 2020-12-30 | 2021-05-25 | 北京化工大学 | Method for electrochemically depolymerizing lignin |
| CN114184722A (en) * | 2021-12-17 | 2022-03-15 | 南亚新材料科技(江西)有限公司 | Method for analyzing acid-catalyzed lignin depolymerization product by using ultra-efficient polymer gel chromatography |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107890871A (en) * | 2017-12-01 | 2018-04-10 | 东北石油大学 | The method that lignosulfonates catalytic degradation produces compound aromatic base |
| CN107890871B (en) * | 2017-12-01 | 2020-04-28 | 东北石油大学 | Method for preparing aryl compound by catalytic depolymerization of lignosulfonate |
| 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 |
| 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 |
| CN111807573A (en) * | 2020-07-16 | 2020-10-23 | 湖南中湘春天环保科技有限公司 | Treatment device and method for thallium-containing wastewater |
| CN112831799A (en) * | 2020-12-30 | 2021-05-25 | 北京化工大学 | Method for electrochemically depolymerizing lignin |
| CN112831799B (en) * | 2020-12-30 | 2022-12-23 | 北京化工大学 | Method for electrochemically depolymerizing lignin |
| CN114184722A (en) * | 2021-12-17 | 2022-03-15 | 南亚新材料科技(江西)有限公司 | Method for analyzing acid-catalyzed lignin depolymerization product by using ultra-efficient polymer gel chromatography |
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