CN114551953A - High-value utilization method of industrial lignin - Google Patents
High-value utilization method of industrial lignin Download PDFInfo
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- CN114551953A CN114551953A CN202210144971.8A CN202210144971A CN114551953A CN 114551953 A CN114551953 A CN 114551953A CN 202210144971 A CN202210144971 A CN 202210144971A CN 114551953 A CN114551953 A CN 114551953A
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- anolyte
- industrial lignin
- acid
- lignin
- ferric
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- 229920005610 lignin Polymers 0.000 title claims abstract description 109
- 238000000034 method Methods 0.000 title claims abstract description 48
- 239000002253 acid Substances 0.000 claims abstract description 40
- 239000002028 Biomass Substances 0.000 claims abstract description 38
- 238000006731 degradation reaction Methods 0.000 claims abstract description 36
- 239000003513 alkali Substances 0.000 claims abstract description 25
- 229920001732 Lignosulfonate Polymers 0.000 claims abstract description 16
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 46
- 239000003792 electrolyte Substances 0.000 claims description 38
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 33
- 230000015556 catabolic process Effects 0.000 claims description 31
- 239000000446 fuel Substances 0.000 claims description 31
- 150000003839 salts Chemical class 0.000 claims description 22
- 238000005286 illumination Methods 0.000 claims description 18
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 18
- 150000003681 vanadium Chemical class 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 15
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 12
- 230000000593 degrading effect Effects 0.000 claims description 10
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- -1 hydrogen ions Chemical class 0.000 claims description 9
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
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- 238000003756 stirring Methods 0.000 claims description 7
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- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- NRKQBMOGOKEWPX-UHFFFAOYSA-N vanadyl nitrate Chemical compound [O-][N+](=O)O[V](=O)(O[N+]([O-])=O)O[N+]([O-])=O NRKQBMOGOKEWPX-UHFFFAOYSA-N 0.000 claims description 6
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
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- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 3
- 229940041260 vanadyl sulfate Drugs 0.000 claims description 3
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- 238000010248 power generation Methods 0.000 abstract description 30
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- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 11
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 10
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- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 6
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- FFNDAWOUEUOJQA-UHFFFAOYSA-N 3,4-diethylhex-3-ene Chemical group CCC(CC)=C(CC)CC FFNDAWOUEUOJQA-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
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- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 229910001456 vanadium ion Inorganic materials 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
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- 150000001720 carbohydrates Chemical class 0.000 description 1
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- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
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- 150000002505 iron Chemical class 0.000 description 1
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- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Sustainable Energy (AREA)
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Abstract
The invention belongs to the technical field of comprehensive utilization of industrial lignin, and particularly relates to a high-value utilization method of industrial lignin. Meanwhile, other external conditions are not required to be additionally introduced, and the alkali lignin, the lignosulfonate and other industrial lignins can be degraded only by sunlight irradiation in the nature, so that the energy consumption and the cost are greatly reduced. Meanwhile, biomass energy and solar energy can be converted into clean electric energy. In addition, the acid used in the anolyte and the catholyte is dilute acid, so that the environmental pollution is small. Therefore, the chemical energy released in the industrial lignin degradation process can be fully utilized to couple power generation, so that high-value utilization of the industrial lignin is realized.
Description
Technical Field
The invention belongs to the technical field of comprehensive utilization of industrial lignin, and particularly relates to a high-value utilization method of industrial lignin.
Background
The biomass is rich in variety, large in storage capacity and renewable, and can be converted into other forms of energy and chemicals through a physical and chemical method, so that the biomass is widely concerned by people. Among them, lignin is one of three major components of plant cell walls, and is widely present in various plants. The natural lignin is very complex in structure and is generally formed by connecting three basic structural units, namely p-hydroxyphenyl, guaiacyl and syringyl, through chemical bonds such as C-O, C-C. Due to the existence of various active functional groups and aromatic rings in the lignin, the lignin has wide application value.
The lignocellulose biomass containing natural lignin is subjected to production processes such as pulping, papermaking or biorefinery to produce a large amount of industrial lignin as a byproduct. According to statistics, billions of tons of industrial lignin are produced in the world every year, wherein the annual yield of the industrial lignin in China exceeds 2000 ten thousand tons. At present, the effective utilization rate of industrial lignin is less than 20%, most of industrial lignin is utilized in low-value modes of incineration power generation or heat energy recovery and the like, so that not only is the resource seriously wasted, but also a large amount of CO is discharged to the environment2The achievement of the "carbon peak, carbon neutralization" dual carbon target is severely hindered.
According to different pulping cooking processes, industrial lignin is mainly divided into alkali lignin, lignosulfonate, organic solvent lignin and the like. Wherein the industrial lignin obtained by soda cooking is alkali lignin; the industrial lignin obtained by sulfite cooking in the acid pulping process is lignosulfonate; the sulfate lignin is obtained by a sulfate method; the industrial lignin obtained by the organic solvent method is organic solvent lignin. At present, when lignocellulose biomass is refined by a biorefinery, only value-added utilization of carbohydrates, such as bioethanol, pulping, papermaking and the like, is generally concerned, so that irreversible condensation and polycondensation of lignin components are easily caused in the separation and refining process. Therefore, the by-produced industrial lignin has a series of disadvantages such as poor water solubility, high molecular weight, low reactivity and the like, and the high-value utilization thereof is very challenging. Therefore, research and development of high-value utilization of industrial lignin have important economic and environmental benefits.
Currently, research on the application of industrial lignin has attracted much attention. The industrial lignin is used as a modifying additive of cement to produce high-performance concrete. Abundant hydroxyl groups of industrial lignin can be used for preparing lignin/polyurethane high polymer materials, lignin-based phenolic aldehyde adhesives and the like; the potential application in the daily chemical field can be developed by utilizing the antibacterial and antioxidant performances of the industrial lignin; the industrial lignin is used as a precursor of the activated carbon, and the activated carbon is carbonized and activated in an oxygen-free atmosphere to prepare a porous carbon material with rich micropores and mesoporous structures, so that the porous carbon material can be applied to the fields of supercapacitors, potassium ion batteries, catalysts, adsorbents and the like.
In addition, the current commercialized biomass power generation technology is mainly direct-combustion power generation and the like, and is influenced by the carnot cycle, so that the power generation efficiency is low. The biomass fuel cell technology in the research stage mainly includes solid oxide fuel cells, microbial fuel cells, direct biomass fuel cells and the like. The solid oxide fuel cell needs to gasify or carbonize the biomass at high temperature, so that the energy consumption is too high, the efficiency is lower, and the generated electric energy is far less than the consumed electric energy. Although the microbial fuel cell has low working temperature and dual functions of pollutant degradation and electricity generation, the cell has low electricity generation efficiency, the self metabolic capability and the cyclic utilization rate of the electricity generation microbes are low, the cell is easy to be inactivated by heat or damage of certain chemical substances, and the cell has poor performance stability. The direct biomass fuel cells reported at present all need external heating for energy supply, the consumed electric energy is far higher than the generated electric energy, and no obvious economic value exists.
In summary, industrial lignin is abundant in yield and has a large potential application value, but the actual industrial application of the technology is less. At present, the incineration power generation mode adopted on a large scale is limited by Carnot cycle, the power generation efficiency is low, and a large amount of greenhouse gases can be discharged to the environment. In the biomass fuel cell technology in the research stage, a large amount of electric energy needs to be supplied from the outside for heating, the electric energy consumed by heating is far higher than the generated electric energy, and industrialization cannot be realized. Therefore, the novel industrial lignin high-efficiency clean power generation technology is developed, and the dual aims of high-value utilization of industrial lignin and environmental protection can be achieved.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide a high-value utilization method of industrial lignin.
The second object of the present invention is to provide an electrolyte and a biomass fuel cell, which are extended from the above-mentioned industrial lignin high-value utilization method.
The first object of the present invention is achieved by the following technical solutions:
a method for high-value utilization of industrial lignin is characterized by comprising the following steps:
s1, preparing an anolyte: firstly, preparing a mixed solution containing trivalent ferric salt, acid, nano titanium dioxide and industrial lignin, and then placing the mixed solution under illumination for photoinduced degradation to prepare an anolyte:
preparing an anolyte, adding the anolyte into a photoreactor, and carrying out photoinduced degradation reaction under the illumination condition; the step is to degrade industrial lignin and store electrons in electrolyte, gradually degrade industrial lignin macromolecules, and store and transport electrons released when the molecular valence bonds of the industrial lignin are broken, so that a foundation is laid for supplying power to an external load by using a biomass fuel cell system.
The reaction is carried out under the illumination condition in the step because the ferric salt and the nano titanium dioxide can absorb ultraviolet-visible light, the ferric ion and the titanium dioxide are excited by sunlight to be in a high-energy state, and the chemical bond of the industrial lignin molecule is efficiently broken to degrade the industrial lignin molecule.
In this step, an acid is addedThe method is to increase the solubility and stability of the oxidant ferric salt, is more favorable for exerting the reaction activity of the ferric salt under the acidic condition, and simultaneously provides H+Electrons transferred from the anode to the cathode through the proton exchange membrane to be transported with an external circuit form a closed loop. The addition of the nano titanium dioxide can improve the energy density of the electrolyte and the light-induced degradation capability in a visible light region, so that the catalytic degradation is more efficient.
S2, preparing a cathode electrolyte: firstly, preparing a mixed solution containing pentavalent vanadium salt and acid, and stirring at room temperature until the mixed solution is clear and transparent to prepare a cathode electrolyte, wherein the cathode electrolyte contains pentavalent vanadium salt and acid;
the step is to prepare the catholyte, and lays a foundation for constructing a biomass fuel cell system together with the step S1.
The pentavalent vanadium salt is selected as the cathode electronic carrier in the step, because the standard electrode potential of the pentavalent vanadium salt is about 1V and is higher than the standard potential of the ferric salt of the anode electronic carrier by 0.77V, the open-circuit voltage of the battery can be increased when the pentavalent vanadium salt is used in the cathode, and the battery is endowed with excellent electrical property. The acid is added in the step to increase the solubility and the redox activity of the pentavalent vanadium salt, and the activity of the pentavalent vanadium salt is more favorably exerted under the acidic condition.
S3, constructing a biomass fuel cell system: and (3) adding the anolyte obtained in the step (S1) into an anolyte tank, adding the catholyte obtained in the step (S2) into a catholyte tank, connecting the anolyte tank with an anode inlet and an anode outlet of the battery and an anode pump by using a guide pipe, connecting the catholyte tank with a cathode inlet and a cathode outlet of the battery and a cathode pump, and finally starting the constructed biomass fuel cell system to realize high-value utilization of the industrial lignin.
Preferably, the industrial lignin is one or two of alkali lignin and lignosulfonate.
Further, the alkali lignin is modified carboxylated alkali lignin. The alkali lignin is brown powder or liquid, has no special peculiar smell, is nontoxic, and is easily dissolved in water and acid liquor after carboxylation modification.
Further, the lignosulfonate is sodium lignosulfonate. The sodium lignosulfonate is brown powder, has no special peculiar smell, is non-toxic, is easily soluble in water and acid liquor, and has strong dispersing capacity. The main structural units of the sodium lignosulfonate monomer are shown as follows:
the invention provides a high-value utilization method of industrial lignin, which uses cheap trivalent ferric salt and nano TiO2As a catalytic oxidant, a composite photocatalytic oxidation system is constructed, and chemical energy released in the degradation process can be fully utilized to couple power generation while industrial lignin is efficiently degraded. Compared with the prior art, the method for generating electricity by directly utilizing the industrial lignin by utilizing the biomass fuel cell principle not only can efficiently convert the biomass energy in the industrial lignin into electric energy without a complex conversion process, but also has simple operation and realizes high-value utilization of the industrial lignin.
Preferably, the ferric salt comprises at least one of ferric chloride, ferric sulfate, and ferric nitrate. Specifically, the ferric salt is ferric chloride.
Preferably, in the anolyte, the concentration of the ferric iron salt is 1-4 mol/L, the concentration of hydrogen ions of the acid is 1-4 mol/L, the content of the nano titanium dioxide is 40-100 g/L, the particle size of the nano titanium dioxide is 10-200 nm, and the content of the industrial lignin is 10-50 g/L. Specifically, the concentration of the ferric iron salt is 1mol/L, the hydrogen ion concentration of the acid is 2mol/L, the content of the titanium dioxide is 80g/L, and the content of the industrial lignin is 40 g/L.
In the anolyte, the amount of acid added needs to be controlled, and if the amount of acid is too small, the solubility and the stability of the trivalent ferric salt are insufficient; if too much, the reaction system is too acidic and has strong corrosion to equipment.
Preferably, the light source used for illumination comprises at least one of sunlight, ultraviolet light, visible light and infrared light, and the illumination time is 3-20 h. Specifically, the light source adopted by the illumination is sunlight, and the illumination time is 4 h.
The light intensity and time need to be controlled in the light reaction process, and if the light intensity is too weak and the time is too short, the degradation rate and the degradation degree of the industrial lignin are low; the degradation effect of the industrial lignin is not obviously improved due to over-strong light intensity and over-long time, and the economic effect is not realized.
Further, the temperature of the solar illumination is 10-40 ℃.
The invention directly adopts sunlight to induce, oxidize and degrade industrial lignin such as alkali lignin, lignosulfonate and the like to generate clean electric energy, and has three advantages: firstly, molecules of industrial lignin such as alkali lignin, lignosulfonate and the like can be efficiently degraded, secondly, the energy consumption cost of heating treatment of electrolyte is saved, and thirdly, clean electric energy can be generated.
Preferably, the pentavalent vanadium salt includes at least one of vanadium pentoxide, vanadyl sulfate, and vanadyl nitrate. Specifically, the pentavalent vanadium salt is vanadium pentoxide (V)2O5)。
Preferably, in the catholyte, the concentration of the pentavalent vanadium salt is 0.05-5 mol/L, and the concentration of the hydrogen ions of the acid is 0.05-8.0 mol/L.
In the cathode electrolyte, the amount of acid added needs to be controlled, and if the amount of acid added is too small, the solubility and stability of the pentavalent iron salt are insufficient; if too much, acid is wasted, and acid with too high concentration also causes environmental pollution, thus having lower economic and environmental benefits.
Preferably, in the anolyte or catholyte, the acid is at least one of hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid.
More preferably, in the catholyte, the acid is nitric acid.
Nitric acid is added as an active agent, and the low-valence vanadium in a catalytic reduction state is regenerated into high-valence vanadium in time, so that the catholyte is regenerated in time, and the stable operation of a power generation system is maintained.
Preferably, the battery can adopt a biomass fuel cell commonly used in the field of electricity generation.
Further, the battery includes graphite plates, graphite felt, separators, fixed end plates, pipes, wires, loads, and the like.
Furthermore, the preparation method of the battery comprises the following steps: and filling a graphite felt in the S-shaped flow channel in the graphite plate, and then assembling the graphite plate, the diaphragm, the fixed end plate, the pipeline, the lead, the load and the like into the battery in sequence.
The second object of the present invention is achieved by the following technical solutions:
an electrolyte for degrading industrial lignin, which comprises a ferric salt, acid, nano titanium dioxide and industrial lignin.
The invention also provides a biomass fuel cell, the biomass fuel cell takes the electrolyte as an anolyte, the anolyte needs to be degraded by illumination induction, and a catholyte of the biomass fuel cell comprises pentavalent vanadium salt and acid.
Preferably, the biomass fuel cell further comprises a graphite plate, a graphite felt, a diaphragm, a fixed end plate, a pipeline, a lead, a load, and the like.
Preferably, in the electrolyte or biomass fuel cell, the lignin is at least one of alkali lignin and lignosulfonate. Specifically, the lignosulfonate is sodium lignosulfonate.
Preferably, in the electrolyte or biomass fuel cell, the ferric salt comprises at least one of ferric chloride, ferric sulfate and ferric nitrate. Specifically, the ferric salt is ferric chloride.
Preferably, in the electrolyte or the biomass fuel cell, in the anolyte, the concentration of the ferric iron salt is 1-4 mol/L, the concentration of hydrogen ions of the acid is 1-4 mol/L, the content of the nano titanium dioxide is 40-100 g/L, the particle size of the nano titanium dioxide is 10-200 nm, and the content of the industrial lignin is 10-50 g/L. Specifically, the concentration of the ferric iron salt is 1mol/L, the hydrogen ion concentration of the acid is 2mol/L, the content of the titanium dioxide is 80g/L, the particle size of the nano titanium dioxide is 60nm, and the content of the industrial lignin is 40 g/L.
Preferably, in the electrolyte or the biomass fuel cell, the light source used for illumination comprises at least one of sunlight, ultraviolet light, visible light and infrared light, and the illumination time is 3-20 h. Specifically, the light source adopted by the illumination is sunlight, and the illumination time is 4 h.
Further, in the electrolyte or the biomass fuel cell, the temperature of solar illumination is 10-40 ℃.
Preferably, in the electrolyte or biomass fuel cell, the pentavalent vanadium salt includes at least one of vanadium pentoxide, vanadyl sulfate, and vanadyl nitrate. Specifically, the pentavalent vanadium salt is vanadium pentoxide (V)2O5)。
Preferably, in the electrolyte or the biomass fuel cell, the concentration of the pentavalent vanadium salt in the catholyte is 0.05-5 mol/L, and the hydrogen ion concentration of the acid is 0.05-8.0 mol/L.
Preferably, in the electrolyte or the biomass fuel cell, the acid in the anolyte or catholyte is at least one of hydrochloric acid, sulfuric acid, and nitric acid.
Compared with the prior art, the invention has the beneficial effects that:
the invention discloses a high-value utilization method of industrial lignin, which adopts a low-price, green and environment-friendly trivalent ferric salt and nano titanium dioxide to form a composite photocatalytic oxidation system, can use the industrial lignin to generate clean electric energy under illumination, has low cost and realizes the high-value utilization of the industrial lignin. Meanwhile, other external conditions are not required to be additionally introduced, and the industrial lignin can be degraded only by sunlight irradiation in the nature, so that the energy consumption and the cost are greatly reduced. Meanwhile, biomass energy and solar energy can be converted into clean electric energy. In addition, the acid used in the anolyte and the catholyte is dilute acid, so that the environmental pollution is small. Therefore, the invention can efficiently degrade macromolecules in the industrial lignin such as alkali lignin, lignosulfonate and the like, and can fully utilize chemical energy released in the degradation process to couple and generate power, thereby realizing high-value utilization of the industrial lignin.
Drawings
FIG. 1 is a flow chart of a process for producing electricity by degrading alkali lignin;
FIG. 2 is a graph of current density-voltage-output power output by an alkali lignin-based power generation device under solar irradiation;
FIG. 3 is a process flow diagram for power generation by degradation of sodium lignosulfonate;
FIG. 4 is a graph of current density versus voltage versus output power output by power generation devices under different light sources;
FIG. 5 is a graph of current density-voltage-output power output by a power generation device for different catalyst systems;
FIG. 6 is a graph of current density-voltage-output power output by a power generation device under heat treatment and solar radiation;
FIG. 7 is a graph of current density versus time output by a power generation device under heat treatment and solar radiation;
FIG. 8 is a graph of current density-voltage-output power output by a power generation device using an anolyte of ferrous chloride and nano titanium dioxide;
FIG. 9 is a graph of current density-voltage-output power output by a power generation device using iron trichloride + titanyl sulfate anolyte;
fig. 10 is a graph of current density-voltage-output power output by a lignosulfonate power plant in the absence of light and heat treatment.
Detailed Description
The following further describes the embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The experimental procedures in the following examples were carried out by conventional methods unless otherwise specified, and the test materials used in the following examples were commercially available by conventional methods unless otherwise specified.
Example 1 Electricity production Performance by degradation of alkali Lignin under sunlight
According to the process flow diagram of fig. 1, the method comprises the following steps:
(1) carboxylation of alkali lignin to modify carboxylated alkali lignin: the method comprises the following specific steps:
1) adding 5g of alkali lignin and 12.5g of NaOH aqueous solution with the mass fraction of 20% into a beaker, and continuously stirring at 30-40 ℃ until the alkali lignin and the NaOH aqueous solution are dissolved;
2) mixing 3g of monochloroacetic acid and 5mL of pure water to prepare a solution, slowly adding the solution into the beaker filled with the alkali lignin-NaOH solution, and uniformly stirring;
3) stirring and reacting for 90min at 70 ℃, cooling and then adjusting the pH value to 5 +/-0.1 by using 2mol/L HCl; and then centrifuging for 10min at 8000 rpm by using a centrifuge, taking the centrifuged supernatant, and drying in a 60 ℃ oven to obtain the modified carboxylated alkali lignin.
(2) Preparing an anolyte: 6.75g ferric chloride hexahydrate, 2.0g nano titanium dioxide (60nm) and 4.2mL concentrated hydrochloric acid (12mol/L) are dissolved in deionized water, and then 1g modified carboxylation alkali lignin is added to prepare 25mL FeCl of 1mol/L3+80g/L nano titanium dioxide +40g/L carboxylated alkali lignin mixed solution (H)+The concentration is 2mol/L), evenly mixed and then transferred into a photoreactor, and placed under the sunlight (about 31 ℃) for reaction for 4 hours to prepare the anolyte of the solar light induced degradation.
(3) Preparing a cathode electrolyte: stirring V vigorously2O5(10g) Added to water (262mL) and concentrated H38 mL in an ice bath2SO4(98%) dropwise addition to V2O5Reacting the suspension for 20 hours, and adding 1mL of nitric acid (42%) to prepare a catholyte (the concentration of vanadium ions is 0.8mol/L, and the concentration of H < + > is 2.2 mol/L);
(4) battery system construction and electrical performance testing:
1) filling a graphite felt in an S-shaped flow channel in a graphite plate, then assembling the graphite plate, a load (LED lamp), a lead, a fixed end plate and the like into a battery according to the sequence of a metal cover plate, an anode graphite plate, a poly tetra ethyl ethylene film, a Nafion117 film, a polytetrafluoroethylene film, a cathode graphite plate and a metal cover plate, and connecting the battery and the load by using the lead.
2) And (3) adding the anolyte in the step (2) into an anolyte tank at room temperature, and adding the catholyte in the step (3) into a catholyte tank. Then connecting an anode electrolyte tank with an anode inlet and an anode outlet of the battery and an anode pump by using a guide pipe, and connecting a cathode tank with a cathode inlet and an cathode outlet of the battery and a cathode pump to complete the assembly of the power generation device; after the power generation device is started, the electrical performance of the battery is tested by adopting a scanning current method, and the result is shown in fig. 2.
As can be seen from FIG. 2, the cell performance of the electrolyte composition treated with solar light irradiation had a maximum output voltage of 0.55V and a maximum output current density of 538.8mA/cm2The maximum output power density is 65.4mW/cm2. Therefore, under the irradiation of sunlight, ferric ions and nano titanium dioxide can better oxidize and degrade alkali lignin, higher-power electric energy can be output, additional energy consumption cost is not required to be introduced during the irradiation of the sunlight, and the economy and the environmental protection are highest.
Example 2 electrogenesis performance of sodium lignosulfonate degradation under different light sources
According to the process flow diagram of fig. 3, the method comprises the following steps:
(1) preparing an anolyte: 6.75g of ferric chloride hexahydrate, 2.0g of nano titanium dioxide (60nm) and 4.2mL of concentrated hydrochloric acid (12mol/L) are dissolved in deionized water, and then 1g of sodium lignosulfonate is added to prepare 25mL of FeCl with 1mol/L3+80g/L nano titanium dioxide +40g/L sodium lignosulfonate (H)+The concentration is 2mol/L), evenly mixed and then transferred into a photoreactor, and placed under the sunlight (about 30 ℃) for reaction for 4 hours to prepare the anolyte of the solar light induced degradation.
Preparing another two 25mL mixed solutions by the same method, respectively placing the mixed solutions under a xenon lamp and ultraviolet light (room temperature is 30 ℃) for irradiation reaction for 4h to prepare the anolyte subjected to xenon lamp induced degradation and the anolyte subjected to ultraviolet light induced degradation, and testing the anolyte.
(2) Preparing a cathode electrolyte: stirring V vigorously2O5(10g) Added to water (262mL) and concentrated H38 mL in an ice bath2SO4(98%) dropwise addition to V2O5Reacting the suspension for 20 hours, and adding 1mL of nitric acid (42%) to prepare a catholyte (the concentration of vanadium ions is 0.8mol/L, and the concentration of H < + > is 2.2 mol/L);
(3) battery system construction and electrical performance testing:
1) filling a graphite felt in an S-shaped flow channel in a graphite plate, then assembling the graphite plate, a load (LED lamp), a lead, a fixed end plate and the like into a battery according to the sequence of a metal cover plate, an anode graphite plate, a poly tetra ethyl ethylene film, a Nafion117 film, a polytetrafluoroethylene film, a cathode graphite plate and a metal cover plate, and connecting the battery and the load by using the lead.
2) And (3) adding the anolyte in the step (1) into an anolyte tank at room temperature, and adding the catholyte in the step (2) into a catholyte tank. Then connecting an anode electrolyte tank with an anode inlet and an anode outlet of the battery and an anode pump by using a guide pipe, and connecting a cathode tank with a cathode inlet and a cathode outlet of the battery and the cathode pump to complete the assembly of the power generation device; after the power generation device is started, the electrical performance of the battery is tested by adopting a scanning current method, and the result is shown in fig. 4.
As can be seen from FIG. 4, the cell composed of the electrolyte treated by the solar irradiation exhibited the best performance, with the maximum output voltage of 0.54V and the maximum output current density of 532.7mA/cm2The maximum output power density is 64.5mW/cm2. In contrast, the electrolyte composition treated with uv irradiation had inferior cell performance, and the electrolyte composition treated with xenon irradiation had the worst cell performance. Therefore, compared with the irradiation of a xenon lamp and an ultraviolet lamp, the irradiation of the sunlight can better oxidize and degrade sodium lignosulfonate by ferric ions and nano titanium dioxide, higher-power electric energy is output, extra energy consumption cost is not required to be introduced in the irradiation of the sunlight, and the economy and the environmental protection are highest.
Example 3 Electricity production Performance of different catalytic oxidation systems for degradation of sodium Lignosulfonate
According to the process flow diagram of fig. 3, the method comprises the following steps:
(1) preparing an anolyte: 6.75g ferric chloride hexahydrate, 2.0g nano titanium dioxide and 4.2mL concentrated hydrochloric acid are dissolved in deionized water, then 1g sodium lignosulfonate is added to prepare 25mL FeCl with 1mol/L3+80g/L nano titanium dioxide +40g/L sodium lignosulfonate (H)+The concentration is 2mol/L), evenly mixed and then transferred into a photoreactor, and placed under the sunlight (about 24 ℃) for reaction for 4 hours to prepare the anolyte of the solar light induced degradation.
(2) Preparation of No. 1 control anolyte: 2g of nano titanium dioxide, 1g of sodium lignin sulfonate and 4.2mL of concentrated hydrochloric acid are added into deionized water, and after uniform mixing, 25mL of mixed solution (H) consisting of 80g/L of nano titanium dioxide and 40g/L of sodium lignin sulfonate is prepared+The concentration is 2 mol/L). Then the solution is transferred into a photoreactor and placed under the sunlight (about 24 ℃) to react for 4 hours, and the No. 1 control anolyte of the sunlight induced degradation is prepared.
(3) Preparation of No. 2 control anolyte: 6.75g ferric chloride hexahydrate, 1g sodium lignosulfonate and 4.2mL concentrated hydrochloric acid are added into deionized water to prepare 25mL FeCl with the concentration of 1mol/L3+40g/L Lignosulfonic acid sodium salt mixed solution (H)+The concentration is 2 mol/L). After being uniformly mixed, the mixture is transferred into a photoreactor and is placed under the sunlight (about 24 ℃) for reaction for 4 hours, and the No. 2 control anolyte which is degraded by the induction of the sunlight is prepared.
(4) The catholyte was prepared as in example 1.
(5) The construction of the battery system and the electrical properties were measured in the same manner as in example 1, and the results are shown in FIG. 5.
As can be seen from FIG. 5, the maximum output voltage was 0.50V and the maximum output current density was 352.5mA/cm under 4h irradiation2The maximum output power density is 41.6mW/cm2Proves that under the synergistic effect of ferric trichloride and nano titanium dioxide, the material is more than single nano titanium dioxide and single FeCl3The effect of catalyzing and degrading sodium lignosulfonate to generate electricity is better.
Example 4 comparison of Electricity Generation Properties of light-treated and Heat-treated degraded sodium Lignosulfonate
According to the process flow diagram of fig. 3, the method comprises the following steps:
(1) preparing an anolyte by light treatment: the preparation method is the same as example 2.
(2) Preparing an anolyte by heat treatment: 6.75g ferric chloride hexahydrate, 2.0g nano titanium dioxide and 4.2mL concentrated hydrochloric acid are dissolved in deionized water, then 1g sodium lignosulfonate is added to prepare 25mL FeCl with 1mol/L3+80g/L nano titanium dioxide +40g/L sodium lignosulfonate (H)+The concentration is 2mol/L), evenly mixing, transferring to 60 ℃ for constant temperature reaction for 4h, and preparing the thermal degradation lignin electrolyte.
(3) The catholyte was prepared as in example 1.
(4) The construction of the battery system and the electrical properties were measured in the same manner as in example 1, and the results are shown in fig. 6.
(5) The current density was measured as a function of time (I-t) and the results are shown in FIG. 7. And calculating the power generation capacity of the battery and the energy change condition of the battery for 20min under different conditions, wherein the energy consumption of the heating table can be calculated by the following formula, and the energy change is shown in table 1.
Q＝U·I·t
Wherein: q is the generated energy, U is the heating stage operating voltage (unit: V), I is the operating current (unit: A), and t is the operating time (unit: s).
As can be seen from fig. 6 and 7, the performance of the heat-treated cells was inferior to that of the light-treated cells. Wherein the maximum output voltage of the heat treatment group is 0.44V, and the maximum output current density is 502.7mA/cm2The maximum output power density is 58.4mW/cm2(ii) a The maximum output voltage of the light treatment group is 0.54V, and the maximum output current density is 532.7mA/cm2The maximum output power density is 64.5mW/cm2. Therefore, compared with heating treatment, the battery treated by sunlight has better performance, which shows that the power generation performance is better when sodium lignosulfonate is degraded by sunlight for power generation. Meanwhile, as can be seen from table 1, the degradation process of the light treatment group does not require energy consumption cost generated by heating, and has the advantages of low energy consumption, environmental protection and larger generated energy.
TABLE 1 comparison of Power Generation and energy Change in light-and Heat-treated degradation of sodium Lignosulfonate
Example 5 Effect of different anolyte solutions on the Electricity production Performance of the degradation of sodium Lignosulfonate
According to the process flow diagram of fig. 3, the method comprises the following steps:
(1) preparing an anode electrolyte of ferrous chloride and nano titanium dioxide: 6.75g of ferrous chloride hexahydrate, 2.0g of nano titanium dioxide and 4.2mL of concentrated hydrochloric acid are dissolved in deionized water deoxidized by nitrogen, 1g of sodium lignosulfonate is added, and 25mL of 1mol/L FeCl is prepared2+80g/L nano titanium dioxide +40g/L sodium lignosulfonate (H)+The concentration is 2mol/L), the mixture is evenly mixed and then transferred into a photoreactor, and the mixture is placed under the sunlight (about 30 ℃) for 4 hours to prepare the sunlight induced degradation ferrous chloride and nano titanium dioxide anolyte.
(2) Preparing an iron trichloride and titanyl sulfate anolyte: 6.75g ferric chloride hexahydrate, 2.0g titanyl sulfate and 4.2mL concentrated hydrochloric acid are dissolved in deionized water, and then 1g sodium lignosulfonate is added to prepare 25mL FeCl of 1mol/L3+80g/L titanyl sulfate +40g/L sodium lignosulfonate (H)+The concentration is 2mol/L), the mixture is evenly mixed and then transferred into a photoreactor, and the mixture is placed under the sunlight (about 30 ℃) to react for 4 hours, thus obtaining the ferric trichloride and titanyl sulfate anolyte of the sunlight induced degradation.
(3) Preparing an anolyte without light and heating: 6.75g ferric chloride hexahydrate, 2.0g nano titanium dioxide and 4.2mL concentrated hydrochloric acid are dissolved in deionized water, then 1g sodium lignosulfonate is added to prepare 25mL mixed solution (H) consisting of 1mol/L ferric chloride, 80g/L nano titanium dioxide and 40g/L sodium lignosulfonate+Concentration of 2mol/L), uniformly mixed, transferred into a flask, and reacted at room temperature (about 30 ℃) for 4 hours in a water bath to prepare an anolyte.
(4) Preparing a cathode electrolyte: the same as example 2;
(5) battery system construction and electrical performance testing: the same as in example 2.
As a result, the battery which is formed by the anode electrolyte consisting of the trivalent ferric salt, the acid, the nano titanium dioxide and the sodium lignosulfonate has the best performance when the solar light is adopted, the maximum output voltage is 0.54V, and the maximum output current density is 532.7mA/cm2The maximum output power density is 64.5mW/cm2(ii) a The maximum output voltage of the battery performance of the anolyte consisting of ferrous chloride, acid, nano titanium dioxide and sodium lignosulfonate is only 0.47V, and the maximum output current density is 87.35mA/cm2The maximum output power density is 15.3mW/cm2(FIG. 8). The reason is that the ferrous salt has reducing property and no oxidizing property, and can not degrade sodium lignosulfonate. The battery performance of the anolyte composed of ferric salt, acid, titanyl sulfate and sodium lignosulfonate is that the maximum voltage is 0.48V, and the maximum current density is 57.35mA/cm2Maximum power density of 9.01mW/cm2(FIG. 9). Therefore, the effect of degrading lignosulfonate by photocatalysis of ferrous chloride or titanyl sulfate is not excellent than that of degrading ferric trichloride or nano titanium dioxide. Therefore, the effect of catalyzing and degrading sodium lignosulfonate by the anolyte consisting of the ferric salt, the acid, the nano titanium dioxide and the sodium lignosulfonate to generate electricity is better.
In addition, the battery composed of the sodium lignosulfonate anolyte degraded by the method without light and heat treatment has poor performance, wherein the maximum output voltage is 0.49V, and the maximum output current density is 23.6mA/cm2The maximum output power density is 3.23mW/cm2. The power generation performance was much lower than the light addition treatment and the heat treatment (fig. 10). The method shows that when a catalytic oxidation system consisting of ferric salt and nano titanium dioxide generates electricity, light-induced degradation or heating-induced degradation is needed to achieve a better effect, and the effect of the light-induced degradation is better.
Example 6 degradation of Electricity Generation Properties of other Biomass
According to the process flow diagram of fig. 3, the method comprises the following steps:
(1) preparing a cathode electrolyte: the same as in example 1.
(2) Preparing the rice straw-containing anolyte: 6.75g ferric chloride hexahydrate, 2.0g nano titanium dioxide and 4.2mL concentrated hydrochloric acid are dissolved in deionized water, then 1g rice straw is added to prepare 25mL FeCl with 1mol/L3+80g/L nano titanium dioxide +40g/L rice straw (H)+The concentration is 2mol/L), transferring the solution into a photoreactor, and placing the solution under the sunlight (about 30 ℃) to react for 4 hours to prepare the anolyte of the sunlight induced degradation.
(3) Preparation of bagasse-containing anolyte: 6.75g ferric chloride hexahydrate, 2.0g nano titanium dioxide and 4.2mL concentrated hydrochloric acid are dissolved in deionized water, then 1g bagasse is added to prepare 25mL FeCl with 1mol/L3+80g/L nano titanium dioxide +40g/L bagasse (H)+The concentration is 2mol/L), transferring the solution into a photoreactor, and placing the solution under the sunlight (about 30 ℃) to react for 4 hours to prepare the anolyte of the sunlight induced degradation.
(4) Preparing glucose-containing anolyte: 6.75g ferric chloride hexahydrate, 2.0g nano titanium dioxide and 4.2mL concentrated hydrochloric acid are dissolved in deionized water, and then 1g glucose is added to prepare 25mL FeCl with 1mol/L3+80g/L Titania +40g/L glucose (H)+The concentration is 2mol/L), evenly mixed and then transferred into a photoreactor, and placed under the sunlight (about 30 ℃) for reaction for 4 hours to prepare the anolyte of the solar light induced degradation.
(5) Battery system construction and electrical performance testing: the same as in example 1.
As a result, it was found that the battery comprising the sodium lignosulfonate-containing anolyte had the best performance, the maximum voltage was 0.54V, and the maximum current density was 532.7mA/cm2The maximum power density is 64.5mW/cm2. The maximum voltage of the battery containing the rice straw anode electrolyte is only 0.28V, and the maximum current density is 287.6mA/cm2Maximum power density of 29.1mW/cm2. The performance of the battery containing bagasse anolyte is 0.31V at the maximum voltage and 320.1mA/cm at the maximum current density2Maximum power density of33.2mW/cm2. The performance of the battery containing the glucose anolyte was 0.36V at the maximum voltage and 311.91mA/cm at the maximum current density2Maximum power density of 45.7mW/cm2. Therefore, the biomass such as rice straw, bagasse and the like has poor solubility in an acidic aqueous solution, cannot be fully contacted with a catalytic oxidant, and has poor performance. The sodium lignosulfonate has good solubility in an acidic aqueous solution, and can play an excellent synergistic effect with an iron chloride/titanium dioxide composite photocatalytic oxidation system, so that the prepared anolyte has better power generation performance. Therefore, the catalytic oxidation system consisting of the ferric salt and the nano titanium dioxide has better effect of degrading the sodium lignosulfonate to generate electricity.
Comparative example 1 study on power generation performance of sodium lignosulfonate degraded by ferric trichloride and hydrogen peroxide composite system
According to the process flow diagram of fig. 3, the method comprises the following steps:
(1) preparing an anolyte containing sodium lignosulfonate: 6.75g of ferric chloride hexahydrate, 1mL of 30% hydrogen peroxide solution and 4.2mL of concentrated hydrochloric acid are dissolved in deionized water, and then 1g of sodium lignosulfonate is added to prepare 25mL of mixed solution (H) consisting of 1.1mol/L hydrogen peroxide, 1mol/L ferric chloride and 40g/L sodium lignosulfonate+The concentration is 2mol/L), evenly mixed and then transferred into a photoreactor to react for 4 hours at room temperature (about 30 ℃) in the sunlight to prepare the anolyte.
(2) Preparing a cathode electrolyte: the same as in example 1.
(3) Battery system construction and electrical performance testing: the same as in example 1.
As a result, the performance of the battery formed by degrading the sodium lignosulfonate anolyte by using the ferric trichloride and hydrogen peroxide composite catalytic system is found, the maximum output voltage of the ferric trichloride and hydrogen peroxide composite system is 0.47V, and the maximum output current density is 187.5mA/cm2The maximum output power density is 13.48mW/cm2. The power generation performance is lower than that of a composite catalytic system using ferric trichloride and titanium dioxide, hydrogen peroxide and ferric trichloride compete for electrons in the reaction process, the power storage performance of ferric ions is inhibited, and the battery generates powerThe electrical properties are degraded. Compared with the example 2, the electricity generation performance of the catalytic oxidation system composed of ferric salt and titanium dioxide for degrading sodium lignosulfonate is better than that of a ferric trichloride and hydrogen peroxide composite catalytic oxidation system.
It can be seen from the above examples and comparative examples that the direct sunlight induced degradation of the alkali lignin, sodium lignosulfonate, and other industrial lignins has three advantages, one is to efficiently degrade the industrial lignin macromolecules, the other is to save the energy consumption cost of heating the electrolyte, and the other is to generate clean electric energy.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, and the scope of protection is still within the scope of the invention.
Claims (10)
1. A method for high-value utilization of industrial lignin is characterized by comprising the following steps:
s1, preparing an anolyte: preparing a mixed solution containing trivalent ferric salt, acid, nano titanium dioxide and industrial lignin, and then placing the mixed solution under illumination for photoinduced degradation to prepare an anolyte;
s2, preparing a cathode electrolyte: firstly, preparing a mixed solution containing pentavalent vanadium salt and acid, and stirring at room temperature until the mixed solution is clear and transparent to prepare a cathode electrolyte;
s3, constructing a biomass fuel cell system: and (3) adding the anolyte obtained in the step (S1) into an anolyte tank, adding the catholyte obtained in the step (S2) into a catholyte tank, connecting the anolyte tank with an anode inlet and an anode outlet of the battery and an anode pump by using a guide pipe, connecting the catholyte tank with a cathode inlet and a cathode outlet of the battery and a cathode pump, and finally starting the constructed biomass fuel cell system to realize high-value utilization of the industrial lignin.
2. The method for utilizing industrial lignin at a high value according to claim 1, wherein the industrial lignin is one or both of alkali lignin and lignosulfonate.
3. The method for high-value utilization of industrial lignin according to claim 1, wherein the ferric salt comprises at least one of ferric chloride, ferric sulfate and ferric nitrate.
4. The method for high-valued utilization of industrial lignin according to claim 1, wherein in the anolyte, the concentration of the ferric iron salt is 1-4 mol/L, the concentration of hydrogen ions of the acid is 1-4 mol/L, the content of the nano titanium dioxide is 40-100 g/L, the particle size of the nano titanium dioxide is 10-200 nm, and the content of the industrial lignin is 10-50 g/L.
5. The method for high-valued utilization of industrial lignin according to claim 1, wherein the light source used for illumination comprises at least one of sunlight, ultraviolet light, visible light and infrared light, and the illumination time is 3-20 h.
6. The method of claim 1, wherein the pentavalent vanadium salt comprises at least one of vanadium pentoxide, vanadyl sulfate, and vanadyl nitrate.
7. The method for high-value utilization of industrial lignin according to claim 1, wherein the concentration of said pentavalent vanadium salt is 0.05 to 5mol/L and the concentration of said acid hydrogen ion is 0.05 to 8.0mol/L in said catholyte.
8. The method for high-value utilization of industrial lignin according to claim 1, wherein said acid in the anolyte or catholyte is at least one of hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid.
9. An electrolyte for degrading industrial lignin, which is characterized by comprising a ferric salt, acid, nano titanium dioxide and industrial lignin.
10. A biomass fuel cell, characterized in that the electrolyte of claim 9 is used as an anolyte, the anolyte needs to be degraded by light, and the catholyte of the biomass fuel cell comprises pentavalent vanadium salt and acid.
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