CN114551953B - High-value utilization method of industrial lignin - Google Patents
High-value utilization method of industrial lignin Download PDFInfo
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- CN114551953B CN114551953B CN202210144971.8A CN202210144971A CN114551953B CN 114551953 B CN114551953 B CN 114551953B CN 202210144971 A CN202210144971 A CN 202210144971A CN 114551953 B CN114551953 B CN 114551953B
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- lignin
- anolyte
- acid
- industrial lignin
- catholyte
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- 229920005610 lignin Polymers 0.000 title claims abstract description 111
- 238000000034 method Methods 0.000 title claims abstract description 51
- 239000002253 acid Substances 0.000 claims abstract description 41
- 239000002028 Biomass Substances 0.000 claims abstract description 39
- 238000006731 degradation reaction Methods 0.000 claims abstract description 37
- 239000003513 alkali Substances 0.000 claims abstract description 25
- 229920001732 Lignosulfonate Polymers 0.000 claims abstract description 14
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 44
- 239000003792 electrolyte Substances 0.000 claims description 34
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 33
- 239000000446 fuel Substances 0.000 claims description 33
- 230000015556 catabolic process Effects 0.000 claims description 32
- 239000011259 mixed solution Substances 0.000 claims description 30
- 150000003839 salts Chemical class 0.000 claims description 25
- 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
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 230000000593 degrading effect Effects 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 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
- 238000003756 stirring Methods 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 230000006698 induction Effects 0.000 claims description 3
- 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
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 238000010248 power generation Methods 0.000 abstract description 25
- 238000005265 energy consumption Methods 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 8
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 37
- 210000004027 cell Anatomy 0.000 description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 21
- 238000010438 heat treatment Methods 0.000 description 19
- 229910002804 graphite Inorganic materials 0.000 description 17
- 239000010439 graphite Substances 0.000 description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 15
- 230000008569 process Effects 0.000 description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 11
- 230000003197 catalytic effect Effects 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
- -1 p-hydroxyphenyl Chemical group 0.000 description 11
- 230000005611 electricity Effects 0.000 description 10
- 238000010586 diagram Methods 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 229920005552 sodium lignosulfonate Polymers 0.000 description 8
- 238000011282 treatment Methods 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- 238000010276 construction Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000004408 titanium dioxide Substances 0.000 description 7
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 229960002089 ferrous chloride Drugs 0.000 description 6
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 6
- 241000609240 Ambelania acida Species 0.000 description 5
- 241000209094 Oryza Species 0.000 description 5
- 235000007164 Oryza sativa Nutrition 0.000 description 5
- 239000010905 bagasse Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 235000009566 rice Nutrition 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000010902 straw Substances 0.000 description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000008103 glucose Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000004537 pulping Methods 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000000813 microbial effect Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 108091006149 Electron carriers Proteins 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000021523 carboxylation Effects 0.000 description 2
- 238000006473 carboxylation reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 229910001447 ferric ion Inorganic materials 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 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
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000011276 addition treatment Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 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
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000004574 high-performance concrete Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229920005611 kraft lignin Polymers 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000011197 physicochemical method Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Microbiology (AREA)
- Sustainable Energy (AREA)
- Sustainable Development (AREA)
- Manufacturing & Machinery (AREA)
- Biochemistry (AREA)
- Fuel Cell (AREA)
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, the invention can degrade the industrial lignin such as alkali lignin, lignin sulfonate and the like only by the irradiation of the sun light in the nature without additionally introducing other external conditions, thereby greatly reducing the energy consumption and the cost. Simultaneously, 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 fully utilize chemical energy released in the degradation process of the industrial lignin to couple power generation, thereby realizing the high-value utilization of the industrial lignin.
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
Biomass is abundant in variety, large in reserves, renewable, and can be converted into other forms of energy and chemicals through a physicochemical method, so that the biomass is widely paid attention to. Among them, lignin is one of three major components of plant cell walls, and is widely present in various plants. The natural lignin structure is very complex, and is generally formed by connecting three basic structural units of p-hydroxyphenyl, guaiacyl and syringyl through chemical bonds such as C-O, C-C. The lignin has a wide application value due to various active functional groups and aromatic rings.
The lignocellulose biomass containing natural lignin is produced with great amount of industrial lignin as side product in pulping, papermaking, biorefinery and other production process. It is counted that annual industrial lignin production in the world is hundreds of millions of tons, and the annual industrial lignin production in China is over 2000 tens of thousands of tons. At present, the effective utilization rate of the industrial lignin is less than 20%, most of the industrial lignin is utilized in a low-value mode such as power generation by incineration or heat energy recovery, so that not only is the resource seriously wasted, but also a large amount of CO 2 is discharged to the environment, and the realization of carbon peak and carbon neutralization double-carbon targets is seriously hindered.
According to the different pulping and cooking processes, industrial lignin is mainly classified into alkali lignin, lignin sulfonate, lignin sulfate, organic solvent lignin and the like. Wherein the industrial lignin obtained by digestion with caustic soda method is alkali lignin; the industrial lignin obtained by steaming by a sulfite method in the acid pulping process is lignin sulfonate; the kraft process yields kraft lignin; and the industrial lignin obtained when the separation is carried out by adopting an organic solvent method is the organic solvent lignin. At present, when lignocellulose biomass is refined by a biorefinery, only the value-added utilization of carbohydrate, such as bioethanol, pulping, papermaking and the like, is generally concerned, so that irreversible condensation polycondensation of lignin components is easily caused in the separation and refining process. Therefore, the byproduct industrial lignin has a series of defects of poor water solubility, high molecular weight, low reactivity and the like, and the high-value utilization of the byproduct industrial lignin is very challenging. Therefore, research and development of high-value utilization of industrial lignin has important economic and environmental benefits.
Currently, application studies of industrial lignin have attracted a great deal of attention. The industrial lignin is used as a modifying additive of cement to produce high-performance concrete. Hydroxyl rich in industrial lignin can be used for preparing lignin/polyurethane polymer materials, lignin-based phenolic adhesives and the like; the potential application in the field of daily chemicals can be developed by utilizing the antibacterial, antioxidant and other performances of the industrial lignin; the industrial lignin is used as a precursor of the activated carbon, and is carbonized and activated in an oxygen-free atmosphere to prepare the porous carbon material with abundant 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 mainly comprises technologies such as direct-fired power generation and the like, is influenced by Carnot cycle, and has low power generation efficiency. While biomass fuel cell technologies still under investigation mainly include solid oxide fuel cells, microbial fuel cells, direct biomass fuel cells, and the like. The solid oxide fuel cell needs to gasify or carbonize biomass at high temperature, has high energy consumption and low efficiency, and generates electric energy far smaller than consumed electric energy. The microbial fuel cell has the dual functions of degrading pollutants and generating electricity although the working temperature is low, but the electricity generating efficiency of the cell is low, and the metabolism capability and the recycling rate of electricity generating microorganisms are low, so that the microbial fuel cell is easy to be heated or damaged by certain chemical substances to be deactivated, and the performance stability of the cell is poor. The direct biomass fuel cells reported at present all need external heating to supply energy, and the consumed electric energy is far higher than the generated electric energy, so that the direct biomass fuel cells have no obvious economic value.
In conclusion, the industrial lignin has abundant yield and great potential application value, but the actual industrialized application technology is less. At present, the large-scale incineration power generation mode is limited by Carnot cycle, so that the power generation efficiency is low, and a large amount of greenhouse gases can be discharged to the environment. The biomass fuel cell technology still in research stage needs to be heated by supplying a large amount of electric energy from outside, and the electric energy consumed by heating is far higher than the generated electric energy, so that industrialization cannot be realized. Therefore, the novel industrial lignin efficient clean power generation technology is developed, and the dual purposes of high-value utilization of the industrial lignin and environmental protection can be realized.
Disclosure of Invention
In order to overcome the defects in the prior art, the primary purpose of the invention is 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:
The high-value utilization method of the industrial lignin is characterized by comprising the following steps of:
s1, preparing an anolyte: firstly preparing a mixed solution containing ferric salt, acid, nano titanium dioxide and industrial lignin, and then placing the mixed solution under illumination for photoinduction degradation to prepare an anolyte:
Preparing an anolyte, and adding the anolyte into a photoreactor to perform photoinduced degradation reaction under the illumination condition; the step is to degrade industrial lignin and store electrons in electrolyte, and store and transport electrons released when molecular bonds of the industrial lignin break while gradually degrading industrial lignin macromolecules, so as to lay a foundation for supplying power to external loads by using a biomass fuel cell system.
The reaction is carried out under the illumination condition because ferric iron salt and nano titanium dioxide can absorb ultraviolet-visible light, and the ferric iron ion and the titanium dioxide are excited by sunlight to be in a high-energy state, so that chemical bonds of industrial lignin molecules are efficiently broken to degrade the industrial lignin molecules.
The acid is added in the step to increase the solubility and stability of the ferric salt of the oxidant, so that the reaction activity of the ferric salt is more beneficial to being exerted under the acidic condition, and meanwhile, the H + is transmitted from the anode to the cathode through the proton exchange membrane to form a closed loop with electrons transported by an external circuit. The nano titanium dioxide is added, so that the energy density of the electrolyte and the light-induced degradation capability in a visible light region can be improved, and the catalytic degradation is more efficient.
S2, preparing a catholyte: firstly, preparing a mixed solution comprising pentavalent vanadium salt and acid, and stirring at room temperature until the mixed solution is clear and transparent to prepare a catholyte, wherein the catholyte comprises pentavalent vanadium salt and acid;
The step is to prepare the catholyte, so as to lay a foundation for constructing a biomass fuel cell system together with the step S1.
In the step, pentavalent vanadium salt is selected as a cathode electron carrier, and the standard electrode potential of the pentavalent vanadium salt is about 1V and is higher than the standard potential of ferric salt of an anode electron carrier by 0.77V, so that the use of the pentavalent vanadium salt as a cathode can increase the open-circuit voltage of the battery, and the excellent electrical property of the battery is provided. The acid is added in the step to increase the solubility and redox activity of the pentavalent vanadium salt, and the activity of the pentavalent vanadium salt is more beneficial to be exerted under the acidic condition.
S3, constructing a biomass fuel cell system: adding the anolyte in the step S1 into an anolyte tank, adding the catholyte in the step S2 into a catholyte tank, connecting the anolyte tank with an anode inlet and an anode pump of a battery by a conduit, connecting the catholyte tank with a cathode inlet and an cathode pump of the battery, and finally starting the constructed biomass fuel cell system to realize high-value utilization of 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 and no toxicity, and is easy to dissolve in water and acid liquid after carboxylation modification.
Further, the lignosulfonate is sodium lignosulfonate. The sodium lignin sulfonate is brown powder, has no special peculiar smell, is nontoxic, is easily dissolved in water and acid liquor, and has stronger dispersing capability. The main structural units of the sodium lignin sulfonate monomer are as follows:
The invention provides a high-value utilization method of industrial lignin, which uses cheap ferric salt and nano TiO 2 as catalytic oxidants to construct a composite photocatalytic oxidation system, so that the industrial lignin can be efficiently degraded, and chemical energy released in the degradation process can be fully utilized to couple power generation. Compared with the prior art, the method for directly utilizing the biomass fuel cell principle to generate electricity by utilizing the industrial lignin has the advantages that biomass energy in the industrial lignin can be efficiently converted into electric energy without a complex conversion process, the operation is simple, and the high-value utilization of the industrial lignin is realized.
Preferably, the ferric salt includes 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 trivalent ferric 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 salt is 1mol/L, the concentration of hydrogen ions of the acid is 2mol/L, the content of the titanium dioxide is 80g/L, and the content of the industrial lignin is 40g/L.
In the anolyte, the amount of the added acid needs to be controlled, and if the amount of the added acid is too small, the solubility and the stability of the ferric salt are insufficient; if the acid content of the reaction system is too high, the corrosion to equipment is strong.
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 illumination is sunlight, and the illumination time is 4 hours.
The light intensity and time need to be controlled in the photoreaction process, and the light intensity is too weak and the time is too short, so that the degradation rate and the degradation degree of the industrial lignin are low; the light intensity is too strong and the time is too long, so that the degradation effect of the industrial lignin is not remarkably improved, and the economic effect is not achieved.
Further, the temperature of the solar illumination is 10-40 ℃.
The invention directly adopts solar light to induce oxidation and degrade alkali lignin, lignosulfonate and other industrial lignin to generate clean electric energy, and has three advantages: the method can degrade molecules of industrial lignin such as alkali lignin, lignosulfonate and the like efficiently, save energy consumption cost of heating treatment electrolyte, and generate clean electric energy.
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 hydrogen ions of the acid is 0.05-8.0 mol/L.
In the catholyte, the amount of the added acid needs to be controlled, and if the amount of the added acid is too small, the solubility and the stability of the pentavalent iron salt are insufficient; if too much acid is wasted, too high concentration of acid also causes environmental pollution, and the economic and environmental benefits are lower.
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 timely regenerated into high-valence vanadium, so that the timely regeneration of the catholyte is realized, and the stable operation of the power generation system is further maintained.
Preferably, the cell may be a biomass fuel cell commonly used in the field of power generation.
Further, the battery includes graphite plates, graphite felt, separator, fixed end plates, piping, wires, loads, and the like.
Further, the preparation method of the battery comprises the following steps: and filling graphite felt in an S-shaped runner in the graphite plate, and then sequentially assembling the graphite plate, the diaphragm, the fixed end plate, the pipeline, the lead, the load and the like into the battery.
The second object of the present invention is achieved by the following technical solutions:
an electrolyte for degrading industrial lignin, the electrolyte comprising ferric salt, acid, nano titanium dioxide and industrial lignin.
The invention also provides a biomass fuel cell, wherein the electrolyte is taken as an anode electrolyte, the anode electrolyte is required to be degraded through illumination induction, and the cathode electrolyte of the biomass fuel cell comprises pentavalent vanadium salt and acid.
Preferably, the biomass fuel cell further comprises graphite plates, graphite felts, diaphragms, fixed end plates, pipelines, wires, loads, and the like.
Preferably, in the electrolyte or the biomass fuel cell, the lignin is at least one of alkali lignin and lignin sulfonate. Specifically, the lignosulfonate is sodium lignosulfonate.
Preferably, in the electrolyte or biomass fuel cell, the ferric salt includes 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, the concentration of the ferric salt in the anolyte is 1-4 mol/L, the concentration of the hydrogen ion in 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 salt is 1mol/L, the concentration of hydrogen ions 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 40g/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 illumination is sunlight, and the illumination time is 4 hours.
Further, in the electrolyte or the biomass fuel cell, the temperature of the solar light 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 concentration of the hydrogen ion in the acid is 0.05-8.0 mol/L.
Preferably, in the electrolyte or the biomass fuel cell, the acid is at least one of hydrochloric acid, sulfuric acid, and nitric acid in the anolyte or the catholyte.
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-cost, green and environment-friendly ferric salt and nano titanium dioxide to form a composite photocatalytic oxidation system, and can use the industrial lignin for generating clean electric energy under illumination, so that the cost is low, and the high-value utilization of the industrial lignin is realized. Meanwhile, the invention can degrade the industrial lignin by only irradiation of the sun in nature without additionally introducing other external conditions, thereby greatly reducing energy consumption and cost. Simultaneously, 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 simultaneously can fully utilize chemical energy released in the degradation process to couple power generation, thereby realizing the high-value utilization of the industrial lignin.
Drawings
FIG. 1 is a process flow diagram of electricity generation by degradation of alkali lignin;
FIG. 2 is a graph of current density versus voltage versus output power based on an alkali lignin power plant output under sunlight;
FIG. 3 is a process flow diagram of the degradation of sodium lignin sulfonate to produce electricity;
FIG. 4 is a graph of current density versus voltage versus output power of a power plant output for different light sources;
FIG. 5 is a graph of current density versus voltage versus output power from a power plant under different catalytic systems;
FIG. 6 is a graph of current density versus voltage versus output power from a power generation device under heat treatment and sunlight;
FIG. 7 is a graph of current density versus time for the output of the power generation device under heat treatment and sunlight;
FIG. 8 is a graph of current density versus voltage versus output power from a power plant under a ferrous chloride + nano titania anolyte;
FIG. 9 is a graph of current density versus voltage versus output power from a power plant under a ferric trichloride+titanyl sulfate anolyte;
FIG. 10 is a graph of current density versus voltage versus output power of a lignosulfonate power plant without heat treatment.
Detailed Description
The following describes the invention in more detail. The description of these embodiments is provided to assist understanding of the present invention, but is not intended to limit the present invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The experimental methods in the following examples, unless otherwise specified, are conventional, and the experimental materials used in the following examples, unless otherwise specified, are commercially available.
Example 1 electrogenic Properties of degradation of alkali lignin under sunlight
According to the process flow diagram of fig. 1, the method comprises the steps of:
(1) Carboxylation modification of alkali lignin to prepare carboxylated alkali lignin: the method comprises the following specific steps:
1) Adding 5g of alkali lignin and 12.5g of NaOH aqueous solution with 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) 3g of monochloroacetic acid and 5mL of pure water are mixed to prepare a solution, and the solution is slowly added into the beaker filled with the alkali lignin-NaOH solution and stirred uniformly;
3) Stirring at 70deg.C for reaction for 90min, cooling, and regulating pH to 5+ -0.1 with 2mol/L HCl; and centrifuging for 10min at 8000 rpm with a centrifuge, collecting supernatant, and oven drying at 60deg.C to obtain modified carboxylated alkali lignin.
(2) Preparation of an anolyte: 6.75g of ferric trichloride hexahydrate, 2.0g of nano titanium dioxide (60 nm) and 4.2mL of concentrated hydrochloric acid (12 mol/L) are dissolved in deionized water, then 1g of modified carboxylated alkali lignin is added to prepare 25mL of mixed solution (H + concentration is 2 mol/L) consisting of 1mol/L FeCl 3 +80g/L nano titanium dioxide+40 g/L carboxylated alkali lignin, the mixed solution is uniformly mixed and then transferred into a photoreactor, and the photoreactor is placed under sunlight (about 31 ℃) to react for 4 hours, so that the sunlight-induced degradation anolyte is prepared.
(3) Preparation of a catholyte: v 2O5 (10 g) was added to water (262 mL) with vigorous stirring, and 38mL of concentrated H 2SO4 (98%) was added dropwise to the V 2O5 suspension in an ice bath, reacted for 20 hours, and 1mL of nitric acid (42%) was added to make a catholyte (vanadium ion concentration 0.8mol/L, H+ concentration: 2.2 mol/L);
(4) Battery system construction and electrical performance testing:
1) And filling graphite felt in an S-shaped runner in the graphite plate, assembling the graphite plate, a load (LED lamp), a wire, a fixed end plate and the like into a battery according to the sequence of the metal cover plate, the anode graphite plate, the polyethylene film, the Nafion117 film, the polytetrafluoroethylene film, the cathode graphite plate and the metal cover plate, and connecting the battery and the load by using the wire.
2) 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 the anode electrolyte tank with the anode inlet and outlet of the battery and the anode pump by using a guide pipe, and connecting the cathode tank with the cathode inlet and outlet of the battery and the cathode pump to complete the assembly of the power generation device; after the power generation device is started, a scanning current method is adopted to test the electrical performance of the battery, and the result is shown in fig. 2.
As can be seen from FIG. 2, the battery performance of the electrolyte solution treated with solar light irradiation had a maximum output voltage of 0.55V, a maximum output current density of 538.8mA/cm 2, and a maximum output power density of 65.4mW/cm 2. Therefore, under the irradiation of sunlight, ferric ions and nano titanium dioxide can be better oxidized and degraded to alkali lignin, higher-power electric energy can be output, and the sunlight irradiation does not need to introduce extra energy consumption cost, so that the economy and the environmental protection performance are highest.
Example 2 electrical properties of degradation of sodium Lignosulfonate under different light sources
According to the process flow diagram of fig. 3, the method comprises the steps of:
(1) Preparation of an anolyte: 6.75g of ferric trichloride hexahydrate, 2.0g of nano titanium dioxide (60 nm) and 4.2mL of concentrated hydrochloric acid (12 mol/L) are dissolved in deionized water, then 1g of sodium lignin sulfonate is added to prepare 25mL of mixed solution (H + concentration is 2 mol/L) consisting of 1mol/L of FeCl 3 +80g/L of nano titanium dioxide and 40g/L of sodium lignin sulfonate, the mixed solution is uniformly mixed and then transferred into a photoreactor, and the photoreactor is placed under sunlight (about 30 ℃) to react for 4 hours, so that the sunlight-induced degradation anolyte is prepared.
And preparing another two 25mL mixed solutions by adopting the same method, and respectively placing the mixed solutions under a xenon lamp and ultraviolet light (room temperature of 30 ℃) to carry out irradiation reaction for 4 hours to prepare an anode electrolyte for induced degradation of the xenon lamp and an anode electrolyte for induced degradation of the ultraviolet light, wherein the anode electrolyte and the anode electrolyte are to be tested.
(2) Preparation of a catholyte: v 2O5 (10 g) was added to water (262 mL) with vigorous stirring, and 38mL of concentrated H 2SO4 (98%) was added dropwise to the V 2O5 suspension in an ice bath, reacted for 20 hours, and 1mL of nitric acid (42%) was added to make a catholyte (vanadium ion concentration 0.8mol/L, H+ concentration: 2.2 mol/L);
(3) Battery system construction and electrical performance testing:
1) And filling graphite felt in an S-shaped runner in the graphite plate, assembling the graphite plate, a load (LED lamp), a wire, a fixed end plate and the like into a battery according to the sequence of the metal cover plate, the anode graphite plate, the polyethylene film, the Nafion117 film, the polytetrafluoroethylene film, the cathode graphite plate and the metal cover plate, and connecting the battery and the load by using the wire.
2) 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 the anode electrolyte tank with the anode inlet and outlet of the battery and the anode pump by using a guide pipe, and connecting the cathode tank with the cathode inlet and outlet of the battery and the cathode pump to complete the assembly of the power generation device; after the power generation device is started, a scanning current method is adopted to test the electrical performance of the battery, and the result is shown in fig. 4.
As can be seen from fig. 4, the battery composed of the electrolyte treated with solar light irradiation had the best performance, the maximum output voltage was 0.54V, the maximum output current density was 532.7mA/cm 2, and the maximum output power density was 64.5mW/cm 2. In contrast, the battery composed of the electrolyte irradiated with the ultraviolet lamp had inferior performance, and the battery composed of the electrolyte irradiated with the xenon lamp had the worst performance. Compared with the irradiation of a xenon lamp and an ultraviolet lamp, the irradiation of sunlight can better oxidize and degrade sodium lignin sulfonate and output higher-power electric energy, and the irradiation of the sunlight does not need to introduce extra energy consumption cost, so that the method has highest economical efficiency and environmental protection performance.
Example 3 different catalytic Oxidation systems degrade the electrogenic Properties of sodium Lignosulfonate
According to the process flow diagram of fig. 3, the method comprises the steps of:
(1) Preparation of an anolyte: 6.75g of ferric trichloride hexahydrate, 2.0g of nano titanium dioxide and 4.2mL of concentrated hydrochloric acid are dissolved in deionized water, then 1g of sodium lignin sulfonate is added to prepare 25mL of mixed solution (H + concentration is 2 mol/L) consisting of 1mol/L FeCl 3 +80g/L nano titanium dioxide+40 g/L sodium lignin sulfonate, the mixed solution is uniformly mixed and then transferred into a photoreactor, and the photoreactor is placed under sunlight (about 24 ℃) to react for 4 hours, so that the sunlight-induced degradation anolyte is prepared.
(2) Preparation of control anolyte No. 1: 2g of nano titanium dioxide, 1g of sodium lignin sulfonate and 4.2mL of concentrated hydrochloric acid are added into deionized water, and 25mL of mixed solution (H + concentration is 2 mol/L) consisting of 80g/L of nano titanium dioxide and 40g/L of sodium lignin sulfonate is prepared after uniform mixing. Then transferring the mixture into a photoreactor, and placing the mixture into sunlight (about 24 ℃) to react for 4 hours to prepare the sunlight-induced degradation No. 1 control anolyte.
(3) Preparation of control anolyte No. 2: 6.75g of ferric trichloride hexahydrate, 1g of sodium lignin sulfonate and 4.2mL of concentrated hydrochloric acid were added to deionized water to prepare 25mL of a mixed solution (H + concentration: 2 mol/L) consisting of 1mol/L FeCl 3 +40g/L sodium lignin sulfonate. And (3) uniformly mixing, transferring into a photoreactor, and placing into sunlight (about 24 ℃) to react for 4 hours to prepare the No. 2 control anolyte degraded by sunlight.
(4) Catholyte was prepared as in example 1.
(5) The battery system construction and electrical performance test method were the same as in example 1, and the results are shown in fig. 5.
As can be seen from fig. 5, under the irradiation for 4 hours, the maximum output voltage is 0.50V, the maximum output current density is 352.5mA/cm 2, and the maximum output power density is 41.6mW/cm 2, which proves that under the synergistic effect of ferric trichloride and nano titanium dioxide, the effect of catalyzing and degrading sodium lignin sulfonate to generate electricity is better than that of single nano titanium dioxide and single FeCl 3.
Example 4 comparison of the electrogenic Properties of light-treated and Heat-treated degraded sodium Lignosulfonate
According to the process flow diagram of fig. 3, the method comprises the steps of:
(1) Preparing an anode electrolyte by light treatment: the preparation method is the same as in example 2.
(2) Preparing an anode electrolyte by heat treatment: 6.75g of ferric trichloride hexahydrate, 2.0g of nano titanium dioxide and 4.2mL of concentrated hydrochloric acid are dissolved in deionized water, then 1g of sodium lignin sulfonate is added to prepare 25mL of mixed solution (H + concentration is 2 mol/L) consisting of 1mol/L FeCl 3 +80g/L nano titanium dioxide+40 g/L sodium lignin sulfonate, and the mixed solution is transferred to 60 ℃ for constant temperature reaction for 4 hours after being uniformly mixed, so that the thermal degradation lignin electrolyte is prepared.
(3) Catholyte was prepared as in example 1.
(4) The battery system construction and electrical performance test method were the same as in example 1, and the results are shown in fig. 6.
(5) The current density was tested over time (I-t) and the results are shown in FIG. 7. And calculating the power generation amount 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 expression, and the energy change is shown in table 1.
Q＝U·I·t
Wherein: q is the generated energy, U is the working voltage (unit: V) of the heating table, I is the working current (unit: A), and t is the working time (unit: s).
As can be seen from fig. 6 and 7, the performance of the heat treatment group battery was inferior to that of the light treatment group. Wherein, the maximum output voltage of the heat treatment group is 0.44V, the maximum output current density is 502.7mA/cm 2, and the maximum output power density is 58.4mW/cm 2; the maximum output voltage of the light treatment group was 0.54V, the maximum output current density was 532.7mA/cm 2, and the maximum output power density was 64.5mW/cm 2. Therefore, compared with the heating treatment, the solar battery has better performance, which indicates that the solar power generation performance is better when the sodium lignin sulfonate is degraded by solar induction to generate power. Meanwhile, as can be seen from table 1, the degradation process of the light treatment group does not need energy consumption cost generated by heating, and the light treatment group has low energy consumption, is environment-friendly and has larger generated energy.
TABLE 1 comparison of the amount of Power generated and the energy variation of degradation of sodium Lignosulfonate by light treatment and Heat treatment
Example 5 Effect of different anolyte on the electrogenic Properties of degradation of sodium Lignosulfonate
According to the process flow diagram of fig. 3, the method comprises the steps of:
(1) Preparing ferrous chloride and nano titanium dioxide anolyte: 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, then 1g of sodium lignin sulfonate is added to prepare 25mL of mixed solution (H + concentration is 2 mol/L) consisting of 1mol/L FeCl 2 +80g/L nano titanium dioxide+40 g/L sodium lignin sulfonate, the mixed solution is uniformly mixed and then transferred into a photoreactor, and the photoreactor is placed under sunlight (about 30 ℃) for 4 hours to prepare the sunlight-induced degradation ferrous chloride+nano titanium dioxide anolyte.
(2) Preparing ferric trichloride and titanyl sulfate anolyte: 6.75g of ferric trichloride hexahydrate, 2.0g of titanyl sulfate and 4.2mL of concentrated hydrochloric acid are dissolved in deionized water, then 1g of sodium lignin sulfonate is added to prepare 25mL of mixed solution (H + concentration is 2 mol/L) consisting of 1mol/L FeCl 3 +80g/L titanyl sulfate+40 g/L sodium lignin sulfonate, the mixed solution is uniformly mixed and then transferred into a photoreactor, and the photoreactor is placed under sunlight (about 30 ℃) to react for 4 hours, so that the sunlight-induced degradation ferric trichloride+titanyl sulfate anolyte is prepared.
(3) Preparation of anolyte without adding light and heating: 6.75g of ferric trichloride hexahydrate, 2.0g of nano titanium dioxide and 4.2mL of concentrated hydrochloric acid are dissolved in deionized water, then 1g of sodium lignin sulfonate is added to prepare 25mL of mixed solution (H + concentration is 2 mol/L) consisting of 1mol/L of ferric trichloride, 80g/L of nano titanium dioxide and 40g/L of sodium lignin sulfonate, the mixed solution is uniformly mixed and then transferred into a flask, and the mixture is reacted for 4 hours at room temperature (about 30 ℃) under a water bath, so that the anolyte is prepared.
(4) Preparation of a catholyte: same as in example 2;
(5) Battery system construction and electrical performance testing: as in example 2.
As a result, it was found that when solar light was used, the battery performance was optimal with an anolyte composed of trivalent iron salt, acid, nano titanium dioxide and sodium lignin sulfonate, the maximum output voltage was 0.54V, the maximum output current density was 532.7mA/cm 2, and the maximum output power density was 64.5mW/cm 2; and the battery performance of the anolyte consisting of ferrous chloride, acid, nano titanium dioxide and sodium lignin sulfonate, the maximum output voltage was only 0.47V, the maximum output current density was 87.35mA/cm 2, and the maximum output power density was 15.3mW/cm 2 (fig. 8). The reason is that ferrous salts are reducing but not oxidizing and cannot degrade sodium lignin sulfonate. The cell performance of the anolyte consisting of ferric salt, acid, titanyl sulfate and sodium lignin sulfonate was at a maximum voltage of 0.48V, maximum current density of 57.35mA/cm 2 and maximum power density of 9.01mW/cm 2 (fig. 9). Therefore, the effect of photocatalytic degradation of lignin sulfonate by ferrous chloride or titanyl sulfate is not excellent in the degradation effect of ferric trichloride or nano titanium dioxide. Therefore, the anolyte composed of ferric salt, acid, nano titanium dioxide and sodium lignin sulfonate has better effect of catalyzing and degrading sodium lignin sulfonate to generate electricity.
In addition, the battery consisting of the sodium lignin sulfonate anolyte degraded by the no-light and no-heat treatment method had poor performance, wherein the maximum output voltage was 0.49V, the maximum output current density was 23.6mA/cm 2, and the maximum output power density was 3.23mW/cm 2. The power generation performance is far lower than that of the light addition treatment and the heat treatment (fig. 10). The description shows that when the catalytic oxidation system composed of ferric salt and nano titanium dioxide generates electricity, the photo-induced degradation or the heating-induced degradation is needed to achieve better effect, and the photo-induced degradation effect is better.
Example 6 degradation of other Biomass electrogenic Properties
According to the process flow diagram of fig. 3, the method comprises the steps of:
(1) Preparation of a catholyte: as in example 1.
(2) Preparation of rice straw-containing anolyte: 6.75g of ferric trichloride hexahydrate, 2.0g of nano titanium dioxide and 4.2mL of concentrated hydrochloric acid are dissolved in deionized water, then 1g of rice straw is added to prepare 25mL of solid-liquid mixture (H + concentration is 2 mol/L) consisting of 1mol/L FeCl 3 +80g/L nano titanium dioxide+40 g/L rice straw, the mixture is transferred into a photo-reactor and reacted for 4 hours under sunlight (about 30 ℃) to prepare the sunlight induced degradation anolyte.
(3) Preparing bagasse-containing anolyte: 6.75g of ferric trichloride hexahydrate, 2.0g of nano titanium dioxide and 4.2mL of concentrated hydrochloric acid are dissolved in deionized water, then 1g of bagasse is added to prepare 25mL of solid-liquid mixture (H + concentration is 2 mol/L) consisting of 1mol/L FeCl 3 +80g/L nano titanium dioxide+40 g/L bagasse, the mixture is transferred into a photoreactor and placed under sunlight (about 30 ℃) to react for 4 hours, and then the sunlight-induced degradation anolyte is prepared.
(4) Preparing a glucose-containing anolyte: 6.75g of ferric trichloride hexahydrate, 2.0g of nano titanium dioxide and 4.2mL of concentrated hydrochloric acid are dissolved in deionized water, then 1g of glucose is added to prepare 25mL of mixed solution (H + concentration is 2 mol/L) consisting of 1mol/L FeCl 3 +80g/L titanium dioxide+40 g/L glucose, the mixed solution is uniformly mixed and then transferred into a photoreactor, and the photoreactor is placed under sunlight (about 30 ℃) to react for 4 hours, so that the sunlight-induced degradation anolyte is prepared.
(5) Battery system construction and electrical performance testing: as in example 1.
As a result, it was found that the battery composed of the sodium lignin sulfonate-containing anolyte had the best performance, the maximum voltage was 0.54V, the maximum current density was 532.7mA/cm 2, and the maximum power density was 64.5mW/cm 2. The battery performance of the rice straw-containing anolyte has the maximum voltage of only 0.28V, the maximum current density of 287.6mA/cm 2 and the maximum power density of 29.1mW/cm 2. The battery performance of the bagasse anolyte contained a maximum voltage of 0.31V, a maximum current density of 320.1mA/cm 2, and a maximum power density of 33.2mW/cm 2. The cell performance with glucose anolyte had a maximum voltage of 0.36V, a maximum current density of 311.91mA/cm 2 and a maximum power density of 45.7mW/cm 2. It can be seen that the biomass such as rice straw, bagasse and the like has poor solubility in acidic aqueous solution, cannot be fully contacted with the catalytic oxidant, and has poor performance. The sodium lignin sulfonate has good solubility in acidic aqueous solution, and can play a good 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 composed of ferric salt and nano titanium dioxide has better effect of degrading sodium lignin sulfonate to generate electricity.
Comparative example 1 study on the Power Generation Performance of a ferric trichloride and Hydrogen peroxide Complex System to degrade sodium Lignosulfonate
According to the process flow diagram of fig. 3, the method comprises the steps of:
(1) Preparation of an anolyte containing sodium lignin sulfonate: 6.75g of ferric trichloride hexahydrate, 1mL of 30% hydrogen peroxide solution and 4.2mL of concentrated hydrochloric acid were dissolved in deionized water, then 1g of sodium lignin sulfonate was added to prepare 25mL of a mixed solution (H + concentration: 2 mol/L) consisting of 1.1mol/L hydrogen peroxide +1mol/L ferric trichloride +40g/L sodium lignin sulfonate, and the mixed solution was transferred to a photo-reactor after being uniformly mixed and reacted at room temperature (about 30 ℃) under sunlight for 4 hours to prepare an anolyte.
(2) Preparation of a catholyte: as in example 1.
(3) Battery system construction and electrical performance testing: as in example 1.
As a result, it was found that the maximum output voltage of the iron trichloride and hydrogen peroxide composite system was 0.47V, the maximum output current density was 187.5mA/cm 2, and the maximum output power density was 13.48mW/cm 2, using the iron trichloride and hydrogen peroxide composite catalytic system to degrade the battery performance composed of the sodium lignin sulfonate anolyte. The power generation performance is lower than that of a composite catalytic system using ferric trichloride and titanium dioxide, and hydrogen peroxide and ferric trichloride compete for electrons in the reaction process, so that the power storage performance of ferric ions is inhibited, and the power generation performance of the battery is reduced. In comparison with example 2, it is demonstrated that the catalytic oxidation system consisting of ferric salt and titanium dioxide can achieve better electrical performance than the ferric chloride+hydrogen peroxide composite catalytic oxidation system.
The above examples and comparative examples show that the direct solar light induced degradation of alkali lignin, sodium lignin sulfonate and other industrial lignin has three advantages, namely, the high efficiency degradation of industrial lignin macromolecules, the saving of the energy consumption cost of heating the electrolyte and the generation of clean electric energy.
The embodiments of the present invention have been described in detail above, 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 to these embodiments without departing from the principles and spirit of the invention, and yet fall within the scope of the invention.
Claims (9)
1. The high-value utilization method of the industrial lignin is characterized by comprising the following steps of:
s1, preparing an anolyte: firstly preparing a mixed solution containing ferric salt, acid, nano titanium dioxide and industrial lignin, and then placing the mixed solution under illumination for photoinduction degradation to prepare an anolyte; the ferric salt comprises at least one of ferric chloride, ferric sulfate and ferric nitrate;
S2, preparing a catholyte: firstly, preparing a mixed solution comprising pentavalent vanadium salt and acid, and stirring at room temperature until the mixed solution is clear and transparent to prepare a catholyte;
S3, constructing a biomass fuel cell system: adding the anolyte in the step S1 into an anolyte tank, adding the catholyte in the step S2 into a catholyte tank, connecting the anolyte tank with an anode inlet and an anode pump of a battery by a conduit, connecting the catholyte tank with a cathode inlet and an cathode pump of the battery, and finally starting the constructed biomass fuel cell system to realize high-value utilization of industrial lignin.
2. The method for high-value utilization of industrial lignin according to claim 1, wherein said industrial lignin is one or both of alkali lignin and lignin sulfonate.
3. The method for high-value utilization of industrial lignin according to claim 1, wherein the concentration of the ferric salt in the anolyte is 1-4 mol/L, the concentration of the hydrogen ion 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.
4. The method for high-value 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.
5. The method for high value utilization of industrial lignin according to claim 1, wherein said pentavalent vanadium salt comprises at least one of vanadium pentoxide, vanadyl sulfate and vanadyl nitrate.
6. The method for high-value utilization of industrial lignin according to claim 1, wherein the concentration of the pentavalent vanadium salt in the catholyte is 0.05-5 mol/L, and the concentration of the hydrogen ion of the acid is 0.05-8.0 mol/L.
7. The method for high-value utilization of industrial lignin according to claim 1, wherein said acid is at least one of hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid in said anolyte or catholyte.
8. An electrolyte for degrading industrial lignin, characterized in that the electrolyte comprises ferric salt, acid, nano titanium dioxide and industrial lignin.
9. A biomass fuel cell, characterized in that the electrolyte of claim 7 is taken as an anolyte of the biomass fuel cell, the anolyte is required to be degraded by illumination induction, and the catholyte of the biomass fuel cell comprises pentavalent vanadium salt and acid.
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