CN116328729A - Modified lignin-based biochar material, preparation method thereof and application thereof in wastewater defluorination - Google Patents
Modified lignin-based biochar material, preparation method thereof and application thereof in wastewater defluorination Download PDFInfo
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- 229920005610 lignin Polymers 0.000 title claims abstract description 105
- 239000002351 wastewater Substances 0.000 title claims abstract description 102
- 239000000463 material Substances 0.000 title claims abstract description 72
- 238000006115 defluorination reaction Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 76
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 24
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 15
- 230000023556 desulfurization Effects 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 15
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003546 flue gas Substances 0.000 claims abstract description 6
- 230000004048 modification Effects 0.000 claims abstract description 3
- 238000012986 modification Methods 0.000 claims abstract description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 24
- 238000001994 activation Methods 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 23
- 238000002791 soaking Methods 0.000 claims description 20
- 230000004913 activation Effects 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- 239000003610 charcoal Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 239000002028 Biomass Substances 0.000 claims description 13
- 238000005345 coagulation Methods 0.000 claims description 8
- 230000015271 coagulation Effects 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 7
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 7
- 235000005822 corn Nutrition 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000010453 quartz Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 241000209149 Zea Species 0.000 claims 2
- 239000010907 stover Substances 0.000 claims 1
- 239000011737 fluorine Substances 0.000 abstract description 63
- 229910052731 fluorine Inorganic materials 0.000 abstract description 63
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 56
- 238000003756 stirring Methods 0.000 abstract description 20
- 230000001376 precipitating effect Effects 0.000 abstract description 8
- 239000002352 surface water Substances 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 21
- 150000002500 ions Chemical class 0.000 description 14
- -1 fluorine ions Chemical class 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 238000001179 sorption measurement Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 6
- 238000004364 calculation method Methods 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 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 description 6
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 6
- 240000008042 Zea mays Species 0.000 description 5
- 238000009388 chemical precipitation Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 3
- 229910001634 calcium fluoride Inorganic materials 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 229920002401 polyacrylamide Polymers 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 2
- 150000001449 anionic compounds Chemical class 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000701 coagulant Substances 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910001412 inorganic anion Inorganic materials 0.000 description 2
- 238000004255 ion exchange chromatography Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 206010016818 Fluorosis Diseases 0.000 description 1
- 208000001132 Osteoporosis Diseases 0.000 description 1
- 238000013494 PH determination Methods 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 206010003246 arthritis Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 208000004042 dental fluorosis Diseases 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
-
- 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
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention belongs to the technical field of biochar materials, and particularly relates to a modified lignin-based biochar material, a preparation method thereof and application thereof in wastewater defluorination. The modified lignin-based biochar material is prepared through the preparation of lignin-based biochar raw materials, the preparation of lignin-based biochar materials and the modification of lignin-based biochar materials. The modified lignin-based biochar material can effectively reduce the fluorine content of wastewater to below 1.0mg/L in the treatment application of the fluorine-containing wastewater in the flue gas desulfurization process wastewater, and meets three water treatment standards in the quality standard of the surface water environment. The invention can finish the preparation of the modified lignin-based biochar for defluorination within 24 hours, and has high efficiency, simplicity and strong practicability. In the treatment process of the invention, only stirring and precipitating equipment is used, so that the investment is less.
Description
Technical Field
The invention belongs to the technical field of biochar materials, and particularly relates to a modified lignin-based biochar material, a preparation method thereof and application thereof in wastewater defluorination.
Background
The agricultural biomass resources in China are rich, the yield is high, and the annual yield is up to 7 hundred million tons. The biomass resource has the characteristics of high heat value, huge volume, rich crude fiber content, developed pores and the like, and the adsorption capacity of the product carbon material obtained after the dehydrogenation and deoxidation treatment at high temperature is remarkable, so that the biomass resource is an effective way for biomass utilization, and has been widely applied to the field of sewage treatment in recent years. For example, the biochar is used as a novel biomass-based adsorbent, has multiple functional groups such as polycyclic aromatic hydrocarbon on the surface, shows multiple properties such as hydrophilicity and hydrophobicity, and can effectively remove multiple pollutants in water.
Fluorine is one of the microelements which are indispensable for maintaining normal physiological activities of human bodies, but excessive intake can cause problems of fluorosis, osteoporosis, arthritis and the like. In life, the fluorine content in the drinking water is generally required to be not more than 1mg/L, and the fluorine ion content in industrial wastewater is required to be less than 10mg/L. Many industrial manufacturing industries, such as aluminum smelting, electroplating, steel, chemical fertilizers and the like, discharge a large amount of high-fluorine wastewater, particularly the power industry, and the fluorine content in the desulfurization wastewater is up to 3800mg/L when the 1000 liter smoke discharge amount is treated. Therefore, the fluorine-containing wastewater must be treated and then discharged after reaching the standard.
At present, fluoride removal methods in research and development or application include chemical precipitation methods, coagulation precipitation methods, adsorption methods, ion exchange methods, membrane filtration methods, electrochemical methods, and the like. Among the above methods, the chemical precipitation method, the coagulation precipitation method and the adsorption method have relatively low investment cost, and are easy to operate, so that the method has strong practicability and has more application cases. The chemical precipitation method for removing fluoride mainly comprises the steps of adding calcium salts such as lime, calcium chloride and the like into fluorine-containing wastewater to enable fluorine ions and the calcium salts to be combined to form calcium fluoride precipitate with low solubility, and then carrying out solid-liquid separation to remove the fluoride in the form of calcium fluoride. The method has simple operation and equipment, low investment and suitability for large-scale treatment of high-concentration fluorine-containing wastewater. However, the solubility of calcium fluoride was 13.8mg/L, which was 7.8mg/L in terms of fluoride ion. In practical operation, the minimum value is hardly reached, the fluorine content of wastewater is 10-30 mg/L after the wastewater is treated by a chemical precipitation method, the wastewater discharge standard is hardly reached, meanwhile, the problems of large sludge quantity and difficult recovery exist, and the treatment cost is increased. The coagulating sedimentation method is to add coagulant and coagulant aid into the fluorine-containing wastewater, and remove fluorine ions in the water by utilizing adsorption bridging and precipitation net capturing actions. Has the advantages of large wastewater treatment amount, simple and convenient operation, and the like, but has the defects of large medicament addition amount, large sludge amount, and the like. The defluorination flocculating agent commonly used at present is ferric salt, aluminum salt, magnesium salt and the like. The adsorption method is a widely applied defluorination method at present, has more practical application cases, and can be applied to the treatment of low-concentration fluorine-containing wastewater and can also be used as the subsequent treatment of a chemical precipitation method and a coagulating sedimentation method. The adsorbents commonly used in the adsorption method include diatomite, modified lignin-based biochar, activated alumina, hydroxyapatite and the like, but the adsorption performance of the adsorbent material needs to be further improved.
In view of the complex water quality of the wastewater produced by the desulfurization process in the power industry, the salt content can reach 3%, the suspended matter content is high, and the Ca is contained 2+ 、Mg 2+ 、SO 4 2- 、Cl - The plasma may interfere with the complexing and precipitating effect of the fluorine scavenger and the fluoride ions. The characteristics cause difficult removal of fluorine in desulfurization wastewater, large dosage and high cost. Therefore, the novel efficient multi-mechanism compound formula defluorination medicament is especially prepared by using the biochar material, and the key point for solving the problem of difficult defluorination of desulfurization wastewater in the power industry is to effectively reduce the running cost.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a modified lignin-based biochar material which can effectively reduce the fluorine content of wastewater to below 1.0 mg/L.
The invention further aims to provide a preparation method of the modified lignin-based biochar material, which can finish the preparation of the modified lignin-based biochar for defluorination within 24 hours, and has the advantages of high efficiency, simplicity and strong practicability.
The invention also aims to provide an application of the modified lignin-based biochar material in wastewater defluorination, which provides a new solution for the difficult problem of removing fluorine pollutants in desulfurization wastewater in the power industry.
The technical scheme adopted by the invention is as follows:
the preparation method of the modified lignin-based biochar material comprises the following steps:
(1) Preparing lignin-based biochar raw materials: preparing biochar from solid residues (UHS) remained after enzymolysis of pretreated corn stalks produced by bioethanol, drying the solid residues at 60-70 ℃ for 36-60 hours, grinding to obtain powder, and mixing the powder with 80-90 wt.% of H 3 PO 4 Soaking in the solution for 10-20 min, and concentrating to obtain ZnCl with concentration of 20-30% 2 Mixing the solution and the soaked powder for 5-10 hours according to a mass ratio of 10:1, and drying the obtained mixture at 100-120 ℃ for 36-60 hours to obtain lignin-based biochar raw material (ZnCl) 2 -H 3 PO 4 -UHS co-precipitated feedstock);
(2) Preparing a lignin-based biochar material: placing lignin-based biochar raw materials into a quartz tube reactor for activation and drying, wherein the activation temperature is 400-600 ℃, the activation time is 30-90 min, the heating rate is 7-125 ℃/min, and the activation process is carried out in N 2 The method comprises the steps of performing under flowing conditions, cooling to 20-30 ℃ after activation, washing with 35% hydrochloric acid at 40-60 ℃, washing with deionized water, and drying after washing to obtain lignin-based biochar materials;
(3) Modification of lignin-based biochar materials: screening out 100-200 mu m modified lignin-based biochar material particles, and adding the particles into Fe 2 (SO 4 ) 3 Soaking in the solution for 20-28 h; the soaked modified lignin-based biochar material particlesAdding the particles into AlCl 3 Soaking the biomass charcoal in the solution for 20-28 h, carrying out suction filtration on the biomass charcoal, and drying the solid particles subjected to suction filtration at 100-120 ℃ to obtain the modified lignin-based biomass charcoal material.
The solid residue remained after the enzymolysis of the pretreated corn stalks in the bioethanol production consists of the following components: lignin: 40-60%; silicon: 5-15%; ash content: 35-45%.
The specific surface area of the modified lignin-based biochar is 363-423 m 2 /g。
Said Fe 2 (SO 4 ) 3 The mass content of iron element in the solution is 11-13%, and the pH value is 0.5-1.
Said AlCl 3 The mass content of the alumina in the solution is 6-7.5%, and the pH value is 0.4-2.
The modified lignin-based biochar material is prepared by the preparation method.
The application of the modified lignin-based biochar material in wastewater defluorination is used for removing fluorine in wastewater in a flue gas desulfurization process.
Before the fluorine in the wastewater is removed, the pH value of the wastewater is adjusted to be 6-7 by hydrochloric acid. The fluoride ion concentration of the wastewater was measured by the ion selective electrode method (GB 7484-87).
The addition amount of the modified lignin-based biochar material in the wastewater is as follows: 50-100 ppm of modified lignin-based biochar material is added into each 1ppm of fluoride in the wastewater.
In the flue gas desulfurization process, polyaluminium chloride is added to assist coagulation. According to 1ppm fluoride in the wastewater, 10ppm polyaluminum chloride is added to assist coagulation.
The invention adopts a composite medicament combining three mechanisms of precipitation, coagulation and adsorption to remove fluorine. The preparation process of the defluorination material comprises three steps: 1. preparation of lignin-based biochar raw materials. The mixture of the active pore-forming agent and the straw fermentation product is prepared by a coprecipitation method, so that the active agent is uniformly distributed in the biomass, and a powerful condition is created for pore-forming activation. 2. And (3) preparing the lignin-based biochar material. The biochar is prepared under the conditions of a certain temperature, a heating speed and a reaction time. The reaction temperature determines the carbonization proportion of the biochar material and the residual proportion of functional groups such as hydroxyl groups, carboxyl groups and the like, the higher the temperature is, the higher the carbonization proportion of the biomass raw material is, the lower the residual proportion of the functional groups is, and the bonding characteristic of the functional groups is utilized in the subsequent step, so that the activation temperature is not too high. The heating speed influences the gas production and the solid production ratio of the raw material of the biochar, and determines the yield of the biochar. The reaction time determines the degree of stability of the biochar. 3. Modifying lignin-based biochar materials. The porous characteristic and special functional group structure of the biochar material are utilized to bond with iron and aluminum elements with fluorine removal effect, so that the fluorine removal effect of the biochar is improved.
Compared with the prior art, the invention has the following beneficial effects:
(1) The modified lignin-based biochar material can effectively reduce the fluorine content of wastewater to below 1.0mg/L in the treatment application of the fluorine-containing wastewater in the flue gas desulfurization process wastewater, and meets the treatment standard of three types of water in the quality standard of the surface water environment.
(2) The invention can finish the preparation of the modified lignin-based biochar for defluorination within 24 hours, and has high efficiency, simplicity and strong practicability.
(3) In the treatment process of the invention, only stirring and precipitating equipment is used, so that the investment is less.
(4) Compared with the existing fluoride removal method, the modified lignin-based biochar adsorption system-cooperation coagulation method combined application has obvious advantages; provides a new solving way for the difficult problem of removing fluorine pollutants in the desulfurization wastewater in the power industry; the preparation process is simple, the flow is short, complex equipment is not needed, the cost is low, and the application prospect is excellent; the raw materials are easy to obtain and cheap.
Detailed Description
The invention is further illustrated below with reference to examples, which are not intended to limit the practice of the invention.
The test methods used in each of the examples and comparative examples were:
pH in wastewater: HJ1147-2020, electrode method for determination of pH value of Water quality;
chemical oxygen demand in wastewater: HJ828-2017, bichromate method for determination of chemical oxygen demand of Water quality;
biochemical oxygen demand in the wastewater for 5 days: HJ505-2009 "five-day Biochemical Oxygen Demand (BOD) 5 ) Dilution and inoculation method;
total carbon in wastewater: HJ501-2009, "determination of Water quality Total organic carbon Combustion Oxidation-non-dispersive Infrared absorption method";
ammonia nitrogen in wastewater: HJ535-2009, "spectrophotometry for determination of aqueous ammonia-nitrogen" new;
chloride in wastewater: HJ84-2016 inorganic anions (F) - 、Cl - 、NO 2- 、Br - 、NO 3- 、PO 4 3- 、SO 3 2- 、SO 4 2- ) Ion chromatography;
total nitrogen in wastewater: HJ636-2012 "determination of total Nitrogen in Water quality alkaline Potassium persulfate digestion ultraviolet spectrophotometry";
sulfate in wastewater: HJ84-2016 inorganic anions (F) - 、Cl - 、NO 2- 、Br - 、NO 3- 、PO 4 3 -、SO 3 2- 、SO 4 2- ) Ion chromatography;
fluoride ions in wastewater: GB/T7484-1987 ion-selective electrode method for determination of Water-quality fluoride.
Example 1
The water quality index of the fluorine-containing wastewater I is shown in table 1.
TABLE 1 Water quality index of fluorine-containing wastewater I
The modified lignin-based biochar material is prepared by the following method:
(1) Preparing lignin-based biochar raw materials: the method is characterized by preparing biochar from solid residues remained after enzymolysis of pretreated corn stalks in bioethanol production, wherein the components of the raw materials are as follows: lignin:50%; silicon: 10%; ash content: 40%; the solid residue was dried at 65 ℃ for 48H, then ground to obtain a powder, the powder was taken up in 85wt.% H 3 PO 4 Soaking in water for 15min, and collecting ZnCl with concentration of 20% 2 Mixing the solution and soaked powder for 8 hours according to the mass ratio of 10:1, and drying the obtained mixture at 110 ℃ for 48 hours to obtain lignin-based biochar raw materials;
(2) Preparing a lignin-based biochar material: placing lignin-based biochar raw materials into a quartz tube reactor, activating and drying at 500 deg.C for 60min at 60 deg.C/min, and activating at N 2 Is carried out under flowing condition, cooled to 25 ℃ after activation is completed, washed by hydrochloric acid with the concentration of 35 percent at 50 ℃, washing with deionized water, and drying after washing to obtain lignin-based biochar material;
(3) Preparing a modified lignin-based biochar material: taking 125.23g of 150 mu m lignin-based biochar particles, cleaning, and adding 100mL of liquid ferric sulfate Fe 2 (SO 4 ) 3 Soaking the solution for 20 hours, wherein the total iron content in the ferric sulfate solution is 11.3%, the pH value is 0.8, stirring is continuously carried out in the soaking process, and the rotating speed is set to be 120r/min; adding the soaked modified lignin-based biochar material particles into 100mLAlCl 3 Soaking in the solution for 20 hours, wherein the content of alumina in aluminum chloride is 6.5%, and the PH value is 0.42; continuously stirring in the soaking process, setting the rotating speed to 120r/min, washing and drying the filtered solid particles for standby, wherein the drying temperature is 110 ℃; the specific surface area was measured to be 423m 2 /g。
(4) 35% of analytically pure hydrochloric acid was diluted 15 times, and the pH value of the wastewater was adjusted to 6.8 by adding the diluted analytically pure hydrochloric acid to the wastewater, and the concentration of fluorine ions in the fluorine-containing wastewater was measured to be 20.5mg/L by the ion-selective electrode method (GB 7484-87).
(5) 1.54g of modified lignin-based biochar is weighed, added into 1L of fluorine-containing wastewater I, stirred for 10min for complete mixing, added into 0.2g of polyaluminium chloride into the fluorine-containing wastewater, stirred for 12min for complete mixing, stirred at a speed of 150r/min, and then precipitated for 40min.
(6) And (3) filtering the mixture of the modified lignin-based biochar and the fluorine-containing wastewater I by using medium-speed filter paper, measuring the fluorine ion concentration of the filtrate by using an ion selective electrode method (GB 7484-87), and calculating the fluorine ion removal rate.
(7) Fluoride ion removal rate, in w. The numerical values are expressed in%, and the calculation formula is as follows:
wherein:
C 0 -initial fluoride ion concentration, mol/L;
C 1 the concentration of fluoride ions after the reaction, and the mol/L.
The results of the first treatment of fluorine-containing wastewater with the modified lignin-based charcoal material prepared in example 1 are shown in Table 2.
TABLE 2 results after treatment of fluorine-containing wastewater with modified lignin-based charcoal material prepared in example 1
By comparing the indexes of the coking wastewater before and after treatment, the pH of the wastewater after treatment is obviously reduced from 7.8 to 6.7. The treatment method is used for treating various pollution indexes such as Chemical Oxygen Demand (COD), 5-day biochemical oxygen demand (BOD 5), ammonia Nitrogen (NH) 4 N), total Nitrogen (TN), has a removal rate of more than 50%, and the concentration of sulfate and chloride is slightly improved.
The fluoride ion removal rate reaches more than 99% before and after the comparison treatment, and the three water discharge standards in the surface water environment quality standard are met.
Comparative example 1
The method comprises the following steps of:
(1) Adjusting the pH of the wastewater to 7 by using hydrochloric acid, and measuring the fluoride ion concentration of the wastewater by using an ion selective electrode method (GB 7484-87); (2) Adding 2000ppm of polyaluminium chloride with the alumina content of 13% into the coking wastewater, rapidly stirring for 10min to completely mix, adding PAM at the stirring speed of 170r/min, and precipitating for 30min; (3) The precipitate mixture was filtered through medium speed filter paper, and the fluoride ion concentration of the filtrate was measured by the ion selective electrode method (GB 7484-87), and the fluoride ion removal rate was calculated. The calculation method is the same as in example 1.
The results of treating fluorine-containing wastewater with polyaluminum chloride having an alumina content of 13% in comparative example 1 are shown in Table 3.
TABLE 3 results of treatment of fluorine-containing wastewater with polyaluminum chloride having an alumina content of 13% in comparative example 1
The comparison shows that the treatment effect of the embodiment is obviously better than that of the method for removing fluorine by the polyaluminum chloride coagulation method. The chemical oxygen demand removal rate of the preparation method can reach 99 percent, and the discharge requirement of three types of water in the quality standard of the surface water environment is met, the removal rate of the polyaluminum chloride flocculated fluoride is only about 69 percent, and the discharge requirement cannot be met.
Example 2
The water quality index of the fluorine-containing wastewater II is shown in Table 4.
Table 4 Water quality index of fluorine-containing wastewater II
The modified lignin-based biochar material is prepared by the following method:
(1) Preparing lignin-based biochar raw materials: the method is characterized in that solid residues (UHS) remained after enzymolysis of pretreated corn stalks in bioethanol production are used as raw materials for preparing biochar, and the raw materials comprise the following components: lignin: 40%; silicon: 15%; ash content: 45%; the solid residue was dried at 60 ℃ for 36H, then ground to obtain a powder, the powder was taken up in 80wt.% H 3 PO 4 Soaking in the solution for 10min, and concentrating 25% ZnCl 2 Mixing the solution and soaked powder at a mass ratio of 10:1 for 5h, and drying the obtained mixture at 100 ℃ for 36h to obtain lignin-based biochar raw material (ZnCl) 2 -H 3 PO 4 -UHS co-precipitated feedstock);
（2) Preparing a lignin-based biochar material: placing lignin-based biochar raw materials into a quartz tube reactor for activation and drying, wherein the activation temperature is 400 ℃, the activation time is 30min, the heating rate is 20 ℃/min, and the activation process is carried out in N 2 The preparation method comprises the steps of carrying out under flowing conditions, cooling to 20 ℃ after activation, washing with hydrochloric acid with the concentration of 35% at 40 ℃, washing with deionized water, and drying after washing to obtain the lignin-based biochar material;
(3) Preparing a modified lignin-based biochar material: 124.23g of 100 mu m lignin-based biochar particles are washed and added with 100mL of liquid ferric sulfate Fe 2 (SO 4 ) 3 Soaking the solution for 24 hours, wherein the total iron content in the ferric sulfate solution is 12.1 percent, the pH value is 0.7, stirring is continuously carried out during the soaking process, the rotating speed is set to be 120r/min, and the soaked modified lignin-based biochar material particles are added into 100mLAlCl 3 Soaking in the solution for 28 hours, wherein the content of alumina in aluminum chloride is 7.5%, the pH value is 0.4, stirring is continuously carried out in the soaking process, the rotating speed is set to 120r/min, and the filtered solid particles are washed with water and dried for standby, and the drying temperature is 100 ℃. Measurement of the specific surface area of the sample was 403m 2 /g。
(4) 35% of analytically pure hydrochloric acid is diluted by 15 times, the pH value of the wastewater is adjusted to 6.9 by adding the diluted analytically pure hydrochloric acid into the fluorine-containing wastewater, and the concentration of fluorine ions in the wastewater is determined to be 31.5mg/L by using an ion selective electrode method (GB 7484-87).
(5) Weighing 1.575g of modified lignin-based biochar, adding the modified lignin-based biochar into 1L of second fluorine-containing wastewater, stirring for 10min for complete mixing, adding 0.3g of polyaluminium chloride into the second fluorine-containing wastewater, stirring for 15min for complete mixing, stirring at a speed of 150r/min, and precipitating for 40min.
(6) The mixture of modified lignin-based biochar and desulfurization wastewater is filtered and modified by medium-speed filter paper, and the fluoride ion concentration of the filtrate is measured by an ion selective electrode method (GB 7484-87) to calculate the fluoride ion removal rate. The calculation method is the same as in example 1.
The results of wastewater treatment using the modified lignin-based charcoal material prepared in example 2 are shown in Table 5.
TABLE 5 results after wastewater treatment with modified lignin-based biochar material prepared in example 2
By comparing the wastewater indexes before and after treatment, the treatment method can find out the Chemical Oxygen Demand (COD), the 5-day biochemical oxygen demand (BOD 5), the total carbon (TOC) and the ammonia Nitrogen (NH) 4 N) and Total Nitrogen (TN) are removed to different degrees, the first three removal rates can reach more than 40 percent, and the sulfate and chloride contents are improved to a certain extent.
The removal rate of the fluoride ions reaches 99% before and after the comparison treatment, and the fluoride ions reach three water standards in the surface water environment quality standard after the treatment.
Comparative example 2
And (3) removing fluorine from the fluorine-containing wastewater by using polyaluminium chloride with the alumina content of 13%, wherein the method comprises the following steps:
(1) Adjusting pH of the fluorine-containing wastewater to 6-7 by utilizing hydrochloric acid, and measuring the concentration of fluorine ions in the wastewater by utilizing an ion selective electrode method (GB 7484-87); (2) Adding 3000ppm of polyaluminum chloride with the alumina content of 13% into the coking wastewater, rapidly stirring for 10min to completely mix, stirring at the speed of 170r/min, adding the polyacrylamide, and precipitating for 30min. (3) The precipitate mixture was filtered through medium speed filter paper, and the fluoride ion concentration of the filtrate was measured by the ion selective electrode method (GB 7484-87), and the fluoride ion removal rate was calculated. The calculation method is the same as in example 1.
The results of treating fluorine-containing wastewater with polyaluminum chloride having an alumina content of 13% in comparative example 2 are shown in Table 6.
TABLE 6 results of treatment of fluorine-containing wastewater with polyaluminum chloride having an alumina content of 13% in comparative example 2
Example 3
The water quality index of the fluorine-containing wastewater III is shown in Table 7.
Table 7 Water quality index of fluorine-containing wastewater III
The modified lignin-based biochar material is prepared by the following method:
(1) Preparing lignin-based biochar raw materials: the method is characterized by preparing biochar from solid residues remained after enzymolysis of pretreated corn stalks in bioethanol production, wherein the components of the raw materials are as follows: lignin: 60 percent; silicon: 5%; ash content: 35%; the solid residue was dried at 70 ℃ for 60H, then ground to obtain a powder, the powder was taken up in 90wt.% H 3 PO 4 Soaking in water for 20min, and concentrating to 30% ZnCl 2 Mixing the solution and soaked powder for 10 hours according to the mass ratio of 10:1, and adding ZnCl 2 Mixing the solution with the soaked powder completely for 10 hours, and drying the obtained mixture at 120 ℃ for 60 hours to obtain lignin-based biochar raw materials;
(2) Preparing a lignin-based biochar material: placing lignin-based biochar raw materials into a quartz tube reactor for activation and drying, wherein the activation temperature is 600 ℃, the activation time is 90min, the heating rate is 125 ℃/min, and the activation process is carried out in N 2 The preparation method comprises the steps of carrying out under flowing conditions, cooling to 30 ℃ after activation, washing with hydrochloric acid with the concentration of 35% at 60 ℃, washing with deionized water, and drying after washing to obtain the lignin-based biochar material;
(3) Preparing a modified lignin-based biochar material: 200 mu m lignin-based biochar particles (125.73 g) are washed and then 100mL of liquid ferric sulfate Fe is added 2 (SO 4 ) 3 The solution is soaked for 28 hours, the total iron content in the ferric sulfate solution is 12.3 percent, the PH value is 0.5, and the stirring is continuously carried out in the soaking process, and the rotating speed is set to be 120r/min. Adding the soaked modified lignin-based biochar material particles into 100mLAlCl 3 Soaking in the solution for 28 hours, wherein the alumina content in the aluminum chloride is 6%, and the PH value is 2. Stirring is continuously carried out in the soaking process, the rotating speed is set to 120r/min, and the filtered solid particles are washed with water and dried for standby, and the drying temperature is 120 ℃. Measurement of specific surface area of 363m 2 /g。
(4) 35% of analytically pure hydrochloric acid is diluted by 15 times, the pH value of the wastewater is adjusted to 6.78 by adding the diluted analytically pure hydrochloric acid into the fluorine-containing wastewater III, and the concentration of fluorine ions in the wastewater is measured to be 12.9mg/L by using an ion selective electrode method (GB 7484-87).
(5) Weighing 1.29g of modified lignin-based biochar, adding the modified lignin-based biochar into 1L of fluorine-containing wastewater III, stirring for 8min for complete mixing, adding 0.1g of polyaluminium chloride into the fluorine-containing wastewater III, stirring for 10min for complete mixing, stirring at a speed of 150r/min, and precipitating for 40min.
(6) The mixture of modified lignin-based biochar and desulfurization wastewater is filtered and modified by medium-speed filter paper, and the fluoride ion concentration of the filtrate is measured by an ion selective electrode method (GB 7484-87) to calculate the fluoride ion removal rate. The calculation method is the same as in example 1.
The results of treating the fluorine-containing wastewater with the modified lignin-based charcoal material prepared in example 3 are shown in Table 8.
TABLE 8 results after treatment of fluorine-containing wastewater with modified lignin-based charcoal material prepared in example 3
By comparing the indexes of the wastewater before and after treatment, the treatment method can be used for removing various pollution indexes such as Chemical Oxygen Demand (COD), total Carbon (TC) and Total Nitrogen (TN) to different degrees, and the contents of sulfate and chloride are improved to a certain degree.
The removal rate of fluoride ions reaches more than 99% before and after the treatment by the method.
Comparative example 3
The fluorine-containing wastewater III used in example 3 was defluorinated by polyaluminium chloride having an alumina content of 13%, and the procedure was as follows:
(1) Adjusting the pH value of the desulfurization wastewater to 7 by using hydrochloric acid, and measuring the fluoride ion concentration of the fluoride-containing wastewater by using an ion selective electrode method (GB 7484-87); (2) Adding 900ppm of polyaluminum chloride with the alumina content of 13% into the fluorine-containing wastewater III, rapidly stirring for 10min, completely mixing, stirring at the speed of 170r/min, adding PAM, and precipitating for 30min. (3) The precipitate mixture was filtered through medium speed filter paper, and the fluoride ion concentration of the filtrate was measured by the ion selective electrode method (GB 7484-87), and the fluoride ion removal rate was calculated. The calculation method is the same as in example 1.
The results of treating the fluorine-containing wastewater with polyaluminum chloride having an alumina content of 13% in comparative example 3 are shown in Table 9.
TABLE 9 results after treatment of fluorine-containing wastewater with polyaluminum chloride having an alumina content of 13% in comparative example 3
The comparison shows that the treatment effect of the embodiment is obviously better than that of flocculation defluorination of polyaluminum oxychloride. The fluoride ion removal rate of the embodiment can reach 99 percent, which is 39 percent higher than that of the aluminum polychloride.
The embodiment of the invention can find that the invention has stable effect on fluorine-containing wastewater treatment, more than 99 percent and more than 35 percent better than that of fluoride treated by polyaluminum chloride.
Claims (10)
1. The preparation method of the modified lignin-based biochar material is characterized by comprising the following steps of:
(1) Preparing lignin-based biochar raw materials: preparing biochar from solid residues left after enzymolysis of pretreated corn stalks produced by bioethanol, drying the solid residues at 60-70 ℃ for 36-60 hours, grinding to obtain powder, and mixing the powder with 80-90 wt.% of H 3 PO 4 Soaking in the solution for 10-20 min, and concentrating to obtain ZnCl with concentration of 20-30% 2 Mixing the solution and the soaked powder for 5-10 hours according to a mass ratio of 10:1, and drying the obtained mixture at 100-120 ℃ for 36-60 hours to obtain lignin-based biochar raw materials;
(2) Preparing a lignin-based biochar material: placing lignin-based biochar raw materials into a quartz tube reactor for activation and drying, wherein the activation temperature is 400-600 ℃, the activation time is 30-90 min, the heating rate is 7-125 ℃/min, and the activation process is carried out in N 2 Is carried out under the flowing condition, is cooled to 20-30 ℃ after the activation is finished, is washed at 40-60 ℃ by hydrochloric acid with the concentration of 35 percent,washing with deionized water, and drying after washing to obtain lignin-based biochar material;
(3) Modification of lignin-based biochar materials: screening out 100-200 mu m modified lignin-based biochar material particles, and adding the particles into Fe 2 (SO 4 ) 3 Soaking in the solution for 20-28 h; adding the soaked modified lignin-based biochar material particles into AlCl 3 Soaking the biomass charcoal in the solution for 20-28 h, carrying out suction filtration on the biomass charcoal, and drying the solid particles subjected to suction filtration at 100-120 ℃ to obtain the modified lignin-based biomass charcoal material.
2. The method for preparing the modified lignin-based charcoal material according to claim 1, wherein the solid residue remaining after enzymolysis of the pretreated corn stover in bioethanol production comprises the following components: lignin: 40-60%; silicon: 5-15%; ash content: 35-45%.
3. The method for preparing the modified lignin-based biochar material according to claim 1, wherein the specific surface area of the modified lignin-based biochar is 363-423 m 2 /g。
4. The method for preparing modified lignin-based charcoal material according to claim 1, wherein the Fe 2 (SO 4 ) 3 The mass content of iron element in the solution is 11-13%, and the pH value is 0.5-1.
5. The method for preparing modified lignin-based charcoal material according to claim 1, wherein the AlCl is 3 The mass content of the alumina in the solution is 6-7.5%, and the pH value is 0.4-2.
6. The modified lignin-based biochar material is characterized by being prepared by the preparation method of any one of claims 1-5.
7. Use of the modified lignin-based biochar material according to claim 6 for wastewater defluorination, wherein the modified lignin-based biochar material is used for defluorination of wastewater in a flue gas desulfurization process.
8. The application of the modified lignin-based biochar material in wastewater defluorination according to claim 7, wherein the pH value of the wastewater is adjusted to 6-7 by hydrochloric acid before the defluorination of the wastewater.
9. The application of the modified lignin-based biochar material in wastewater defluorination according to claim 7, wherein the addition amount of the modified lignin-based biochar material in the wastewater is as follows: 50-100 ppm of modified lignin-based biochar material is added into each 1ppm of fluoride in the wastewater.
10. The application of the modified lignin-based biochar material in wastewater defluorination according to claim 7, wherein polyaluminium chloride is added to assist coagulation in the flue gas desulfurization process.
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| CN117756202A (en) * | 2023-12-28 | 2024-03-26 | 上海勘测设计研究院有限公司 | Fluorine removing agent, preparation method and application thereof and fluorine removing device |
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