CN112915973A - Modified fly ash adsorbent and preparation method and application thereof - Google Patents
Modified fly ash adsorbent and preparation method and application thereof Download PDFInfo
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- CN112915973A CN112915973A CN202110115302.3A CN202110115302A CN112915973A CN 112915973 A CN112915973 A CN 112915973A CN 202110115302 A CN202110115302 A CN 202110115302A CN 112915973 A CN112915973 A CN 112915973A
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- Prior art keywords
- fly ash
- modified
- modified fly
- adsorbent
- desulfurization wastewater
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- 239000010881 fly ash Substances 0.000 title claims abstract description 184
- 239000003463 adsorbent Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 48
- 230000023556 desulfurization Effects 0.000 claims abstract description 48
- 239000002351 wastewater Substances 0.000 claims abstract description 48
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000843 powder Substances 0.000 claims abstract description 36
- 238000001179 sorption measurement Methods 0.000 claims abstract description 31
- 239000003513 alkali Substances 0.000 claims abstract description 21
- 229910052742 iron Inorganic materials 0.000 claims abstract description 21
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003546 flue gas Substances 0.000 claims abstract description 20
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 244000276331 Citrus maxima Species 0.000 claims description 33
- 235000001759 Citrus maxima Nutrition 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 26
- 238000001914 filtration Methods 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 22
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 20
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 20
- 239000004571 lime Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- 239000008267 milk Substances 0.000 claims description 18
- 210000004080 milk Anatomy 0.000 claims description 18
- 235000013336 milk Nutrition 0.000 claims description 18
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 16
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 8
- 239000000292 calcium oxide Substances 0.000 claims description 7
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 4
- 238000005189 flocculation Methods 0.000 claims description 4
- 230000016615 flocculation Effects 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 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
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 240000000560 Citrus x paradisi Species 0.000 abstract description 17
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 12
- 150000002500 ions Chemical class 0.000 abstract description 11
- 239000011651 chromium Substances 0.000 abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 9
- 229910052785 arsenic Inorganic materials 0.000 abstract description 9
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 abstract description 9
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052753 mercury Inorganic materials 0.000 abstract description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052804 chromium Inorganic materials 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 8
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052793 cadmium Inorganic materials 0.000 abstract description 6
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000010440 gypsum Substances 0.000 abstract description 6
- 229910052602 gypsum Inorganic materials 0.000 abstract description 6
- 229910052759 nickel Inorganic materials 0.000 abstract description 6
- 238000003908 quality control method Methods 0.000 abstract description 3
- 238000012544 monitoring process Methods 0.000 abstract description 2
- -1 fluoride ions Chemical class 0.000 description 10
- 238000007873 sieving Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 235000012255 calcium oxide Nutrition 0.000 description 6
- 239000010883 coal ash Substances 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000010802 sludge Substances 0.000 description 5
- 239000002910 solid waste Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000012798 spherical particle Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 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 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910020489 SiO3 Inorganic materials 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 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 class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical group 0.000 description 1
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910021489 α-quartz Inorganic materials 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
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
-
- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- C02F2101/101—Sulfur compounds
-
- 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
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- 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
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- 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
Abstract
The invention provides a modified fly ash adsorbent and a preparation method and application thereof, and relates to the technical field of adsorption. The modified fly ash adsorbent provided by the invention comprises the following components in parts by weight: 50-60 parts of alkali modified fly ash, 30-40 parts of iron modified fly ash and 8-12 parts of modified pomelo peel powder. The modified fly ash adsorbent prepared by the invention can be used for treating flue gas desulfurization wastewater, has good adsorption and removal effects on fluoride, chloride ions, sulfide, mercury, lead, nickel, arsenic, cadmium, chromium and other heavy metal ions in the flue gas desulfurization wastewater, and ensures that the treated water quality meets the standard requirements of the outlet monitoring project of a desulfurization wastewater treatment system in limestone-gypsum wet desulfurization wastewater quality control index of thermal power plant (DL/T997-.
Description
Technical Field
The invention relates to the technical field of adsorption, in particular to a modified fly ash adsorbent and a preparation method and application thereof.
Background
The flue gas desulfurization wastewater of the coal-fired power plant is mainly the discharge water of an absorption tower in the wet desulfurization (limestone/gypsum method) process of boiler flue gas. In order to maintain the balance of the materials of the slurry circulation system of the desulfurization device and ensure the quality of gypsum, when the concentration of chloride ions in the slurry exceeds a specified value, a certain amount of waste water is discharged from the system, and the waste water mainly comes from a gypsum dehydration and cleaning system. The desulfurization wastewater is weakly acidic, the pH value is 4-6, and the impurities mainly comprise suspended matters, supersaturated sulfite, sulfate, chloride ions, fluoride ions, and heavy metal ions such as mercury, lead, nickel, arsenic, cadmium, chromium and the like, wherein a lot of the impurities are first pollutants which are strictly controlled in the national environmental protection standard.
The existing common desulfurization wastewater treatment system of a domestic coal-fired power plant mainly comprises a wastewater pond, a triple box (a combined name of a pH adjusting tank, a settling tank and a flocculation tank), a clarifier, a clean water pond, a sludge treatment device, a dosing device and the like, and the main principle of the system is that the desulfurization wastewater is neutralized by adding alkali, organic sulfide and heavy metal are added to generate precipitate, a flocculating agent is added to concentrate the precipitate into sludge, and then the sludge is compressed into a sludge cake to be transported outside. After the method is adopted for treatment, the pH value and suspended matters of the wastewater can basically reach the standard, but heavy metal ions in the wastewater cannot reach the standard, the concentrations of fluorine ions and chlorine ions are still very high, the standard discharge and the recycling of the wastewater are limited, a large amount of chemical agents are consumed, and the generated sludge containing heavy metals still faces the problem of difficult disposal.
On the basis, some advanced treatment technologies, such as crystallization technology, evaporation concentration technology, membrane concentration technology and the like, are developed, the technologies have the defects of high investment cost, high operation cost, high failure rate and low availability, and the generated miscellaneous salt containing heavy metals is also difficult to dispose. At present, effective treatment and standard discharge of desulfurization waste water still are a great problem faced by coal-fired power plants.
Fly ash, also known as fly ash or fly ash, is a tiny soot particle discharged from coal combustion. Due to the action of surface tension, most of the fly ash is spherical, the surface is smooth, and micropores are small; some of the particles are adhered by colliding with each other in a molten state, and thus, they become honeycomb-shaped composite particles having rough surfaces and many edges.
At present, many studies have been made on the use of fly ash as wastewater treatment, and for the treatment of desulfurization wastewater, fly ash can be used for filter-aid removal of most suspended matters, and has a certain adsorption removal effect on fluoride, chloride ions, sulfide, and heavy metal ions such as mercury, lead, nickel, arsenic, cadmium, and chromium, but unmodified fly ash has a low adsorption removal rate on these ions, and especially has a poor adsorption removal effect on fluoride, chloride ions, and arsenic and chromium ions mainly existing in the form of anions. Therefore, the fly ash needs to be modified to improve the adsorption removal efficiency of the ions, so that the flue gas desulfurization wastewater which is difficult to treat in the coal-fired power plant can be deeply treated by using the solid waste fly ash generated by the coal-fired power plant, the waste is treated by the waste, and the desulfurization wastewater can reach the standard for discharge or recycling.
Disclosure of Invention
The invention mainly aims to provide a modified fly ash adsorbent and a preparation method and application thereof, and aims to solve the problem that the adsorption removal effect of fluoride, chloride ions, sulfide, mercury, lead, nickel, arsenic, cadmium, chromium and other heavy metal ions in the flue gas desulfurization wastewater is poor at present.
In order to achieve the above purpose, in a first aspect, the present invention provides a modified fly ash adsorbent, which comprises the following components in parts by weight: 50-60 parts of alkali modified fly ash, 30-40 parts of iron modified fly ash and 8-12 parts of modified pomelo peel powder,
the preparation method of the alkali modified fly ash comprises the following steps: mixing and dipping the fly ash and lime milk, and filtering, drying and crushing to obtain the alkali modified fly ash;
according to the technical scheme, lime milk is formed after slaking quicklime, on one hand, lime particles form a calcium hydroxide colloid structure, the particle size is about 1 mu m, and the specific surface area reaches 10-30 m2The water-soluble organic silicon compound is attached to the surface of the fly ash and is beneficial to adsorbing and removing heavy metal cations; on the other hand, the lime has strong alkalinity, and can exist with SiO in the fly ash in a vitreous phase and crystal minerals such as alpha-quartz, mullite and the like at normal temperature2、Al2O3The active substances are subjected to chemical reaction to generate-SiO3 2-、-AlO2 -And the plasma group provides an ion exchange active group for the chemical adsorption removal of anions in the wastewater.
The preparation method of the iron modified fly ash comprises the following steps: dissolving ferric salt in water to form a ferric salt solution, heating to 80-100 ℃, adding fly ash into the ferric salt solution, mixing and dipping, cooling, filtering, drying and crushing to obtain the iron-modified fly ash;
in the technical scheme of the invention, ferric salt is adopted to modify the fly ash, and ferric salt reacts with active substances of the fly ash under certain conditions to form iron substances and groups with various forms on the surface of the fly ash. Wherein, part of the waste water is amorphous ferrosilicous mineral, the microstructure is loose, the specific surface area is extremely large, and the waste water can react with Cr (VI), As (III) and As (V) in the waste water to generate chemical adsorption and surface precipitation to be removed; a large number of-OH groups are formed on the surface of the fly ash, so that heavy metal cations can be adsorbed and removed; ferric ions can perform a complex reaction with fluoride ions so as to adsorb and remove the fluoride ions.
The preparation method of the modified pomelo peel powder comprises the following steps: the preparation method comprises the steps of drying and crushing shaddock peel to obtain shaddock peel powder, adding the shaddock peel powder into a hydrochloric acid solution, uniformly mixing, cooling after heating reaction, filtering, drying and crushing to obtain the modified shaddock peel powder.
The shaddock peel has a compact fibrous tissue structure, a large number of pores exist in the shaddock peel, the pore sizes are different, the general macropore is 2-20 mu m, the wall thickness of a pore canal is about 2 mu m, and some pores are arrangedThe fiber is compact, some are loose in arrangement and are in a honeycomb shape, and some display a large amount of fiber tissues and micropores. The shaddock peel is rich in cellulose, hemicellulose, lignin and the like, has high pectin content, contains 50-70% of insoluble components by mass, and also contains water-soluble components such as glucose, fructose, sucrose, xylose and the like, so that a large number of functional groups such as hydroxyl, carbonyl, aldehyde, carboxyl and the like exist in the shaddock peel, and the functional groups can perform complexation, electrostatic adsorption and the like. The pericarpium Citri Grandis can release K+、Ca2+、Na+Plasma metal ions which can perform ion exchange with heavy metal cations in the wastewater; hydroxyl, amino, carbonyl, carboxyl, phosphate ester or sulfate ester and other active groups in the shaddock peel play an important role in adsorbing various ions in water; and the surface of the shaddock peel has amphiphilic behavior, can adsorb cations and anions in water at the same time, and is favorable for treating various complex polluted anions and cations in the desulfurization wastewater.
According to the technical scheme, the surface treatment of the shaddock peel is carried out by using the hydrochloric acid solution at a certain temperature, so that the surface microstructure of the shaddock peel can be improved, a large number of rich gaps are formed, and rich active groups on the shaddock peel are reserved; meanwhile, part of the chloride ions retained on the surface of the pomelo peel powder can provide adsorption exchange sites for Cr (VI), As (III), As (V) and other ions existing in the form of anions in the wastewater.
The modified fly ash adsorbent prepared by the invention mainly utilizes the byproduct solid waste fly ash produced by a coal-fired power plant as a wastewater treatment adsorbent, has rich raw material sources, low cost, inexhaustibility and realization of secondary utilization of solid waste; the prepared modified fly ash adsorbent has good adsorption and removal effects on fluoride, chloride ions, sulfide, mercury, lead, nickel, arsenic, cadmium, chromium and other heavy metal ions in flue gas desulfurization wastewater.
As a preferred embodiment of the modified fly ash adsorbent of the present invention, in the process of preparing the alkali-modified fly ash and/or the iron-modified fly ash, the particle size of the fly ash is 200-650 meshes.
Technical scheme of the inventionIn the method, 650-mesh fine fly ash with the particle size of 200-650 meshes is used as a raw material, and compared with the common fly ash, the fine fly ash has the advantages of smooth surface, regular shape, more spherical shape, small water demand, fine particles, large specific surface area, good adsorption effect and silicon oxide (SiO)2) And alumina (Al)2O3) The content of the fly ash is higher than that of the common fly ash, the fly ash is easy to dissolve out, and the chemical activity is strong.
As a preferable embodiment of the modified fly ash adsorbent, in the process of preparing the alkali modified fly ash, the mass concentration of the lime milk is 5-10% calculated by calcium oxide, and the addition amount of the fly ash in the lime milk is 0.5-1 kg/L.
As a preferred embodiment of the modified fly ash adsorbent of the present invention, in the process of preparing the iron-modified fly ash, the mass fraction of the ferric salt in the ferric salt solution is 1 to 5%, and the addition amount of the fly ash in the ferric salt solution is 0.5 to 1 kg/L.
As a preferred embodiment of the modified fly ash adsorbent of the present invention, in the process of preparing the iron-modified fly ash, the ferric salt includes any one or both of ferric chloride and ferric sulfate.
As a preferable embodiment of the modified fly ash adsorbent of the present invention, the concentration of the hydrochloric acid solution in the process of preparing the modified pomelo peel powder is 0.1-0.2 mol/L.
As a preferred embodiment of the preparation method of the modified fly ash adsorbent, the temperature of mixing and granulating in the process of preparing the modified pomelo peel powder is 65-85 ℃.
In a second aspect, the present invention also provides a method for preparing a modified fly ash adsorbent, the method comprising: and mixing and granulating the alkali modified fly ash, the iron modified fly ash and the modified pomelo peel powder to obtain the modified fly ash adsorbent.
In a third aspect, the invention further provides an application of the modified fly ash adsorbent, such as the application of the modified fly ash adsorbent in flue gas desulfurization wastewater treatment.
In a fourth aspect, the invention further provides a flue gas desulfurization wastewater treatment method, which is characterized by comprising the following steps:
(1) adsorption and filtration treatment of fly ash: introducing desulfurization wastewater with suspended matter concentration less than or equal to 100mg/L after neutralization, flocculation and precipitation pretreatment into a reaction tank, adding fly ash into the reaction tank, wherein the particle size of the fly ash is 200-650 meshes, and the adding amount of the fly ash is 1-5 kg/m3Uniformly stirring and mixing the fly ash and the desulfurization wastewater, enabling the fly ash to be in a suspension state, treating for 1-2 hours, and filtering after the treatment;
(2) treating the modified fly ash adsorbent: introducing the filtered desulfurization wastewater into an adsorption tower, filling the modified fly ash adsorbent into the adsorption tower, and allowing the desulfurization wastewater to flow through the adsorption tower to obtain the deep treatment water.
The flue gas desulfurization wastewater treatment process is simple, strong in practicability and high in reliability, can ensure normal production of a coal-fired power plant to the maximum extent, and reduces the operation cost, the labor cost and the environmental protection cost of the coal-fired power plant.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the technical scheme, the coal ash is subjected to alkali modification treatment and iron modification treatment respectively, the prepared alkali modified coal ash, iron modified coal ash and modified pomelo peel powder are mixed to prepare the modified coal ash adsorbent, the modified coal ash adsorbent is used for treating flue gas desulfurization wastewater, and the prepared modified coal ash adsorbent has a good adsorption removal effect on fluoride, chloride ions, sulfide, mercury, lead, nickel, arsenic, cadmium, chromium and other heavy metal ions in the flue gas desulfurization wastewater, so that the treated water quality meets the standard requirements of an outlet monitoring project of a desulfurization wastewater treatment system in the thermal power plant limestone-gypsum wet desulfurization wastewater quality control index (DL/T997-2006).
(2) The modified fly ash adsorbent prepared by the invention mainly utilizes the byproduct solid waste fly ash produced by a coal-fired power plant as a wastewater treatment adsorbent, has rich raw material sources, low cost, inexhaustibility and realization of secondary utilization of solid waste.
(3) The flue gas desulfurization wastewater treatment process is simple, strong in practicability and high in reliability, can ensure normal production of a coal-fired power plant to the maximum extent, and reduces the operation cost, the labor cost and the environmental protection cost of the coal-fired power plant.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
Example 1
The preparation of the modified fly ash adsorbent comprises the following steps:
(1) mixing the fly ash and lime milk at normal temperature, soaking for 24h, filtering, drying and crushing to obtain alkali modified fly ash;
(2) preparing iron modified fly ash: heating the ferric chloride solution to 80-100 ℃, adding the fly ash into the ferric chloride solution, mixing and soaking for 30min, cooling, filtering, drying and crushing to obtain iron modified fly ash;
(3) preparing modified pomelo peel powder: drying fresh shaddock peel at 85 ℃, then crushing, sieving by a 40-mesh sieve to obtain shaddock peel powder with the particle size of less than or equal to 0.42mm, adding the shaddock peel powder into a hydrochloric acid solution, uniformly mixing, heating at 120 ℃ for 2h, cooling after reaction, washing with water, filtering, drying at 85 ℃, then crushing, and sieving by the 40-mesh sieve to obtain particles with the particle size of less than or equal to 0.42mm, namely modified shaddock peel powder;
(4) preparing a modified fly ash adsorbent: mixing 60 parts by weight of alkali modified fly ash, 30 parts by weight of iron modified fly ash and 12 parts by weight of modified pomelo peel powder, and granulating and molding to obtain the modified fly ash adsorbent.
In this embodiment, the fly ash in step (1) and step (2) is fine fly ash with a particle size of less than or equal to 20 μm, which is obtained by sieving a 625-mesh sieve;
in the step (1), the mass fraction of calcium oxide in the lime milk is 10%, and the addition amount of the fine fly ash in the lime milk is 1 kg/L; in the step (2), the mass fraction of ferric chloride in the ferric chloride solution is 5%, and the addition amount of the fine fly ash in the ferric chloride solution is 1 kg/L;
in the step (3), the concentration of the hydrochloric acid solution is 0.2 mol/L;
in the step (4), the temperature of mixing granulation is 85 ℃, and the prepared modified fly ash adsorbent is spherical particles with the diameter of 2-3 cm.
Example 2
The preparation of the modified fly ash adsorbent comprises the following steps:
(1) mixing the fly ash and lime milk at normal temperature, soaking for 20h, filtering, drying and crushing to obtain alkali modified fly ash;
(2) preparing iron modified fly ash: heating the ferric chloride solution to 80-100 ℃, adding the fly ash into the ferric chloride solution, mixing and soaking for 20min, cooling, filtering, drying and crushing to obtain iron modified fly ash;
(3) preparing modified pomelo peel powder: drying fresh shaddock peel at 95 ℃, then crushing, sieving by a 40-mesh sieve to obtain shaddock peel powder with the particle size of less than or equal to 0.42mm, adding the shaddock peel powder into a hydrochloric acid solution, uniformly mixing, heating at 140 ℃ for 1.5h, cooling, washing, filtering after reaction, drying at 95 ℃, then crushing, sieving by the 40-mesh sieve to obtain particles with the particle size of less than or equal to 0.42mm, namely modified shaddock peel powder;
(4) preparing a modified fly ash adsorbent: mixing 55 parts by weight of alkali modified fly ash, 35 parts by weight of iron modified fly ash and 10 parts by weight of modified pomelo peel powder, and granulating and molding to obtain the modified fly ash adsorbent.
In this embodiment, the fly ash in step (1) and step (2) is fine fly ash with a particle size of 45 μm or less, which is obtained by sieving with a 325-mesh sieve;
in the step (1), the mass fraction of calcium oxide in the lime milk is 8%, and the addition amount of the fine fly ash in the lime milk is 1 kg/L; in the step (2), the mass fraction of ferric chloride in the ferric chloride solution is 3%, and the addition amount of the fine fly ash in the ferric chloride solution is 1 kg/L;
in the step (3), the concentration of the hydrochloric acid solution is 0.15 mol/L;
in the step (4), the temperature of mixing granulation is 75 ℃, and the prepared modified fly ash adsorbent is spherical particles with the diameter of 2-3 cm.
Example 3
The preparation of the modified fly ash adsorbent comprises the following steps:
(1) mixing the fly ash and lime milk at normal temperature, soaking for 24h, filtering, drying and crushing to obtain alkali modified fly ash;
(2) preparing iron modified fly ash: heating the ferric chloride solution to 80-100 ℃, adding the fly ash into the ferric sulfate solution, mixing and soaking for 30min, cooling, filtering, drying and crushing to obtain iron modified fly ash;
(3) preparing modified pomelo peel powder: drying fresh shaddock peel at 105 ℃, then crushing, sieving by a 40-mesh sieve to obtain shaddock peel powder with the particle size of less than or equal to 0.42mm, adding the shaddock peel powder into a hydrochloric acid solution, uniformly mixing, heating at 160 ℃ for 2h, cooling, washing with water, filtering after reaction, drying at 105 ℃, then crushing, and sieving by the 40-mesh sieve to obtain particles with the particle size of less than or equal to 0.42mm, namely modified shaddock peel powder;
(4) preparing a modified fly ash adsorbent: mixing 50 parts by weight of alkali modified fly ash, 40 parts by weight of iron modified fly ash and 8 parts by weight of modified pomelo peel powder, and granulating and molding to obtain the modified fly ash adsorbent.
In this embodiment, the fly ash in step (1) and step (2) is fine fly ash with a particle size of 74 μm or less obtained by sieving with a 200-mesh sieve;
in the step (1), the mass fraction of calcium oxide in the lime milk is 5%, and the addition amount of the fine fly ash in the lime milk is 1 kg/L; in the step (2), the mass fraction of ferric chloride in the ferric chloride solution is 5%, and the addition amount of the fine fly ash in the ferric chloride solution is 1 kg/L;
in the step (3), the concentration of the hydrochloric acid solution is 0.1 mol/L;
in the step (4), the temperature of mixing granulation is 65 ℃, and the prepared modified fly ash adsorbent is spherical particles with the diameter of 2-3 cm.
Example 4
The difference between this example and example 1 is that the raw materials for preparing the modified fly ash adsorbent in step (4) of this example include: 45 parts of alkali modified fly ash, 45 parts of iron modified fly ash and 10 parts of modified pomelo peel powder.
Example 5
The difference between this example and example 1 is that the particle size of the fly ash in step (1) and step (2) is not less than 20 μm.
Example 6
The difference between the present example and example 1 is that in step (1) of the present example, the mass fraction of calcium oxide in the lime milk is 3%, and the addition amount of the fine fly ash in the lime milk is 1.5 kg/L.
The modified fly ash adsorbent prepared in examples 1 to 6 was used for treating flue gas desulfurization wastewater of a coal fired power plant, and the flue gas desulfurization wastewater treatment included fly ash adsorption filtration treatment and modified fly ash adsorption treatment performed in sequence. Wherein the fly ash adsorption filtration treatment step is to introduce desulfurization wastewater with suspended matter concentration less than or equal to 100mg/L and chemical oxygen demand less than or equal to 150mg/L, pH 6-9 after pretreatment such as neutralization, flocculation, precipitation and the like into a reaction tank, and to add 3.5kg/m of fly ash into the tank3Stirring in the tank to uniformly mix the fly ash and the desulfurization wastewater, enabling the fly ash to be in a suspended state, filtering after treatment, and recording the filtered wastewater as first-stage desulfurization wastewater;
the modified fly ash adsorbent treatment step is to introduce the desulfurization wastewater (namely, the first-stage desulfurization wastewater) treated by the fly ash adsorption filtration treatment step into an adsorption tower, fill the modified fly ash adsorbent in the adsorption tower, flow the desulfurization wastewater through the adsorption tower for advanced treatment, and mark the treated water as second-stage desulfurization wastewater (namely, outlet concentration). And (3) detecting the concentration of substances such as heavy metal elements, suspended matters and the like contained in the second-stage desulfurization wastewater, and comparing the detection result with the most allowable discharge concentration in a limestone-gypsum wet desulphurization wastewater quality control index (DL/T997-2006) of a thermal power plant. The results of wastewater treatment of the modified fly ash adsorbents prepared in examples 1 to 6 are shown in Table 1.
TABLE 1 results of wastewater treatment of modified fly ash adsorbents prepared in examples 1-6
As can be seen from the data in Table 1, the modified fly ash adsorbents prepared in examples 1-6 can achieve the emission standard specified in DL/T997-. However, the modified fly ash adsorbents prepared in examples 4 to 5 exhibited a relatively low degree of purification by adsorption of wastewater as compared to examples 1 to 3.
Comparative example 1
The difference between this example and example 1 is that in step (1), no alkali modification treatment is performed on the fly ash, i.e., the alkali-modified fly ash is replaced by unmodified fly ash.
Comparative example 2
The difference between this example and example 1 is that in step (2), no iron modification treatment is performed on the fly ash, i.e., the iron-modified fly ash is replaced by unmodified fly ash.
Comparative example 3
This example differs from example 1 in that no modified grapefruit peel powder was added in step (4).
The modified fly ash adsorbents prepared in comparative examples 1 to 3 were tested by the same test method as in example 1, and the test results are shown in table 2.
TABLE 2 results of wastewater treatment of the modified fly ash adsorbents prepared in comparative examples 1 to 3
As can be seen from table 2, in comparative example 1, the fly ash is not subjected to alkali modification treatment, and the prepared fly ash adsorbent has large residual amounts of mercury, fluoride, sulfide and fluoride ions in the water body after being used for flue gas desulfurization wastewater treatment; in the comparative example 2, the fly ash is not subjected to iron modification treatment, and the prepared fly ash adsorbent has larger residual amounts of mercury, chromium, arsenic and fluoride in water after being used for flue gas desulfurization wastewater treatment; in the comparative example 3, modified pomelo peel powder is not added, and the prepared fly ash adsorbent has larger residual quantity of mercury, chromium, arsenic and fluoride in water after being used for flue gas desulfurization wastewater treatment.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (9)
1. The modified fly ash adsorbent is characterized by comprising the following components in parts by weight: 50-60 parts of alkali modified fly ash, 30-40 parts of iron modified fly ash and 8-12 parts of modified pomelo peel powder,
the preparation method of the alkali modified fly ash comprises the following steps: mixing and dipping the fly ash and lime milk, and filtering, drying and crushing to obtain the alkali modified fly ash;
the preparation method of the iron modified fly ash comprises the following steps: dissolving ferric salt in water to form a ferric salt solution, heating to 80-100 ℃, adding fly ash into the ferric salt solution, mixing and dipping, cooling, filtering, drying and crushing to obtain the iron-modified fly ash;
the preparation method of the modified pomelo peel powder comprises the following steps: the preparation method comprises the steps of drying and crushing shaddock peel to obtain shaddock peel powder, adding the shaddock peel powder into a hydrochloric acid solution, uniformly mixing, cooling after heating reaction, filtering, drying and crushing to obtain the modified shaddock peel powder.
2. The modified fly ash adsorbent of claim 1, wherein the particle size of fly ash is 200-650 mesh during the preparation of the alkali-modified fly ash and/or the iron-modified fly ash.
3. The modified fly ash adsorbent of claim 1, wherein in the process of preparing the alkali-modified fly ash, the mass concentration of the lime milk is 5-10% by weight of calcium oxide, and the addition amount of the fly ash in the lime milk is 0.5-1 kg/L.
4. The modified fly ash adsorbent of claim 1, wherein in the process of preparing the iron-modified fly ash, the mass fraction of the ferric salt in the ferric salt solution is 1-5%, and the addition amount of the fly ash in the ferric salt solution is 0.5-1 kg/L.
5. The modified fly ash adsorbent of claim 1, wherein the ferric salt comprises either or both of ferric chloride and ferric sulfate during the preparation of the iron-modified fly ash.
6. The modified fly ash adsorbent according to claim 1, wherein the concentration of the hydrochloric acid solution in the process of preparing the modified pomelo peel powder is 0.1 to 0.2 mol/L.
7. The method for preparing the modified fly ash adsorbent according to any one of claims 1 to 6, wherein the modified fly ash adsorbent is obtained by mixing and granulating the alkali-modified fly ash, the iron-modified fly ash and the modified pomelo peel powder.
8. Use of a modified fly ash adsorbent according to any one of claims 1 to 6 in flue gas desulfurization wastewater treatment.
9. The flue gas desulfurization wastewater treatment method is characterized by comprising the following steps of:
(1) adsorption and filtration treatment of fly ash: introducing desulfurization wastewater with suspended matter concentration less than or equal to 100mg/L after neutralization, flocculation and precipitation pretreatment into a reaction tank, adding fly ash into the reaction tank, wherein the particle size of the fly ash is 200-650 meshes, and the adding amount of the fly ash is 1-5 kg/m3Uniformly stirring and mixing the fly ash and the desulfurization wastewater, enabling the fly ash to be in a suspension state, treating for 1-2 hours, and filtering after the treatment;
(2) treating the modified fly ash adsorbent: introducing the filtered desulfurization waste water into an adsorption tower, filling the modified fly ash adsorbent in any one of claims 1-6 in the adsorption tower, and allowing the desulfurization waste water to flow through the adsorption tower to obtain the deep-treated water.
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