CN116251563A - Preparation method of coal coking industrial wastewater purifying agent based on modified zeolite - Google Patents
Preparation method of coal coking industrial wastewater purifying agent based on modified zeolite Download PDFInfo
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- CN116251563A CN116251563A CN202211724167.3A CN202211724167A CN116251563A CN 116251563 A CN116251563 A CN 116251563A CN 202211724167 A CN202211724167 A CN 202211724167A CN 116251563 A CN116251563 A CN 116251563A
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- zeolite
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- deionized water
- filtering
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 237
- 239000012629 purifying agent Substances 0.000 title claims abstract description 55
- 238000004939 coking Methods 0.000 title claims abstract description 40
- 239000003245 coal Substances 0.000 title claims abstract description 30
- 239000010842 industrial wastewater Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 177
- 239000010457 zeolite Substances 0.000 claims abstract description 177
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 133
- 230000001699 photocatalysis Effects 0.000 claims abstract description 93
- 239000002245 particle Substances 0.000 claims abstract description 84
- 239000011246 composite particle Substances 0.000 claims abstract description 72
- 229910001868 water Inorganic materials 0.000 claims abstract description 38
- 239000002131 composite material Substances 0.000 claims abstract description 36
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 32
- 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 abstract description 28
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims abstract description 28
- 230000004048 modification Effects 0.000 claims abstract description 16
- 238000012986 modification Methods 0.000 claims abstract description 16
- 238000007781 pre-processing Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000008367 deionised water Substances 0.000 claims description 83
- 229910021641 deionized water Inorganic materials 0.000 claims description 83
- 238000001914 filtration Methods 0.000 claims description 76
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 69
- 238000002791 soaking Methods 0.000 claims description 56
- 238000001035 drying Methods 0.000 claims description 54
- 239000000203 mixture Substances 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- 239000006185 dispersion Substances 0.000 claims description 40
- 238000009210 therapy by ultrasound Methods 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 27
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- 238000004140 cleaning Methods 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 22
- OVBPIULPVIDEAO-LBPRGKRZSA-N folic acid Chemical compound C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-LBPRGKRZSA-N 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- 229910052717 sulfur Inorganic materials 0.000 claims description 22
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 22
- 229910052799 carbon Inorganic materials 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- 238000000502 dialysis Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- -1 polytetrafluoroethylene Polymers 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 17
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 13
- 239000012153 distilled water Substances 0.000 claims description 12
- 239000011780 sodium chloride Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 11
- OVBPIULPVIDEAO-UHFFFAOYSA-N N-Pteroyl-L-glutaminsaeure Natural products C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)NC(CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-UHFFFAOYSA-N 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 11
- 229960000304 folic acid Drugs 0.000 claims description 11
- 235000019152 folic acid Nutrition 0.000 claims description 11
- 239000011724 folic acid Substances 0.000 claims description 11
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 10
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 10
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 10
- 238000004108 freeze drying Methods 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000012528 membrane Substances 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- 230000000694 effects Effects 0.000 abstract description 20
- 238000001179 sorption measurement Methods 0.000 abstract description 17
- 238000013329 compounding Methods 0.000 abstract description 9
- 238000010525 oxidative degradation reaction Methods 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 75
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 239000002351 wastewater Substances 0.000 description 8
- 239000011148 porous material Substances 0.000 description 7
- 238000004065 wastewater treatment Methods 0.000 description 7
- 238000002386 leaching Methods 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000000593 degrading effect Effects 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 230000010718 Oxidation Activity Effects 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229960000892 attapulgite Drugs 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052625 palygorskite Inorganic materials 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 238000002306 biochemical method Methods 0.000 description 1
- 239000011575 calcium Substances 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
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000010351 charge transfer process Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 description 1
- 229940061634 magnesium sulfate heptahydrate Drugs 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- GNHOJBNSNUXZQA-UHFFFAOYSA-J potassium aluminium sulfate dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GNHOJBNSNUXZQA-UHFFFAOYSA-J 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
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000011206 ternary composite Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
Images
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- 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
- B01J20/16—Alumino-silicates
- B01J20/165—Natural alumino-silicates, e.g. zeolites
-
- 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
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F2101/30—Organic compounds
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Analytical Chemistry (AREA)
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- Health & Medical Sciences (AREA)
- Toxicology (AREA)
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Abstract
The invention discloses a preparation method of a coal coking industrial wastewater purifying agent based on modified zeolite, which comprises the following steps of: s1, preprocessing natural zeolite; s2, modification of Fe 3 O 4 ‑CeO 2 Composite particles; s3, grafting photocatalytic particles to obtain composite modified zeolite; s4, mixing the composite modified zeolite with polymeric ferric sulfate and polymeric aluminum chloride to obtain the water purifying agent. The invention is realized by grafting Fe on zeolite 3 O 4 ‑CeO 2 The composite particles and the photocatalytic particles realize functional modification of zeolite, the obtained composite modified zeolite not only has obviously improved physical adsorption capacity, but also has the performance of photocatalytic oxidative degradation of organic matters, so that the water treatment effect of the composite modified zeolite can be greatly improved, and finally, the water purifying agent suitable for deep treatment of coal coking industrial wastewater is obtained through compounding the composite modified zeolite, polymeric ferric sulfate and polymeric aluminum chloride.
Description
Technical Field
The invention relates to the field of wastewater treatment, in particular to a preparation method of a coal coking industrial wastewater purifying agent based on modified zeolite.
Background
The coking wastewater is industrial wastewater with high CODcr, high ammonia nitrogen and high phenol which is generated in coking, gas purification, coking product recovery and other processes, has high toxicity and can be discharged after being treated.
The biochemical method is a common coking wastewater treatment method, which can effectively reduce phenol and cyanide substances in wastewater, but has low removal rate of refractory organic substances and ammonia nitrogen, so that the coking wastewater is subjected to further advanced treatment after biochemical treatment, for example, the coking wastewater is subjected to recleaning by adding a water purifying agent with functions of adsorption, flocculation, oxidation and the like.
Patent CN111646534A discloses a coking phenol-cyanogen wastewater purifying agent, a preparation method and application thereof, which adopts attapulgite, bentonite, fly ash, zeolite powder, a silane coupling agent, dimethyl diallyl ammonium chloride, potassium persulfate, sodium carboxymethyl cellulose, polymeric ferric sulfate, polymeric aluminum ferric silicate, ferrous sulfate, magnesium sulfate heptahydrate, trisodium phosphate, polyacrylamide, polyvinylpyrrolidone and calcium hydroxide as raw materials to compound the water purifying agent for advanced treatment of biochemical effluent in the coking wastewater treatment process, thereby obtaining better effect, but the components are complex.
Patent CN110577254a discloses a water purifying agent for coal chemical industry, coking industry and other chemical industry and a preparation method thereof, wherein the water purifying agent is prepared from raw materials such as carboxymethyl cellulose, modified chitosan, phenolic aldehyde, composite aluminum ferric diacid, xanthan gum, cationic guar gum, acid solution, aluminum potassium sulfate dodecahydrate, polyacrylamide, polymeric ferric sulfate, ST and the like and is used for advanced treatment of biochemical effluent in a coking wastewater treatment process, but the removal effect of COD is poor.
The zeolite is a renewable mineral with rich pore structures, acid and alkali resistance and corrosion resistance, has strong stability and low cost, and is widely applied to the field of water treatment as an adsorption material, such as a zeolite-porous carbon-photocatalyst ternary composite material disclosed in patent CN110302828A, a preparation method and a wastewater treatment device thereof, a zeolite-activated carbon composite filter material cascade biological filter water treatment system and treatment process disclosed in patent CN106186579A, and the like. However, natural zeolite mainly removes pollutants through physical adsorption, and has the defect of limited adsorption capacity for ammonia nitrogen and organic pollutants.
Therefore, there is a need in the art for improvements that provide a more reliable solution.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a coal coking industrial wastewater purifying agent based on modified zeolite aiming at the defects in the prior art.
In order to solve the technical problems, the invention adopts the following technical scheme: a preparation method of a coal coking industrial wastewater purifying agent based on modified zeolite comprises the following steps:
s1, preprocessing natural zeolite;
s2, modifying Fe on the pretreated zeolite 3 O 4 -CeO 2 Composite particles;
s3, modifying Fe 3 O 4 -CeO 2 Grafting photocatalytic particles on the zeolite of the composite particles to obtain composite modified zeolite, wherein the photocatalytic particles are S, N doped carbon points;
s4, mixing the composite modified zeolite with polymeric ferric sulfate and polymeric aluminum chloride to obtain the water purifying agent.
Preferably, the step S1 specifically includes:
s1-1, crushing natural zeolite, then adding the crushed natural zeolite into distilled water, soaking for 0.5-2h, filtering and drying;
s1-2, roasting at 200-300 ℃ for 1-6h, and naturally cooling;
s1-3, adding the mixture into a sodium hydroxide solution, soaking for 1-4 hours, filtering, and cleaning with deionized water;
s1-4, adding the mixture into sodium chloride solution, soaking for 0.5-2h, filtering, washing with deionized water, and drying to obtain pretreated zeolite.
Preferably, the step S1 specifically includes:
s1-1, crushing natural zeolite to a mass fraction of more than 95% below 200 meshes, then adding the crushed natural zeolite into distilled water, soaking for 1h, filtering and drying;
s1-2, roasting for 3 hours at 250 ℃, and naturally cooling;
s1-3, adding the mixture into a sodium hydroxide solution with the concentration of 0.5mol/L, soaking for 2 hours, filtering, and cleaning with deionized water;
s1-4, adding the mixture into a sodium chloride solution with the concentration of 0.5mol/L, soaking for 1h, filtering, washing with deionized water, and drying to obtain pretreated zeolite.
Preferably, the step S2 specifically includes:
s2-1, adding pretreated zeolite into ethanol, soaking for 5-20min, filtering, then adding into deionized water, and performing ultrasonic treatment for 10-30min to obtain zeolite dispersion;
s2-2, 0.01-0.05mol Fe (NO) 3 ) 3 ·9H 2 O、0.005-0.03mol Ce(NO 3 ) 3 ·6H 2 Dissolving O in 150mL deionized water, adding the obtained solution into zeolite dispersion, stirring for 5-30min, and then adding 20-100mL NaOH solution with concentration of 1.0M under stirring to obtain a mixture;
s2-3, transferring the mixture into a reaction kettle, reacting for 4-12h at 160-240 ℃, drying after the reaction is finished, and calcining for 2-6h at 400-600 ℃ in nitrogen atmosphere to obtain the modified Fe 3 O 4 -CeO 2 Zeolite of composite particles.
Preferably, the step S2 specifically includes:
s2-1, adding pretreated zeolite into ethanol, soaking for 10min, filtering, then adding into deionized water, and performing ultrasonic treatment for 20min to obtain zeolite dispersion;
s2-2, 0.02mol of Fe (NO) 3 ) 3 ·9H 2 O、0.015Ce(NO 3 ) 3 ·6H 2 Dissolving O in 150mL of deionized water, adding the obtained solution into zeolite dispersion, stirring for 15min, and then adding 50mL of NaOH solution with the concentration of 1.0M under stirring to obtain a mixture;
s2-3, transferring the mixture into a reaction kettle, reacting for 6 hours at 220 ℃, drying after the reaction is finished, and calcining for 4 hours at 480 ℃ in nitrogen atmosphere to obtain the modified Fe 3 O 4 -CeO 2 Zeolite of composite particles.
Preferably, in the step S2-2, the raw material is added in a mass ratio of Fe to zeolite of 3:2.
Preferably, the step S3 specifically includes:
s3-1, preparing photocatalytic particles:
s3-1-1, adding folic acid, thiourea and ethylenediamine into deionized water, and performing ultrasonic treatment for 2-10min to obtain a precursor solution;
s3-1-2, adding the precursor solution into a reaction kettle of a polytetrafluoroethylene substrate, and reacting for 3-12h at 160-230 ℃;
s3-1-3, naturally cooling after the reaction is finished, filtering by using a filter membrane, dialyzing filtrate in deionized water for 6-24h by using a dialysis bag with the molecular weight cut-off of 600-1200D, collecting dialysate in the dialysis bag, and freeze-drying to obtain the S, N doped carbon dots, namely the photocatalytic particles;
s3-2, in modification of Fe 3 O 4 -CeO 2 Grafting photocatalytic particles on zeolite of the composite particles:
s3-2-1, adding the photocatalytic particles prepared in the step S3-1 into deionized water, and performing ultrasonic treatment for 10-30min to prepare a photocatalytic particle dispersion liquid;
s3-2-2, modified Fe prepared in step S2 3 O 4 -CeO 2 Adding zeolite of composite particles into ethanol water solution, soaking for 1-4h, filtering, and drying;
s3-2-3, modified Fe obtained in step S3-2-2 3 O 4 -CeO 2 Adding zeolite with composite particles into the photocatalytic particle dispersion liquid obtained in the step S3-2-1, adding EDCI, oscillating at 55-95deg.C for 6-24 hr, filtering, adding ethanol and deionized waterAnd (5) cleaning and drying sequentially to obtain the composite modified zeolite.
Preferably, the step S3 specifically includes:
s3-1, preparing photocatalytic particles:
s3-1-1, adding 6.2g of folic acid, 4.7g of thiourea and 2.5g of ethylenediamine into 180mL of deionized water, and performing ultrasonic treatment for 5min to obtain a precursor liquid;
s3-1-2, adding the precursor solution into a 200mL polytetrafluoroethylene substrate reaction kettle, and reacting for 6 hours at 190 ℃;
s3-1-3, naturally cooling after the reaction is finished, filtering with a filter membrane with the molecular weight cut-off of 0.25 mu m, dialyzing filtrate in deionized water for 12 hours with a dialysis bag with the molecular weight cut-off of 800D, collecting dialysate in the dialysis bag, and freeze-drying to obtain the S, N doped carbon dots, namely the photocatalytic particles;
s3-2, in modification of Fe 3 O 4 -CeO 2 Grafting photocatalytic particles on zeolite of the composite particles:
s3-2-1, adding the photocatalytic particles prepared in the step S3-1 into deionized water, and performing ultrasonic treatment for 20min to prepare a photocatalytic particle dispersion liquid with the concentration of 2 mg/mL;
s3-2-2, modified Fe prepared in step S2 3 O 4 -CeO 2 Adding zeolite of the composite particles into ethanol water solution, soaking for 2h, filtering and drying;
s3-2-3, modified Fe obtained in step S3-2-2 3 O 4 -CeO 2 Adding zeolite of composite particles into the photocatalytic particle dispersion liquid obtained in the step S3-2-1, adding EDCI, oscillating for 12 hours at 75 ℃, filtering, sequentially cleaning with ethanol and deionized water, and drying to obtain the composite modified zeolite.
Preferably, in the step S3-2-2, fe is modified 3 O 4 -CeO 2 Zeolite of composite particles: the mass ratio of the photocatalytic particles is 10:1-10:3.5, and the raw materials are added.
Preferably, the step S4 specifically includes: the composite modified zeolite and polymeric ferric sulfate and polymeric aluminum chloride are compounded according to the mass ratio: polymeric ferric sulfate: polyaluminum chloride=1:0.8:0.5, heating for 2 hours at 95 ℃, and grinding until the mass ratio below 200 meshes is more than 95%, thus obtaining the water purifying agent.
The beneficial effects of the invention are as follows:
the invention provides a preparation method of a coal coking industrial wastewater purifying agent based on modified zeolite, which comprises the steps of roasting, alkaline leaching and salt leaching the zeolite, so that the pore volume and specific surface area of the zeolite can be effectively increased, and the physical adsorption capacity of the zeolite is improved; then by grafting Fe 3 O 4 -CeO 2 The composite particles and the photocatalytic particles realize the functional modification of zeolite, the physical adsorption capacity of the obtained composite modified zeolite is obviously improved, and the photocatalytic oxidation degradation performance of organic matters is realized, so that the water treatment effect of the composite modified zeolite can be greatly improved, and finally, the water purifying agent suitable for the deep treatment of the coal coking industrial wastewater is obtained through the compounding preparation of the composite modified zeolite, polymeric ferric sulfate and polymeric aluminum chloride;
in the invention, S, N doped carbon dots with photocatalytic oxidation capability are prepared and grafted to modified Fe 3 O 4 -CeO 2 The zeolite of the composite particles has the capability of degrading organic matters by photocatalytic oxidation and Fe 3 O 4 -CeO 2 The composite particles have promotion effect on the oxidation capability, and finally the degradation efficiency of organic matters can be improved;
in the invention, fe is formed by in-situ grafting on the surface of zeolite 3 O 4 -CeO 2 The composite particles have a certain adsorption effect on organic matters on one hand and a promotion effect on photocatalysis on the other hand; and Fe (Fe) 3 O 4 The water purifying agent has magnetism, so that the water purifying agent can be conveniently recycled when a magnetic field is applied.
Drawings
FIG. 1 is a scanning electron microscope image of carbon dots prepared in example 3;
FIG. 2 is a scanning electron microscope image of the composite modified zeolite prepared in example 3.
Detailed Description
The present invention is described in further detail below with reference to examples to enable those skilled in the art to practice the same by referring to the description.
It will be understood that terms, such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
The test methods used in the following examples are conventional methods unless otherwise specified. The material reagents and the like used in the following examples are commercially available unless otherwise specified. The following examples were conducted under conventional conditions or conditions recommended by the manufacturer, without specifying the specific conditions. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The invention provides a preparation method of a coal coking industrial wastewater purifying agent based on modified zeolite, which comprises the following steps:
s1, preprocessing natural zeolite:
s1-1, crushing natural zeolite, then adding the crushed natural zeolite into distilled water, soaking for 0.5-2h, filtering and drying;
s1-2, roasting at 200-300 ℃ for 1-6h, and naturally cooling;
s1-3, adding the mixture into a sodium hydroxide solution, soaking for 1-4 hours, filtering, and cleaning with deionized water;
s1-4, adding the mixture into sodium chloride solution, soaking for 0.5-2h, filtering, washing with deionized water, and drying to obtain pretreated zeolite.
S2, modifying Fe on the pretreated zeolite 3 O 4 -CeO 2 Composite particles:
s2-1, adding pretreated zeolite into ethanol, soaking for 5-20min, filtering, then adding into deionized water, and performing ultrasonic treatment for 10-30min to obtain zeolite dispersion;
s2-2, 0.01-0.05mol Fe (NO) 3 ) 3 ·9H 2 O、0.005-0.03mol Ce(NO 3 ) 3 ·6H 2 Dissolving O in 150mL deionized water, adding the obtained solution into zeolite dispersion, stirring for 5-30min, and then adding 20-100mL NaOH solution with concentration of 1.0M under stirring to obtain a mixture;
s2-3, transferring the mixture into a reaction kettle, reacting for 4-12h at 160-240 ℃, drying after the reaction is finished, and calcining for 2-6h at 400-600 ℃ in nitrogen atmosphere to obtain the modified Fe 3 O 4 -CeO 2 Zeolite of composite particles.
S3, modifying Fe 3 O 4 -CeO 2 Grafting photocatalytic particles on the zeolite of the composite particles to obtain composite modified zeolite, wherein the photocatalytic particles are S, N doped carbon points:
s3-1, preparing photocatalytic particles:
s3-1-1, adding folic acid, thiourea and ethylenediamine into deionized water, and performing ultrasonic treatment for 2-10min to obtain a precursor solution;
s3-1-2, adding the precursor solution into a reaction kettle of a polytetrafluoroethylene substrate, and reacting for 3-12h at 160-230 ℃;
s3-1-3, naturally cooling after the reaction is finished, filtering by using a filter membrane, dialyzing filtrate in deionized water for 6-24h by using a dialysis bag with the molecular weight cut-off of 600-1200D, collecting dialysate in the dialysis bag, and freeze-drying to obtain S, N doped carbon points, namely photocatalytic particles;
s3-2, in modification of Fe 3 O 4 -CeO 2 Grafting photocatalytic particles on zeolite of the composite particles:
s3-2-1, adding the photocatalytic particles prepared in the step S3-1 into deionized water, and performing ultrasonic treatment for 10-30min to prepare a photocatalytic particle dispersion liquid;
s3-2-2, modified Fe prepared in step S2 3 O 4 -CeO 2 Adding zeolite of composite particles into ethanol water solution, soaking for 1-4h, filtering, and drying;
s3-2-3, modified Fe obtained in step S3-2-2 3 O 4 -CeO 2 Adding zeolite of composite particles into the photocatalytic particle dispersion liquid obtained in the step S3-2-1, adding EDCI, oscillating for 6-24 hours at 55-95 ℃, filtering, sequentially cleaning with ethanol and deionized water, and drying to obtain the composite modified zeolite.
S4, compounding the compound modified zeolite with polymeric ferric sulfate and polymeric aluminum chloride according to the mass ratio: polymeric ferric sulfate: polyaluminium chloride=1:0.8:0.5, heating for 1-4h at 75-120 ℃, and grinding until the mass ratio below 200-300 meshes is more than 95%, thus obtaining the water purifying agent.
The water purifying agent has the property of degrading organic matters by photocatalytic oxidation, and can obtain better effect by matching with illumination and aeration processes when the coal coking industrial wastewater treatment is carried out.
Zeolite is a renewable mineral with rich pore structure, acid and alkali resistance and corrosion resistance, has strong stability and low cost, and is widely applied to the field of water treatment as an adsorption material. However, natural zeolite mainly removes pollutants through physical adsorption, and has the defect of limited adsorption capacity for ammonia nitrogen and organic pollutants. In the invention, firstly, the zeolite is subjected to roasting, alkaline leaching and salt leaching treatment, so that the pore volume and specific surface area of the zeolite can be effectively increased, and the physical adsorption capacity of the zeolite is improved; then by grafting Fe 3 O 4 -CeO 2 The composite particles and the photocatalytic particles realize functional modification of zeolite, the obtained composite modified zeolite not only has obviously improved physical adsorption capacity, but also has the performance of photocatalytic oxidative degradation of organic matters, so that the water treatment effect of the composite modified zeolite can be greatly improved, and finally, the composite modified zeolite, polymeric ferric sulfate and polymeric aluminum chloride are compounded to prepare the water purifying agent suitable for advanced treatment of coal coking industrial wastewater, and the principle of the water purifying agent is explained in detail below.
In the invention, firstly, the bound water in the pores of the natural zeolite can be removed through roasting treatment, so that the pore volume is increased; micropores can be further enlarged by alkaline leaching, and the divalent cations (Ca) having a larger particle diameter in the attapulgite clay are replaced by sodium ions having a smaller particle diameter by salt leaching treatment 2+ 、Mg 2+ Etc.), on one hand, the pore volume can be increased, and on the other hand, the electronegativity of the material can be improved, thereby being more beneficial to improving the adsorption and removal effects on cations such as ammonia nitrogen, etc.;
in the invention, fe is formed by in-situ grafting on the surface of zeolite 3 O 4 -CeO 2 The composite particles have a certain adsorption effect on organic matters on one hand and a promotion effect on photocatalysis on the other hand; at Fe 3 O 4 -CeO 2 In the process of forming the composite particles, iron ions and cerium ions can be uniformly connected to the surface of zeolite through the actions of coordination with hydroxyl groups on the surface of the zeolite, electrostatic adsorption and the like, and then Fe is formed in situ by calcining 3 O 4 -CeO 2 Composite particles;
in the invention, S, N doped carbon dots with photocatalytic oxidation capability are prepared and grafted to modified Fe 3 O 4 -CeO 2 The zeolite of the composite particles has the capability of degrading organic matters by photocatalytic oxidation and Fe 3 O 4 -CeO 2 The composite particles have promotion effect on the oxidizing ability, and the main action principle is as follows: the carbon point absorbs long wavelength visible light and then excites to a high energy state, and emits short wavelength ultraviolet photons, O 2 Or other oxygen-containing oxidants to obtain carbon dots and conduction band electrons of semiconductor heterojunction thereof to form superoxide radical (O) with strong oxidation activity 2- ) And hydroxyl radicals (·oh) which are capable of attacking the organic matter, degrading it; in the process, ce can promote the photoinduction charge transfer process of the carbon point and enhance the light absorption capacity of the carbon point, so that the photooxidation activity of the carbon point is enhanced, and finally the degradation efficiency of organic matters can be improved; at the same time Fe 3 O 4 As a widely used Fenton-like catalyst, the catalyst can also promote the oxidation photo-process, can further improve the generation of strong oxidation active groups, and Fe 3 O 4 The water purifying agent has magnetism, so that the water purifying agent can be conveniently recovered when a magnetic field is applied, and can be reused after being treated by a regeneration reagent (such as sodium hydroxide and the like);
in the modification process of the carbon dots, on one hand, the combination is realized through the reaction of rich carboxyl on the surface of the carbon dots and hydroxyl on the surface of the zeolite, and on the other hand, the coordination effect of oxygen-containing functional groups on the surface of the carbon dots and Ce can promote the uniform and firm combination of the carbon dots on the surface of the zeolite.
According to the invention, folic acid, thiourea and ethylenediamine are taken as main raw materials, a S, N doped carbon dot is synthesized through a hydrothermal method, the surface of the carbon dot is provided with rich carboxyl, amino and other functional groups, the functional groups can adsorb and remove part of heavy metal ion pollutants in water, and S, N doping can improve the visible light absorption range of the carbon dot and improve the photocatalytic efficiency.
Example 1
A preparation method of a coal coking industrial wastewater purifying agent based on modified zeolite comprises the following steps:
s1, preprocessing natural zeolite:
s1-1, crushing natural zeolite to a mass fraction of more than 95% below 200 meshes, then adding the crushed natural zeolite into distilled water, soaking for 1h, filtering and drying;
s1-2, roasting for 3 hours at 250 ℃, and naturally cooling;
s1-3, adding the mixture into a sodium hydroxide solution with the concentration of 0.5mol/L, soaking for 2 hours, filtering, and cleaning with deionized water;
s1-4, adding the mixture into a sodium chloride solution with the concentration of 0.5mol/L, soaking for 1h, filtering, washing with deionized water, and drying to obtain pretreated zeolite.
S2, modifying Fe on the pretreated zeolite 3 O 4 -CeO 2 Composite particles:
s2-1, adding pretreated zeolite into ethanol, soaking for 10min, filtering, then adding into deionized water, and performing ultrasonic treatment for 20min to obtain zeolite dispersion;
s2-2, 0.02mol of Fe (NO) 3 ) 3 ·9H 2 O、0.015Ce(NO 3 ) 3 ·6H 2 Dissolving O in 150mL of deionized water, adding the obtained solution into zeolite dispersion, stirring for 15min, and then adding 50mL of NaOH solution with the concentration of 1.0M under stirring to obtain a mixture;
wherein, the raw materials are added according to the mass ratio of Fe to zeolite of 3:2;
s2-3, transferring the mixture into a reaction kettle, reacting for 6 hours at 220 ℃, drying after the reaction is finished, and calcining for 4 hours at 480 ℃ in nitrogen atmosphere to obtain the modified Fe 3 O 4 -CeO 2 Zeolite of composite particles;
s3, modifying Fe 3 O 4 -CeO 2 Grafting of composite particles onto zeolitePhotocatalytic particles, namely S, N doped carbon points, are obtained:
s3-1, preparing photocatalytic particles:
s3-1-1, adding 6.2g of folic acid, 4.7g of thiourea and 2.5g of ethylenediamine into 180mL of deionized water, and performing ultrasonic treatment for 5min to obtain a precursor liquid;
s3-1-2, adding the precursor solution into a 200mL polytetrafluoroethylene substrate reaction kettle, and reacting for 6 hours at 190 ℃;
s3-1-3, naturally cooling after the reaction is finished, filtering with a filter membrane of 0.25 mu m, dialyzing filtrate in deionized water for 12 hours with a dialysis bag with a molecular weight cut-off of 800D, collecting dialysate in the dialysis bag, and freeze-drying to obtain S, N doped carbon points, namely photocatalytic particles;
s3-2, in modification of Fe 3 O 4 -CeO 2 Grafting photocatalytic particles on zeolite of the composite particles:
s3-2-1, adding the photocatalytic particles prepared in the step S3-1 into deionized water, and performing ultrasonic treatment for 20min to prepare a photocatalytic particle dispersion liquid with the concentration of 2 mg/mL;
s3-2-2, modified Fe prepared in step S2 3 O 4 -CeO 2 Adding zeolite of the composite particles into ethanol water solution, soaking for 2h, filtering and drying;
wherein Fe is modified according to 3 O 4 -CeO 2 Zeolite of composite particles: adding raw materials in a mass ratio of 10:2;
s3-2-3, modified Fe obtained in step S3-2-2 3 O 4 -CeO 2 Adding zeolite of composite particles into the photocatalytic particle dispersion liquid obtained in the step S3-2-1, adding EDCI, oscillating for 12 hours at 75 ℃, filtering, sequentially cleaning with ethanol and deionized water, and drying to obtain the composite modified zeolite.
S4, compounding the compound modified zeolite with polymeric ferric sulfate and polymeric aluminum chloride according to the mass ratio: polymeric ferric sulfate: polyaluminum chloride=1:0.8:0.5, heating for 2h at 95 ℃, and grinding until the mass ratio below 200 meshes is more than 95%, thus obtaining the water purifying agent.
Example 2
A preparation method of a coal coking industrial wastewater purifying agent based on modified zeolite comprises the following steps:
s1, preprocessing natural zeolite:
s1-1, crushing natural zeolite to a mass fraction of more than 95% below 200 meshes, then adding the crushed natural zeolite into distilled water, soaking for 1h, filtering and drying;
s1-2, roasting for 3 hours at 250 ℃, and naturally cooling;
s1-3, adding the mixture into a sodium hydroxide solution with the concentration of 0.5mol/L, soaking for 2 hours, filtering, and cleaning with deionized water;
s1-4, adding the mixture into a sodium chloride solution with the concentration of 0.5mol/L, soaking for 1h, filtering, washing with deionized water, and drying to obtain pretreated zeolite.
S2, modifying Fe on the pretreated zeolite 3 O 4 -CeO 2 Composite particles:
s2-1, adding pretreated zeolite into ethanol, soaking for 10min, filtering, then adding into deionized water, and performing ultrasonic treatment for 20min to obtain zeolite dispersion;
s2-2, 0.02mol of Fe (NO) 3 ) 3 ·9H 2 O、0.015Ce(NO 3 ) 3 ·6H 2 Dissolving O in 150mL of deionized water, adding the obtained solution into zeolite dispersion, stirring for 15min, and then adding 50mL of NaOH solution with the concentration of 1.0M under stirring to obtain a mixture;
wherein, the raw materials are added according to the mass ratio of Fe to zeolite of 1:1;
s2-3, transferring the mixture into a reaction kettle, reacting for 6 hours at 220 ℃, drying after the reaction is finished, and calcining for 4 hours at 480 ℃ in nitrogen atmosphere to obtain the modified Fe 3 O 4 -CeO 2 Zeolite of composite particles;
s3, modifying Fe 3 O 4 -CeO 2 Grafting photocatalytic particles on the zeolite of the composite particles to obtain composite modified zeolite, wherein the photocatalytic particles are S, N doped carbon points:
s3-1, preparing photocatalytic particles:
s3-1-1, adding 6.2g folic acid 4.7g thiourea and 2.5g ethylenediamine into 180mL deionized water, and performing ultrasonic treatment for 5min to obtain a precursor liquid;
s3-1-2, adding the precursor solution into a 200mL polytetrafluoroethylene substrate reaction kettle, and reacting for 6 hours at 190 ℃;
s3-1-3, naturally cooling after the reaction is finished, filtering with a filter membrane of 0.25 mu m, dialyzing filtrate in deionized water for 12 hours with a dialysis bag with a molecular weight cut-off of 800D, collecting dialysate in the dialysis bag, and freeze-drying to obtain S, N doped carbon points, namely photocatalytic particles;
s3-2, in modification of Fe 3 O 4 -CeO 2 Grafting photocatalytic particles on zeolite of the composite particles:
s3-2-1, adding the photocatalytic particles prepared in the step S3-1 into deionized water, and performing ultrasonic treatment for 20min to prepare a photocatalytic particle dispersion liquid with the concentration of 2 mg/mL;
s3-2-2, modified Fe prepared in step S2 3 O 4 -CeO 2 Adding zeolite of the composite particles into ethanol water solution, soaking for 2h, filtering and drying;
wherein Fe is modified according to 3 O 4 -CeO 2 Zeolite of composite particles: adding raw materials in a mass ratio of 10:2;
s3-2-3, modified Fe obtained in step S3-2-2 3 O 4 -CeO 2 Adding zeolite of composite particles into the photocatalytic particle dispersion liquid obtained in the step S3-2-1, adding EDCI, oscillating for 12 hours at 75 ℃, filtering, sequentially cleaning with ethanol and deionized water, and drying to obtain the composite modified zeolite.
S4, compounding the compound modified zeolite with polymeric ferric sulfate and polymeric aluminum chloride according to the mass ratio: polymeric ferric sulfate: polyaluminum chloride=1:0.8:0.5, heating for 2h at 95 ℃, and grinding until the mass ratio below 200 meshes is more than 95%, thus obtaining the water purifying agent.
Example 3
A preparation method of a coal coking industrial wastewater purifying agent based on modified zeolite comprises the following steps:
s1, preprocessing natural zeolite:
s1-1, crushing natural zeolite to a mass fraction of more than 95% below 200 meshes, then adding the crushed natural zeolite into distilled water, soaking for 1h, filtering and drying;
s1-2, roasting for 3 hours at 250 ℃, and naturally cooling;
s1-3, adding the mixture into a sodium hydroxide solution with the concentration of 0.5mol/L, soaking for 2 hours, filtering, and cleaning with deionized water;
s1-4, adding the mixture into a sodium chloride solution with the concentration of 0.5mol/L, soaking for 1h, filtering, washing with deionized water, and drying to obtain pretreated zeolite.
S2, modifying Fe on the pretreated zeolite 3 O 4 -CeO 2 Composite particles:
s2-1, adding pretreated zeolite into ethanol, soaking for 10min, filtering, then adding into deionized water, and performing ultrasonic treatment for 20min to obtain zeolite dispersion;
s2-2, 0.02mol of Fe (NO) 3 ) 3 .·9H 2 O、0.015Ce(NO 3 ) 3 ·6H 2 Dissolving O in 150mL of deionized water, adding the obtained solution into zeolite dispersion, stirring for 15min, and then adding 50mL of NaOH solution with the concentration of 1.0M under stirring to obtain a mixture;
wherein, the raw materials are added according to the mass ratio of Fe to zeolite of 3:2;
s2-3, transferring the mixture into a reaction kettle, reacting for 6 hours at 220 ℃, drying after the reaction is finished, and calcining for 4 hours at 480 ℃ in nitrogen atmosphere to obtain the modified Fe 3 O 4 -CeO 2 Zeolite of composite particles;
s3, modifying Fe 3 O 4 -CeO 2 Grafting photocatalytic particles on the zeolite of the composite particles to obtain composite modified zeolite, wherein the photocatalytic particles are S, N doped carbon points:
s3-1, preparing photocatalytic particles:
s3-1-1, adding 6.2g folic acid 4.7g thiourea and 2.5g ethylenediamine into 180mL deionized water, and performing ultrasonic treatment for 5min to obtain a precursor liquid;
s3-1-2, adding the precursor solution into a 200mL polytetrafluoroethylene substrate reaction kettle, and reacting for 6 hours at 190 ℃;
s3-1-3, naturally cooling after the reaction is finished, filtering with a filter membrane of 0.25 mu m, dialyzing filtrate in deionized water for 12 hours with a dialysis bag with a molecular weight cut-off of 800D, collecting dialysate in the dialysis bag, and freeze-drying to obtain S, N doped carbon points, namely photocatalytic particles;
s3-2, in modification of Fe 3 O 4 -CeO 2 Grafting photocatalytic particles on zeolite of the composite particles:
s3-2-1, adding the photocatalytic particles prepared in the step S3-1 into deionized water, and performing ultrasonic treatment for 20min to prepare a photocatalytic particle dispersion liquid with the concentration of 2 mg/mL;
s3-2-2, modified Fe prepared in step S2 3 O 4 -CeO 2 Adding zeolite of the composite particles into ethanol water solution, soaking for 2h, filtering and drying;
wherein Fe is modified according to 3 O 4 -CeO 2 Zeolite of composite particles: adding raw materials in a mass ratio of 10:3;
s3-2-3, modified Fe obtained in step S3-2-2 3 O 4 -CeO 2 Adding zeolite of composite particles into the photocatalytic particle dispersion liquid obtained in the step S3-2-1, adding EDCI, oscillating for 12 hours at 75 ℃, filtering, sequentially cleaning with ethanol and deionized water, and drying to obtain the composite modified zeolite.
S4, compounding the compound modified zeolite with polymeric ferric sulfate and polymeric aluminum chloride according to the mass ratio: polymeric ferric sulfate: polyaluminum chloride=1:0.8:0.5, heating for 2h at 95 ℃, and grinding until the mass ratio below 200 meshes is more than 95%, thus obtaining the water purifying agent.
Example 4
A preparation method of a coal coking industrial wastewater purifying agent based on modified zeolite comprises the following steps:
s1, preprocessing natural zeolite:
s1-1, crushing natural zeolite to a mass fraction of more than 95% below 200 meshes, then adding the crushed natural zeolite into distilled water, soaking for 1h, filtering and drying;
s1-2, roasting for 3 hours at 250 ℃, and naturally cooling;
s1-3, adding the mixture into a sodium hydroxide solution with the concentration of 0.5mol/L, soaking for 2 hours, filtering, and cleaning with deionized water;
s1-4, adding the mixture into a sodium chloride solution with the concentration of 0.5mol/L, soaking for 1h, filtering, washing with deionized water, and drying to obtain pretreated zeolite.
S2, modifying Fe on the pretreated zeolite 3 O 4 -CeO 2 Composite particles:
s2-1, adding pretreated zeolite into ethanol, soaking for 10min, filtering, then adding into deionized water, and performing ultrasonic treatment for 20min to obtain zeolite dispersion;
s2-2, 0.02mol of Fe (NO) 3 ) 3 ·9H 2 O、0.015Ce(NO 3 ) 3 ·6H 2 Dissolving O in 150mL of deionized water, adding the obtained solution into zeolite dispersion, stirring for 15min, and then adding 50mL of NaOH solution with the concentration of 1.0M under stirring to obtain a mixture;
wherein, the raw materials are added according to the mass ratio of Fe to zeolite of 3:2;
s2-3, transferring the mixture into a reaction kettle, reacting for 6 hours at 220 ℃, drying after the reaction is finished, and calcining for 4 hours at 480 ℃ in nitrogen atmosphere to obtain the modified Fe 3 O 4 -CeO 2 Zeolite of composite particles;
s3, modifying Fe 3 O 4 -CeO 2 Grafting photocatalytic particles on the zeolite of the composite particles to obtain composite modified zeolite, wherein the photocatalytic particles are S, N doped carbon points:
s3-1, preparing photocatalytic particles:
s3-1-1, adding 6.2g folic acid 4.7g thiourea and 2.5g ethylenediamine into 180mL deionized water, and performing ultrasonic treatment for 5min to obtain a precursor liquid;
s3-1-2, adding the precursor solution into a 200mL polytetrafluoroethylene substrate reaction kettle, and reacting for 6 hours at 190 ℃;
s3-1-3, naturally cooling after the reaction is finished, filtering with a filter membrane of 0.25 mu m, dialyzing filtrate in deionized water for 12 hours with a dialysis bag with a molecular weight cut-off of 800D, collecting dialysate in the dialysis bag, and freeze-drying to obtain S, N doped carbon points, namely photocatalytic particles;
s3-2, in modification of Fe 3 O 4 -CeO 2 Grafting photocatalytic particles on zeolite of the composite particles:
s3-2-1, adding the photocatalytic particles prepared in the step S3-1 into deionized water, and performing ultrasonic treatment for 20min to prepare a photocatalytic particle dispersion liquid with the concentration of 2 mg/mL;
s3-2-2, modified Fe prepared in step S2 3 O 4 -CeO 2 Adding zeolite of the composite particles into ethanol water solution, soaking for 2h, filtering and drying;
wherein Fe is modified according to 3 O 4 -CeO 2 Zeolite of composite particles: adding raw materials in a mass ratio of 10:3.5;
s3-2-3, modified Fe obtained in step S3-2-2 3 O 4 -CeO 2 Adding zeolite of composite particles into the photocatalytic particle dispersion liquid obtained in the step S3-2-1, adding EDCI, oscillating for 12 hours at 75 ℃, filtering, sequentially cleaning with ethanol and deionized water, and drying to obtain the composite modified zeolite.
S4, compounding the compound modified zeolite with polymeric ferric sulfate and polymeric aluminum chloride according to the mass ratio: polymeric ferric sulfate: polyaluminum chloride=1:0.8:0.5, heating for 2h at 95 ℃, and grinding until the mass ratio below 200 meshes is more than 95%, thus obtaining the water purifying agent.
Comparative example 1
A preparation method of a coal coking industrial wastewater purifying agent based on modified zeolite comprises the following steps:
s1, preprocessing natural zeolite:
s1-1, crushing natural zeolite to a mass fraction of more than 95% below 200 meshes, then adding the crushed natural zeolite into distilled water, soaking for 1h, filtering and drying;
s1-2, roasting for 3 hours at 250 ℃, and naturally cooling;
s1-3, adding the mixture into a sodium hydroxide solution with the concentration of 0.5mol/L, soaking for 2 hours, filtering, and cleaning with deionized water;
s1-4, adding the mixture into a sodium chloride solution with the concentration of 0.5mol/L, soaking for 1h, filtering, washing with deionized water, and drying to obtain pretreated zeolite.
S2, compounding the pretreated zeolite with polymeric ferric sulfate and polymeric aluminum chloride to modify the zeolite according to the mass ratio: polymeric ferric sulfate: polyaluminum chloride=1:0.8:0.5, heating for 2h at 95 ℃, and grinding until the mass ratio below 200 meshes is more than 95%, thus obtaining the water purifying agent.
Comparative example 2
A preparation method of a coal coking industrial wastewater purifying agent based on modified zeolite comprises the following steps:
s1, preprocessing natural zeolite:
s1-1, crushing natural zeolite to a mass fraction of more than 95% below 200 meshes, then adding the crushed natural zeolite into distilled water, soaking for 1h, filtering and drying;
s1-2, roasting for 3 hours at 250 ℃, and naturally cooling;
s1-3, adding the mixture into a sodium hydroxide solution with the concentration of 0.5mol/L, soaking for 2 hours, filtering, and cleaning with deionized water;
s1-4, adding the mixture into a sodium chloride solution with the concentration of 0.5mol/L, soaking for 1h, filtering, washing with deionized water, and drying to obtain pretreated zeolite.
S2, modifying Fe on the pretreated zeolite 3 O 4 -CeO 2 Composite particles:
s2-1, adding pretreated zeolite into ethanol, soaking for 10min, filtering, then adding into deionized water, and performing ultrasonic treatment for 20min to obtain zeolite dispersion;
s2-2, 0.02mol of Fe (NO) 3 ) 3 ·9H 2 O、0.015Ce(NO 3 ) 3 ·6H 2 Dissolving O in 150mL of deionized water, adding the obtained solution into zeolite dispersion, stirring for 15min, and then adding 50mL of NaOH solution with the concentration of 1.0M under stirring to obtain a mixture;
wherein, the raw materials are added according to the mass ratio of Fe to zeolite of 3:2;
s2-3, transferring the mixture into a reaction kettle, reacting for 6 hours at 220 ℃, drying after the reaction is finished, and calcining for 4 hours at 480 ℃ in nitrogen atmosphere to obtain the modified Fe 3 O 4 -CeO 2 Zeolite of composite particles;
s3, to modify Fe 3 O 4 -CeO 2 The zeolite of the composite particles and the polymeric ferric sulfate and polymeric aluminum chloride are compounded with modified zeolite according to the mass ratio: polymeric ferric sulfate: polyaluminum chloride=1:0.8:0.5, heating for 2h at 95 ℃, and grinding until the mass ratio below 200 meshes is more than 95%, thus obtaining the water purifying agent.
Comparative example 3
A preparation method of a coal coking industrial wastewater purifying agent based on modified zeolite comprises the following steps:
s1, preprocessing natural zeolite:
s1-1, crushing natural zeolite to a mass fraction of more than 95% below 200 meshes, then adding the crushed natural zeolite into distilled water, soaking for 1h, filtering and drying;
s1-2, roasting for 3 hours at 250 ℃, and naturally cooling;
s1-3, adding the mixture into a sodium hydroxide solution with the concentration of 0.5mol/L, soaking for 2 hours, filtering, and cleaning with deionized water;
s1-4, adding the mixture into a sodium chloride solution with the concentration of 0.5mol/L, soaking for 1h, filtering, washing with deionized water, and drying to obtain pretreated zeolite.
S2, grafting photocatalytic particles on the pretreated zeolite to obtain composite modified zeolite, wherein the photocatalytic particles are S, N doped carbon points:
s2-1, preparing photocatalytic particles:
s2-1-1, adding 6.2g of folic acid, 4.7g of thiourea and 2.5g of ethylenediamine into 180mL of deionized water, and performing ultrasonic treatment for 5min to obtain a precursor liquid;
s2-1-2, adding the precursor solution into a 200mL polytetrafluoroethylene substrate reaction kettle, and reacting for 6 hours at 190 ℃;
s2-1-3, naturally cooling after the reaction is finished, filtering with a filter membrane of 0.25 mu m, dialyzing filtrate in deionized water for 12 hours by using a dialysis bag with the molecular weight cut-off of 800D, collecting dialysate in the dialysis bag, and freeze-drying to obtain S, N doped carbon points, namely photocatalytic particles;
s2-2, grafting photocatalytic particles on the pretreated zeolite:
s2-2-1, adding the photocatalytic particles prepared in the step S2-1 into deionized water, and performing ultrasonic treatment for 20min to prepare a photocatalytic particle dispersion liquid with the concentration of 2 mg/mL;
s2-2-2, adding the pretreated zeolite prepared in the step S1 into an ethanol water solution, soaking for 2 hours, filtering and drying;
wherein, according to the pretreated zeolite: adding raw materials in a mass ratio of 10:3;
s2-2-3, adding the pretreated zeolite obtained in the step S2-2-2 into the photocatalytic particle dispersion liquid obtained in the step S2-2-1, adding EDCI, oscillating for 12 hours at 75 ℃, filtering, sequentially cleaning with ethanol and deionized water, and drying to obtain the composite modified zeolite.
S3, compounding the compound modified zeolite with polymeric ferric sulfate and polymeric aluminum chloride according to the mass ratio: polymeric ferric sulfate: polyaluminum chloride=1:0.8:0.5, heating for 2h at 95 ℃, and grinding until the mass ratio below 200 meshes is more than 95%, thus obtaining the water purifying agent.
Referring to fig. 1, a scanning electron microscope image of carbon dots prepared in example 3, and fig. 2 is a scanning electron microscope image of composite modified zeolite prepared in example 3.
The water purifying agents prepared in the above examples and comparative examples were tested below using biochemical effluent from a wastewater treatment process in a certain coking plant in Shanxi as wastewater. The main pollutant indexes of the wastewater are shown in the following table 1:
TABLE 1
| Ammonia nitrogen (mg/L) | CODcr(mg/L) | Chromaticity (times) | |
| Biochemical effluent | 339.6 | 57.8 | 204 |
The testing method comprises the following steps: adding 0.2g of water purifying agent into 1L of biochemical effluent, stirring for 1h by aeration, standing for 0.5h, taking supernatant to detect ammonia nitrogen concentration, CODcr concentration and chromaticity, and calculating ammonia nitrogen removal rate, CODcr removal rate and chromaticity removal rate, wherein the measurement results are shown in the following table 2:
TABLE 2
| Ammonia nitrogen removal rate (%) | CODcr removal Rate (%) | Chromaticity removal (%) | |
| Example 1 | 87.3 | 92.7 | 94.9 |
| Example 2 | 88.6 | 93.1 | 95.2 |
| Example 3 | 90.7 | 95.2 | 96.4 |
| Example 4 | 91.2 | 95.8 | 97.1 |
| Comparative example 1 | 49.7 | 63.2 | 75.5 |
| Comparative example 2 | 72.9 | 78.4 | 80.1 |
| Comparative example 3 | 82.4 | 87.6 | 90.3 |
From the above results, it can be seen that the water purifying agents prepared in the methods of examples 1 to 4 have good removal effects on ammonia nitrogen, organic matters and chromaticity in wastewater, the zeolite in comparative example 1 has no functional modification, only has physical adsorption effect, has poor removal effects on ammonia nitrogen and organic matters, the zeolite in comparative example 2 has unmodified photocatalytic particles with photocatalytic oxidation activity, and has poor degradation and removal effects on organic matters, and the zeolite in comparative example 3 has unmodified Fe 3 O 4 -CeO 2 The composite particles obviously reduce the degradation and removal effects of the water purifying agent on organic matters.
Although embodiments of the present invention have been disclosed above, it is not limited to the use of the description and embodiments, it is well suited to various fields of use for the invention, and further modifications may be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the particular details without departing from the general concepts defined in the claims and the equivalents thereof.
Claims (10)
1. The preparation method of the coal coking industrial wastewater purifying agent based on the modified zeolite is characterized by comprising the following steps of:
s1, preprocessing natural zeolite;
s2, modifying Fe on the pretreated zeolite 3 O 4 -CeO 2 Composite particles;
s3, modifying Fe 3 O 4 -CeO 2 Grafting photocatalytic particles on the zeolite of the composite particles to obtain composite modified zeolite, wherein the photocatalytic particles are S, N doped carbon points;
s4, mixing the composite modified zeolite with polymeric ferric sulfate and polymeric aluminum chloride to obtain the water purifying agent.
2. The method for preparing the modified zeolite-based coal coking industrial wastewater purifying agent according to claim 1, wherein the step S1 specifically comprises:
s1-1, crushing natural zeolite, then adding the crushed natural zeolite into distilled water, soaking for 0.5-2h, filtering and drying;
s1-2, roasting at 200-300 ℃ for 1-6h, and naturally cooling;
s1-3, adding the mixture into a sodium hydroxide solution, soaking for 1-4 hours, filtering, and cleaning with deionized water;
s1-4, adding the mixture into sodium chloride solution, soaking for 0.5-2h, filtering, washing with deionized water, and drying to obtain pretreated zeolite.
3. The method for preparing the modified zeolite-based coal coking industrial wastewater purifying agent according to claim 2, wherein the step S1 specifically comprises:
s1-1, crushing natural zeolite to a mass fraction of more than 95% below 200 meshes, then adding the crushed natural zeolite into distilled water, soaking for 1h, filtering and drying;
s1-2, roasting for 3 hours at 250 ℃, and naturally cooling;
s1-3, adding the mixture into a sodium hydroxide solution with the concentration of 0.5mol/L, soaking for 2 hours, filtering, and cleaning with deionized water;
s1-4, adding the mixture into a sodium chloride solution with the concentration of 0.5mol/L, soaking for 1h, filtering, washing with deionized water, and drying to obtain pretreated zeolite.
4. The method for preparing a modified zeolite-based coal coking industrial wastewater purifier according to claim 2 or 3, wherein the step S2 specifically comprises:
s2-1, adding pretreated zeolite into ethanol, soaking for 5-20min, filtering, then adding into deionized water, and performing ultrasonic treatment for 10-30min to obtain zeolite dispersion;
s2-2, 0.01-0.05mol Fe (NO) 3 ) 3 ·9H 2 O、0.005-0.03mol Ce(NO 3 ) 3 ·6H 2 Dissolving O in 150mL deionized water, adding the obtained solution into zeolite dispersion, stirring for 5-30min, and then adding 20-100mL NaOH solution with concentration of 1.0M under stirring to obtain a mixture;
s2-3, transferring the mixture into a reaction kettle, reacting for 4-12h at 160-240 ℃, drying after the reaction is finished, and calcining for 2-6h at 400-600 ℃ in nitrogen atmosphere to obtain the modified Fe 3 O 4 -CeO 2 Zeolite of composite particles.
5. The method for preparing a modified zeolite-based coal coking industrial wastewater purifying agent according to claim 4, wherein the step S2 specifically comprises:
s2-1, adding pretreated zeolite into ethanol, soaking for 10min, filtering, then adding into deionized water, and performing ultrasonic treatment for 20min to obtain zeolite dispersion;
s2-2, 0.02mol of Fe (NO) 3 ) 3 ·9H 2 O、0.015Ce(NO 3 ) 3 ·6H 2 Dissolving O in 150mL of deionized water, adding the obtained solution into zeolite dispersion, stirring for 15min, and then adding 50mL of NaOH solution with the concentration of 1.0M under stirring to obtain a mixture;
s2-3, transferring the mixture into a reaction kettle, reacting for 6 hours at 220 ℃, drying after the reaction is finished, and calcining for 4 hours at 480 ℃ in nitrogen atmosphere to obtain the modified Fe 3 O 4 -CeO 2 Zeolite of composite particles.
6. The method for preparing a modified zeolite-based coal coking industrial wastewater purifying agent according to claim 5, wherein in the step S2-2, raw materials are added according to a mass ratio of Fe to zeolite of 3:2.
7. The method for preparing a modified zeolite-based coal coking industrial wastewater purifying agent according to claim 4, wherein the step S3 specifically comprises:
s3-1, preparing photocatalytic particles:
s3-1-1, adding folic acid, thiourea and ethylenediamine into deionized water, and performing ultrasonic treatment for 2-10min to obtain a precursor solution;
s3-1-2, adding the precursor solution into a reaction kettle of a polytetrafluoroethylene substrate, and reacting for 3-12h at 160-230 ℃;
s3-1-3, naturally cooling after the reaction is finished, filtering by using a filter membrane, dialyzing filtrate in deionized water for 6-24h by using a dialysis bag with the molecular weight cut-off of 600-1200D, collecting dialysate in the dialysis bag, and freeze-drying to obtain the S, N doped carbon dots, namely the photocatalytic particles;
s3-2, in modification of Fe 3 O 4 -CeO 2 Grafting photocatalytic particles on zeolite of the composite particles:
s3-2-1, adding the photocatalytic particles prepared in the step S3-1 into deionized water, and performing ultrasonic treatment for 10-30min to prepare a photocatalytic particle dispersion liquid;
s3-2-2, modified Fe prepared in step S2 3 O 4 -CeO 2 Adding zeolite of composite particles into ethanol water solution, soaking for 1-4h, filtering, and drying;
s3-2-3, modified Fe obtained in step S3-2-2 3 O 4 -CeO 2 Adding zeolite of composite particles into the photocatalytic particle dispersion liquid obtained in the step S3-2-1, adding EDCI, oscillating for 6-24 hours at 55-95 ℃, filtering, sequentially cleaning with ethanol and deionized water, and drying to obtain the composite modified zeolite.
8. The method for preparing a modified zeolite-based coal coking industrial wastewater purifying agent according to claim 7, wherein the step S3 specifically comprises:
s3-1, preparing photocatalytic particles:
s3-1-1, adding 6.2g of folic acid, 4.7g of thiourea and 2.5g of ethylenediamine into 180mL of deionized water, and performing ultrasonic treatment for 5min to obtain a precursor liquid;
s3-1-2, adding the precursor solution into a 200mL polytetrafluoroethylene substrate reaction kettle, and reacting for 6 hours at 190 ℃;
s3-1-3, naturally cooling after the reaction is finished, filtering with a filter membrane with the molecular weight cut-off of 0.25 mu m, dialyzing filtrate in deionized water for 12 hours with a dialysis bag with the molecular weight cut-off of 800D, collecting dialysate in the dialysis bag, and freeze-drying to obtain the S, N doped carbon dots, namely the photocatalytic particles;
s3-2, in modification of Fe 3 O 4 -CeO 2 Grafting photocatalytic particles on zeolite of the composite particles:
s3-2-1, adding the photocatalytic particles prepared in the step S3-1 into deionized water, and performing ultrasonic treatment for 20min to prepare a photocatalytic particle dispersion liquid with the concentration of 2 mg/mL;
s3-2-2, modified Fe prepared in step S2 3 O 4 -CeO 2 Adding zeolite of the composite particles into ethanol water solution, soaking for 2h, filtering and drying;
s3-2-3, modified Fe obtained in step S3-2-2 3 O 4 -CeO 2 Adding zeolite of composite particles into the photocatalytic particle dispersion liquid obtained in the step S3-2-1, adding EDCI, oscillating for 12 hours at 75 ℃, filtering, sequentially cleaning with ethanol and deionized water, and drying to obtain the composite modified zeolite.
9. The method for preparing a modified zeolite-based coal coking industrial wastewater purifying agent according to claim 8, wherein in the step S3-2-2, fe is modified according to the following steps 3 O 4 -CeO 2 Zeolite of composite particles: the mass ratio of the photocatalytic particles is 10:1-10:3.5, and the raw materials are added.
10. The method for preparing the modified zeolite-based coal coking industrial wastewater purifying agent according to claim 1, wherein the step S4 specifically comprises the following steps: the composite modified zeolite and polymeric ferric sulfate and polymeric aluminum chloride are compounded according to the mass ratio: polymeric ferric sulfate: polyaluminum chloride=1:0.8:0.5, heating for 2 hours at 95 ℃, and grinding until the mass ratio below 200 meshes is more than 95%, thus obtaining the water purifying agent.
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