CN117358206A - Heavy metal adsorbent for river channel deep treatment and preparation process thereof - Google Patents
Heavy metal adsorbent for river channel deep treatment and preparation process thereof Download PDFInfo
- Publication number
- CN117358206A CN117358206A CN202311343395.0A CN202311343395A CN117358206A CN 117358206 A CN117358206 A CN 117358206A CN 202311343395 A CN202311343395 A CN 202311343395A CN 117358206 A CN117358206 A CN 117358206A
- Authority
- CN
- China
- Prior art keywords
- heavy metal
- solid waste
- waste powder
- metal adsorbent
- biomass carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003463 adsorbent Substances 0.000 title claims abstract description 59
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000002028 Biomass Substances 0.000 claims abstract description 90
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 72
- 239000002910 solid waste Substances 0.000 claims abstract description 54
- 239000000843 powder Substances 0.000 claims abstract description 52
- 239000002131 composite material Substances 0.000 claims abstract description 51
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002994 raw material Substances 0.000 claims abstract description 34
- 239000002245 particle Substances 0.000 claims abstract description 20
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims abstract description 20
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 17
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 17
- 239000000661 sodium alginate Substances 0.000 claims abstract description 17
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims abstract description 9
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims abstract description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001263 FEMA 3042 Substances 0.000 claims abstract description 9
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims abstract description 9
- 229960000686 benzalkonium chloride Drugs 0.000 claims abstract description 9
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229940033123 tannic acid Drugs 0.000 claims abstract description 9
- 235000015523 tannic acid Nutrition 0.000 claims abstract description 9
- 229920002258 tannic acid Polymers 0.000 claims abstract description 9
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 54
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 23
- 239000010902 straw Substances 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 239000010881 fly ash Substances 0.000 claims description 12
- 239000002893 slag Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000004115 Sodium Silicate Substances 0.000 claims description 11
- 239000010813 municipal solid waste Substances 0.000 claims description 11
- 239000010451 perlite Substances 0.000 claims description 11
- 235000019362 perlite Nutrition 0.000 claims description 11
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 11
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 10
- 239000012498 ultrapure water Substances 0.000 claims description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- DCPMPXBYPZGNDC-UHFFFAOYSA-N hydron;methanediimine;chloride Chemical compound Cl.N=C=N DCPMPXBYPZGNDC-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 6
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 6
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 244000068988 Glycine max Species 0.000 claims description 6
- 235000010469 Glycine max Nutrition 0.000 claims description 6
- 241000209140 Triticum Species 0.000 claims description 6
- 235000021307 Triticum Nutrition 0.000 claims description 6
- 240000008042 Zea mays Species 0.000 claims description 6
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 6
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 6
- 238000013329 compounding Methods 0.000 claims description 6
- 235000005822 corn Nutrition 0.000 claims description 6
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 6
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 6
- XNCMOUSLNOHBKY-UHFFFAOYSA-H iron(3+);trisulfate;heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XNCMOUSLNOHBKY-UHFFFAOYSA-H 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 6
- SHFGJEQAOUMGJM-UHFFFAOYSA-N dialuminum dipotassium disodium dioxosilane iron(3+) oxocalcium oxomagnesium oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Na+].[Na+].[Al+3].[Al+3].[K+].[K+].[Fe+3].[Fe+3].O=[Mg].O=[Ca].O=[Si]=O SHFGJEQAOUMGJM-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 241000609240 Ambelania acida Species 0.000 claims description 4
- 235000017060 Arachis glabrata Nutrition 0.000 claims description 4
- 244000105624 Arachis hypogaea Species 0.000 claims description 4
- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 4
- 235000018262 Arachis monticola Nutrition 0.000 claims description 4
- 239000010905 bagasse Substances 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 235000020232 peanut Nutrition 0.000 claims description 4
- PWKSKIMOESPYIA-UHFFFAOYSA-N 2-acetamido-3-sulfanylpropanoic acid Chemical compound CC(=O)NC(CS)C(O)=O PWKSKIMOESPYIA-UHFFFAOYSA-N 0.000 claims description 2
- 238000012423 maintenance Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 23
- 230000000694 effects Effects 0.000 abstract description 14
- 239000011574 phosphorus Substances 0.000 abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 11
- 150000008442 polyphenolic compounds Chemical class 0.000 abstract description 6
- 235000013824 polyphenols Nutrition 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract description 5
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 abstract description 5
- -1 phosphorus ions Chemical class 0.000 abstract description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 3
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- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
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- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 3
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 3
- 239000010457 zeolite Substances 0.000 abstract description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract 1
- 108091006146 Channels Proteins 0.000 description 14
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- 239000004201 L-cysteine Substances 0.000 description 6
- 235000013878 L-cysteine Nutrition 0.000 description 6
- 239000002957 persistent organic pollutant Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
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- 238000001782 photodegradation Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
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- 229910001431 copper ion Inorganic materials 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000006177 thiolation reaction Methods 0.000 description 3
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 108010052164 Sodium Channels Proteins 0.000 description 2
- 102000018674 Sodium Channels Human genes 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
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- 239000010802 sludge Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- 238000004131 Bayer process Methods 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
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- 230000008094 contradictory effect Effects 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
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- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 150000007944 thiolates Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
Classifications
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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
- B01J20/22—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
-
- 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
- C02F2101/105—Phosphorus compounds
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- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention relates to the technical field of heavy metal adsorption, in particular to a heavy metal adsorbent for river channel deep treatment and a preparation process thereof, wherein solid waste powder and biomass raw materials are selected as preparation raw materials; the mass ratio and the particle size ratio of the solid waste powder are controlled; thiolating the solid waste powder; biomass raw materials are pyrolyzed to generate biomass porous carbon, the biomass porous carbon is compounded with magnetic ferric oxide, a bimetal layered substance is loaded on the surface of the biomass porous carbon, tannic acid and benzalkonium chloride are utilized to generate polyphenol substances, and a zeolite imidazole framework with a core-shell structure is generated on the magnetic composite biomass carbon in situ by taking the polyphenol coating as an interface layer, so that the composite biomass carbon is obtained; sodium alginate is used as a raw material, and methacryloxyethyl trimethyl ammonium chloride, acrylamide and 2-acrylamido-2-methyl-1-propane sulfonic acid are used as monomers, so that the amphoteric sodium alginate-based copolymer is prepared through free radical polymerization, and the adsorption effect of the adsorbent on ammonium and phosphorus ions is effectively improved.
Description
Technical Field
The invention relates to the technical field of heavy metal adsorption, in particular to a heavy metal adsorbent for river deep treatment and a preparation process thereof.
Background
With the development of society, the domestic sewage and industrial wastewater which are not treated or still do not meet the emission standard after being treated are discharged, organic pollutants can be gradually deposited through adsorption, precipitation, flocculation and the like when the self-purification capability of the water body is exceeded, black and odorous substrate sludge in a river channel is formed after dissolved oxygen of the water body is consumed, heavy metals in an industrial pollution site can enter the river channel along with rainfall and surface runoff, and extremely toxic heavy metals such as lead, cadmium, mercury, copper and the like in the river channel are caused to exceed the standard, so that the life health of human beings is seriously influenced.
The adoption of the adsorbent for deep treatment of the river channel is a widely adopted means at present, and the raw materials of the adsorbent mainly comprise activated carbon, bentonite, adsorption resin and the like, and the adsorbent mainly adsorbs pollutants such as organic matters, pigments, heavy metals and the like in the river channel by physical action such as large specific surface area, high porosity, surface charge and the like, but has the problems of single function, unsatisfactory adsorption effect, large sludge amount and the like.
Disclosure of Invention
The invention aims to provide a heavy metal adsorbent for river deep treatment and a preparation process thereof.
In order to solve the technical problems, the invention provides the following technical scheme:
the preparation process of the heavy metal adsorbent for river deep treatment comprises the following steps:
s1: mixing sulfhydrylation solid waste powder, composite biomass carbon, modified sodium alginate, expanded perlite, sodium silicate and deionized water, and granulating to obtain a blank;
s2: and curing the blank to obtain the heavy metal adsorbent for river deep treatment.
Further, the working conditions of maintenance are as follows: standing for 5-6h, heating to 60deg.C, and maintaining at 80% humidity for 1-2h; heating to 90deg.C, humidity of 90%, holding for 2-3 hr, heating to 120deg.C, humidity of 80%, and holding for 1-2 hr; cooling to 18-25deg.C.
Further, the green body comprises the following raw materials in parts by weight: 22-26 parts of sulfhydrylation solid waste powder, 28-32 parts of composite biomass carbon, 1-3 parts of modified sodium alginate, 3-7 parts of expanded perlite, 1-2 parts of sodium silicate and 1-3 parts of deionized water.
Further, the preparation of the sulfhydrylation solid waste powder comprises the following steps: soaking the solid waste powder in sodium hydroxide for 10-12h, taking out, drying, adding deionized water, carbodiimide hydrochloride, N-hydroxysuccinimide and L-cysteine, mixing, heating to 90-100 ℃ and preserving heat for 2-4h to obtain the sulfhydrylation solid waste powder.
Further, the solid waste powder is prepared from fly ash, red mud and garbage incinerator slag according to the mass ratio of 1:2: and 3, compounding to obtain the product.
Further, the particle size of the fly ash is 20-30 mu m, the particle size of the red mud is 10-15 mu m, and the particle size of the garbage incinerator slag is 5-10 mu m.
Further, the preparation of the composite biomass carbon comprises the following steps:
1) Under nitrogen atmosphere, heating the biomass raw material to 240 ℃ and preserving heat for 2 hours, grinding, and sieving with a 100-150 mesh sieve to obtain biomass carbon;
2) Mixing biomass carbon, ferric sulfate heptahydrate, ferric chloride hexahydrate and deionized water, adding sodium hydroxide to enable the pH of the solution to be 9.8-10.2, stirring for 40-50min, washing, filtering, drying, transferring into a mixed solution of zinc nitrate hexahydrate and aluminum nitrate nonahydrate, and performing ultrasonic dispersion for 1-2h to obtain magnetic composite biomass carbon;
3) Mixing tannic acid, ultrapure water and sodium hydroxide solution, adding mixed solution of benzalkonium chloride and ultrapure water, centrifuging, washing, and freeze-drying to obtain modified tannic acid;
4) Mixing magnetic composite biomass carbon, modified tannic acid and methanol, adding a mixed solution of zinc nitrate, 2-methylimidazole and anhydrous methanol, and preserving the temperature at 100 ℃ for 10-12 hours to obtain the composite biomass carbon.
Further, the biomass raw material is one or more of wheat straw, corn straw, soybean straw, peanut shell and bagasse fiber.
Further, the preparation of the modified sodium alginate comprises the following steps:
heating chloridized-1-butyl-3-methylimidazole to 80 ℃ in nitrogen atmosphere, adding sodium alginate and potassium persulfate, stirring, adding methacryloxyethyl trimethyl ammonium chloride, acrylamide and 2-acrylamido-2-methyl-1-propane sulfonic acid, preserving heat for 2-3 hours at 75-80 ℃, cooling, soaking in absolute ethyl alcohol for 4 hours, centrifuging, washing, dialyzing with deionized water for 36 hours, and drying to obtain modified sodium alginate.
The invention has the beneficial effects that:
the method for preparing the heavy metal adsorbent by the existing technology has the advantages of high energy consumption, complex technology and poor adsorption effect on heavy metal, and the method is simple in technology, low in energy consumption, environment-friendly, recyclable and capable of effectively improving pollution conditions of a river channel when being used for deep treatment of the river channel, and the method is used for preparing the baking-free heavy metal adsorbent with high-efficiency heavy metal adsorption capacity and phosphorus and nitrogen removal capacity by adjusting raw materials and technology.
According to the invention, solid waste powder such as fly ash, red mud and garbage incineration slag are selected as preparation raw materials, biomass raw materials such as wheat straw, corn straw, soybean straw, peanut shell, bagasse fiber and the like are used as preparation raw materials, the existing green production requirements are met, the effect of reducing cost and enhancing efficiency is achieved, the solid waste powder can be effectively proportioned with composite sodium alginate when preparing spherical heavy metal adsorbent by controlling the mass ratio and the particle size ratio of the solid waste powder, so that the structural stability of the heavy metal adsorbent is improved, the heavy metal adsorption capacity of the heavy metal adsorbent is improved, the solid waste powder can be effectively improved for solid-liquid separation, the removal process is simplified, hydrated calcium silicate is generated in a river channel, and the heavy metal ions, inorganic and organic pollutants are well removed, so that the purposes of recycling the solid waste and treating the river channel pollution are achieved;
in order to improve the uniformity of the dispersion of the solid waste powder in the heavy metal adsorbent, the solid waste powder is treated by sodium hydroxide, carbodiimide hydrochloride, N-hydroxysuccinimide and L-cysteine in sequence, so that the solid waste powder is thiolated, the homogenization of the heavy metal adsorbent is improved, and meanwhile, the thiolation energy can be used for synergistically improving the adsorption force of the solid waste powder on metal lead, chromium, copper and the like.
Biomass raw materials are selected to prepare biomass porous carbon, so that the adsorbent is light, and the biomass raw materials such as wheat straw, corn straw, soybean straw, peanut shells and bagasse fibers used in the method are main agricultural byproducts, most of the biomass raw materials are discarded and directly combusted, so that the utilization rate is low;
in order to improve the heavy metal adsorption capacity of biomass porous carbon, biomass raw materials are pyrolyzed to generate biomass porous carbon, a bimetal layered substance is loaded on the surface of the biomass porous carbon after the biomass porous carbon is compounded with magnetic ferric oxide, tannic acid and benzalkonium chloride are utilized to generate polyphenol substances, a zeolite imidazole skeleton with a core-shell structure is generated on the magnetic composite biomass carbon in situ in a mode that the polyphenol coating is used as a medium layer, and the composite biomass carbon is obtained, so that the photodegradation activity of the biomass porous carbon under visible light is enhanced, and the photodegradation efficiency of an adsorbent is improved; the composite biomass carbon has the effects of simultaneously adsorbing heavy metals and organic pollutants, the adsorbent has the advantages of small dosage, high adsorption speed and the like, and meanwhile, the magnetism in the composite biomass carbon enables the composite biomass carbon to be easily separated from a liquid medium, so that the recovery performance of the adsorbent is enhanced, and the effect of circulating purification is achieved.
In the invention, sodium alginate is used as a binder, so that a composite effect is achieved on solid waste powder and composite biomass carbon, the bonding strength between adsorbent raw materials is improved, particles are not easy to loosen, and the sediment amount is reduced; in order to improve the removal capability of the adsorbent to nitrogen and phosphorus pollutants in a river channel, sodium alginate is used as a raw material, methacryloxyethyl trimethyl ammonium chloride, acrylamide and 2-acrylamido-2-methyl-1-propane sulfonic acid are used as monomers, and the amphoteric sodium alginate-based copolymer is prepared through free radical polymerization, so that the adsorption effect of the adsorbent to ammonium and phosphorus ions is effectively improved.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that, if the embodiment of the present invention and the embodiments thereof involve directional indications such as up, down, left, right, front, and rear … …, the directional indication is merely used to explain a relative positional relationship, a movement condition, and the like between a specific posture such as the components, and if the specific posture is changed, the directional indication is changed accordingly. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent and not within the scope of protection claimed in the present invention.
The following description of the embodiments of the present invention will be presented in further detail with reference to the examples, which should be understood as being merely illustrative of the present invention and not limiting.
Example 1: the preparation process of the heavy metal adsorbent for river deep treatment comprises the following steps:
s1: mixing sulfhydrylation solid waste powder, composite biomass carbon, modified sodium alginate, expanded perlite, sodium silicate and deionized water, and granulating to obtain a blank;
the green body comprises the following raw materials in parts by weight: 22 parts of sulfhydrylation solid waste powder, 28 parts of composite biomass carbon, 1 part of modified sodium alginate, 3 parts of expanded perlite, 1 part of sodium silicate and 1 part of deionized water;
the preparation of the sulfhydrylation solid waste powder comprises the following steps: 10g of solid waste powder is put into 10% sodium hydroxide to be soaked for 10h, taken out and dried, 100mL of deionized water, 2g of carbodiimide hydrochloride, 1g of N-hydroxysuccinimide and L-cysteine are added to be mixed, and the temperature is raised to 90 ℃ and kept for 4h, so that sulfhydrylation solid waste powder is obtained;
the solid waste powder is prepared from fly ash, red mud and garbage incinerator slag in a mass ratio of 1:2:3, compounding to obtain the compound;
the particle size of the fly ash is 20 mu m, the particle size of the red mud is 10 mu m, and the particle size of the garbage incinerator slag is 5 mu m;
the preparation of the composite biomass carbon comprises the following steps:
1) Under nitrogen atmosphere, heating the biomass raw material to 240 ℃ and preserving heat for 2 hours, grinding, and sieving with a 100-mesh sieve to obtain biomass carbon;
2) Mixing 0.5g of biomass carbon, 1.39g of ferric sulfate heptahydrate, 2.03g of ferric chloride hexahydrate and 100mL of deionized water, adding sodium hydroxide to enable the pH of the solution to be 9.8, stirring for 40min, washing, filtering, drying, transferring into a mixed solution of 0.1mol/L zinc nitrate hexahydrate and 0.1mol/L aluminum nitrate nonahydrate, and performing ultrasonic dispersion for 1h to obtain magnetic composite biomass carbon;
3) Mixing 0.075g tannic acid, 3mL of ultrapure water and 200 mu L of 0.05mol/L sodium hydroxide solution, adding a mixed solution of 0.074g of benzalkonium chloride and 3mL of ultrapure water, centrifuging, washing and freeze-drying to obtain modified tannic acid;
4) Mixing 0.5g of magnetic composite biomass carbon, 0.1g of modified tannic acid and 30mL of methanol, adding a mixed solution of 1.0g of zinc nitrate, 4.4g of 2-methylimidazole and 50mL of anhydrous methanol, and preserving the temperature at 100 ℃ for 10 hours to obtain composite biomass carbon;
the biomass raw material is wheat straw;
the preparation of the modified sodium alginate comprises the following steps:
under nitrogen atmosphere, 5g of chloridized-1-butyl-3-methylimidazole is heated to 80 ℃, 0.5g of sodium alginate and 0.015g of potassium persulfate are added to be stirred, 0.15g of methacryloyloxyethyl trimethyl ammonium chloride, 0.05g of acrylamide and 0.1g of 2-acrylamido-2-methyl-1-propane sulfonic acid are added, the temperature is kept at 75 ℃ for 3 hours, cooling is carried out, the mixture is placed in absolute ethyl alcohol to be soaked for 4 hours, centrifuged and washed, deionized water is used for dialysis for 36 hours, and the mixture is dried to obtain modified sodium alginate;
s2: curing the blank: standing for 5h, heating to 60 ℃, keeping the humidity at 80%, and keeping for 1h; heating to 90 ℃, keeping the humidity at 90% for 2 hours, heating to 120 ℃, keeping the humidity at 80% for 1 hour; and cooling to 18 ℃ to obtain the heavy metal adsorbent for river deep treatment.
Example 2: the preparation process of the heavy metal adsorbent for river deep treatment comprises the following steps:
s1: mixing sulfhydrylation solid waste powder, composite biomass carbon, modified sodium alginate, expanded perlite, sodium silicate and deionized water, and granulating to obtain a blank;
the green body comprises the following raw materials in parts by weight: 23 parts of sulfhydrylation solid waste powder, 30 parts of composite biomass carbon, 2 parts of modified sodium alginate, 5 parts of expanded perlite, 1.5 parts of sodium silicate and 2 parts of deionized water;
the preparation of the sulfhydrylation solid waste powder comprises the following steps: 10g of solid waste powder is put into 10% sodium hydroxide to be soaked for 11h, taken out and dried, 100mL of deionized water, 2g of carbodiimide hydrochloride, 1g of N-hydroxysuccinimide and L-cysteine are added to be mixed, and the temperature is raised to 95 ℃ and kept for 3h, so that sulfhydrylation solid waste powder is obtained;
the solid waste powder is prepared from fly ash, red mud and garbage incinerator slag in a mass ratio of 1:2:3, compounding to obtain the compound;
the particle size of the fly ash is 24 mu m, the particle size of the red mud is 12 mu m, and the particle size of the garbage incinerator slag is 6 mu m;
the preparation of the composite biomass carbon comprises the following steps:
1) Under nitrogen atmosphere, heating the biomass raw material to 240 ℃ and preserving heat for 2 hours, grinding, and sieving with a 120-mesh sieve to obtain biomass carbon;
2) Mixing 0.5g of biomass carbon, 1.39g of ferric sulfate heptahydrate, 2.03g of ferric chloride hexahydrate and 100mL of deionized water, adding sodium hydroxide to enable the pH of the solution to be 10, stirring for 45min, washing, filtering, drying, transferring into a mixed solution of 0.1mol/L zinc nitrate hexahydrate and 0.1mol/L aluminum nitrate nonahydrate, and performing ultrasonic dispersion for 1.5h to obtain magnetic composite biomass carbon;
3) Mixing 0.075g tannic acid, 3mL of ultrapure water and 200 mu L of 0.05mol/L sodium hydroxide solution, adding a mixed solution of 0.074g of benzalkonium chloride and 3mL of ultrapure water, centrifuging, washing and freeze-drying to obtain modified tannic acid;
4) Mixing 0.5g of magnetic composite biomass carbon, 0.1g of modified tannic acid and 30mL of methanol, adding a mixed solution of 1.0g of zinc nitrate, 4.4g of 2-methylimidazole and 50mL of anhydrous methanol, and preserving the temperature at 100 ℃ for 11 hours to obtain composite biomass carbon;
the biomass raw material is corn straw;
the preparation of the modified sodium alginate comprises the following steps:
under nitrogen atmosphere, 5g of chloridized-1-butyl-3-methylimidazole is heated to 80 ℃, 0.5g of sodium alginate and 0.015g of potassium persulfate are added and stirred, 0.15g of methacryloyloxyethyl trimethyl ammonium chloride, 0.05g of acrylamide and 0.1g of 2-acrylamido-2-methyl-1-propane sulfonic acid are added, the temperature is kept for 2.5h at 78 ℃, the mixture is cooled, and the mixture is placed in absolute ethyl alcohol for soaking for 4h, centrifuged and washed, dialyzed for 36h by deionized water and dried to obtain modified sodium alginate;
s2: curing the blank: standing for 5.5h, heating to 60 ℃ and keeping the humidity at 80% for 1.5h; heating to 90 deg.C, keeping the humidity at 90% for 2.5h, heating to 120 deg.C, keeping the humidity at 80% for 1.5h; and cooling to 20 ℃ to obtain the heavy metal adsorbent for river deep treatment.
Example 3: the preparation process of the heavy metal adsorbent for river deep treatment comprises the following steps:
s1: mixing sulfhydrylation solid waste powder, composite biomass carbon, modified sodium alginate, expanded perlite, sodium silicate and deionized water, and granulating to obtain a blank;
the green body comprises the following raw materials in parts by weight: 26 parts of sulfhydrylation solid waste powder, 32 parts of composite biomass carbon, 3 parts of modified sodium alginate, 7 parts of expanded perlite, 2 parts of sodium silicate and 3 parts of deionized water;
the preparation of the sulfhydrylation solid waste powder comprises the following steps: 10g of solid waste powder is put into 10% sodium hydroxide to be soaked for 12 hours, taken out and dried, 100mL of deionized water, 2g of carbodiimide hydrochloride, 1g of N-hydroxysuccinimide and L-cysteine are added to be mixed, and the temperature is raised to 100 ℃ and kept for 4 hours to obtain sulfhydrylation solid waste powder;
the solid waste powder is prepared from fly ash, red mud and garbage incinerator slag in a mass ratio of 1:2:3, compounding to obtain the compound;
the particle size of the fly ash is 30 mu m, the particle size of the red mud is 15 mu m, and the particle size of the garbage incinerator slag is 10 mu m;
the preparation of the composite biomass carbon comprises the following steps:
1) Under nitrogen atmosphere, heating the biomass raw material to 240 ℃ and preserving heat for 2 hours, grinding, and sieving with a 150-mesh sieve to obtain biomass carbon;
2) Mixing 0.5g of biomass carbon, 1.39g of ferric sulfate heptahydrate, 2.03g of ferric chloride hexahydrate and 100mL of deionized water, adding sodium hydroxide to enable the pH of the solution to be 10.2, stirring for 50min, washing, filtering, drying, transferring into a mixed solution of 0.1mol/L zinc nitrate hexahydrate and 0.1mol/L aluminum nitrate nonahydrate, and performing ultrasonic dispersion for 2h to obtain magnetic composite biomass carbon;
3) Mixing 0.075g tannic acid, 3mL of ultrapure water and 200 mu L of 0.05mol/L sodium hydroxide solution, adding a mixed solution of 0.074g of benzalkonium chloride and 3mL of ultrapure water, centrifuging, washing and freeze-drying to obtain modified tannic acid;
4) Mixing 0.5g of magnetic composite biomass carbon, 0.1g of modified tannic acid and 30mL of methanol, adding a mixed solution of 1.0g of zinc nitrate, 4.4g of 2-methylimidazole and 50mL of anhydrous methanol, and preserving the temperature at 100 ℃ for 12 hours to obtain composite biomass carbon;
the biomass raw material is soybean straw;
the preparation of the modified sodium alginate comprises the following steps:
under nitrogen atmosphere, 5g of chloridized-1-butyl-3-methylimidazole is heated to 80 ℃, 0.5g of sodium alginate and 0.015g of potassium persulfate are added to be stirred, 0.15g of methacryloyloxyethyl trimethyl ammonium chloride, 0.05g of acrylamide and 0.1g of 2-acrylamido-2-methyl-1-propane sulfonic acid are added, the temperature is kept for 2 hours at 80 ℃, the mixture is cooled, and the mixture is placed in absolute ethyl alcohol to be soaked for 4 hours, centrifuged and washed, dialyzed for 36 hours by deionized water and dried to obtain modified sodium alginate;
s2: curing the blank: standing for 6h, heating to 60 ℃, keeping the humidity at 80%, and keeping for 2h; heating to 90 ℃, keeping the humidity at 90% for 3 hours, heating to 120 ℃, keeping the humidity at 80% for 2 hours; cooling to 25 ℃ to obtain the heavy metal adsorbent for river deep treatment.
Comparative example 1: taking example 3 as a control group, and mixing fly ash, red mud and garbage incineration slag according to the mass ratio of 1:2:2, compounding, and other working procedures are normal.
Comparative example 2: with example 3 as a control group, the solid waste powder was used to replace the mercapto solid waste powder, and the other procedures were normal.
Comparative example 3: with example 3 as a control group, the magnetic composite biomass carbon was replaced with biomass carbon, and the other processes were normal.
Comparative example 4: with example 3 as a control group, modified tannic acid was not added, and the other steps were normal.
Comparative example 5: with example 3 as a control group, the magnetic composite biomass carbon was used to replace the composite biomass carbon, and the other processes were normal.
Comparative example 6: with example 3 as a control group, sodium alginate was used to replace modified sodium alginate, and the other procedures were normal.
The raw material sources are as follows:
expanded perlite T21400: shanghai Yuan Ye Biotech Co., ltd; carbodiimide hydrochloride E106172, N-hydroxysuccinimide N164062, L-cysteine C108237, ferric sulfate heptahydrate I434044, ferric chloride hexahydrate F419646, zinc nitrate hexahydrate Z111703, aluminum nitrate nonahydrate S492260, tannic acid T305809, benzalkonium chloride a194586, 2-methylimidazole M104839, sodium alginate S100126, methacryloxyethyl trimethylammonium chloride M102201, acrylamide a108467, 2-acrylamido-2-methyl-1-propane sulfonic acid a106798: ala Ding Shiji; fly ash: the main components are as follows: 51.2% of silicon dioxide, 27.21% of aluminum oxide, 5.4% of calcium oxide, 4.51% of ferric oxide and 0.12% of magnesium oxide; waste incineration slag: the main components are as follows: 57.2% of silicon dioxide, 6.21% of aluminum oxide, 4.31% of sodium oxide, 5.4% of calcium oxide, 4.51% of ferric oxide, 1.52% of magnesium oxide, 2.14% of phosphorus oxide, 1.3% of potassium oxide, 0.72% of sulfur trioxide and 0.52% of chlorine; red mud (bayer process red mud): guangxi Hua silver aluminum Co., ltd; wheat straw, corn straw, soybean straw, commercially available; chlorinated-1-butyl-3-methylimidazole 79917-90-1: nanjing Baimuda Biotechnology Co., ltd; sodium silicate, sodium hydroxide, methanol, potassium persulfate, absolute ethanol, analytically pure: national drug group reagent.
Performance test:
testing the adsorption capacity to copper ions: preparation of 100mL400mg/LCu 2+ Adding 10mg of adsorbent into the test solution, shaking uniformly and testing; testing the adsorption capacity to lead ions: preparation of 100mL100mg/LPb 2+ Adding 10mg of adsorbent into the test solution, shaking up and testing, wherein the removal rate D is (A 0 -A i )/A 0 ×100％；A 0 Is Cu 2+ Initial concentration, A i Is the concentration after adsorption;
preparing wastewater with COD value of 800mg/L and total phosphorus of 8mg/L, putting 10mg of adsorbent into 1L of wastewater, sampling and measuring COD value and total phosphorus concentration; the COD values of the sewage before and after adsorption are tested by using a COD ammonia nitrogen dual-parameter tester, and the total phosphorus reference GB11893-89 is measured by adopting an ammonium molybdate spectrophotometry; carrying out 50-time circulation experiments on the wastewater by using the prepared adsorbent, and then measuring the copper ion removal rate, wherein the experimental results are shown in the following table 1;
TABLE 1
As shown in Table 1, the total phosphorus degradation rate of the adsorbent prepared according to the invention reaches 96.1-96.6%, the lead ion removal rate is 98.7-99.4%, and the copper ion removal rate after 50 times of circulation is as high as 88.2-89.1%, which indicates that the green and environment-friendly recyclable baking-free heavy metal adsorbent prepared by the invention has high-efficiency heavy metal adsorption capacity and phosphorus and nitrogen removal capacity, and can effectively improve the pollution condition of river channels when being used for river channel deep treatment.
Compared with comparative example 1, the embodiment 3 has the advantages that the mass ratio and the particle size ratio of the solid waste powder are controlled, so that the solid waste powder can be effectively proportioned with the composite sodium alginate when the spherical heavy metal adsorbent is prepared, the structural stability of the heavy metal adsorbent is improved, the heavy metal adsorption capacity of the heavy metal adsorbent is improved, the solid waste powder can be effectively improved for solid-liquid separation, the removal process is simplified, calcium silicate hydrate is generated in a river channel, and the heavy metal ion and inorganic and organic pollutants are well removed, so that the purposes of recycling the solid waste and treating the river channel pollution are achieved;
example 3 is compared with comparative example 2, in order to improve the uniformity of dispersion of the solid waste powder in the heavy metal adsorbent, the solid waste powder is sequentially treated with sodium hydroxide, carbodiimide hydrochloride, N-hydroxysuccinimide and L-cysteine to thiolate the solid waste powder, so that the thiolation can be used for improving the uniformity of the heavy metal adsorbent and simultaneously, the thiolation can be used for assisting the solid waste powder to effectively improve the adsorption force of the heavy metal adsorbent on metallic lead, chromium, copper and the like.
In order to improve the heavy metal adsorption capacity of the biomass porous carbon, the biomass raw material is pyrolyzed to generate the biomass porous carbon, the biomass porous carbon is compounded with the magnetic ferric oxide and then is loaded with a bimetal layered substance on the surface of the biomass porous carbon, tannic acid and benzalkonium chloride are utilized to generate polyphenol substances, a zeolite imidazole skeleton with a core-shell structure is generated on the magnetic composite biomass carbon in situ by taking the polyphenol coating as a medium layer, and the composite biomass carbon is obtained, so that the photodegradation activity of the biomass porous carbon under visible light is enhanced, and the photodegradation efficiency of the adsorbent is improved; the composite biomass carbon has the effects of simultaneously adsorbing heavy metals and organic pollutants, the adsorbent has the advantages of small dosage, high adsorption speed and the like, and meanwhile, the magnetism in the composite biomass carbon enables the composite biomass carbon to be easily separated from a liquid medium, so that the recovery performance of the adsorbent is enhanced, and the effect of circulating purification is achieved.
Compared with the comparative example 6, the sodium alginate is used as the binder, has a composite effect on solid waste powder and composite biomass carbon, improves the bonding strength between adsorbent raw materials, ensures that particles are not easy to loosen, and reduces the sediment amount; in order to improve the removal capability of the adsorbent to nitrogen and phosphorus pollutants in a river channel, sodium alginate is used as a raw material, methacryloxyethyl trimethyl ammonium chloride, acrylamide and 2-acrylamido-2-methyl-1-propane sulfonic acid are used as monomers, and the amphoteric sodium alginate-based copolymer is prepared through free radical polymerization, so that the adsorption effect of the adsorbent to ammonium and phosphorus ions is effectively improved.
The foregoing description is only exemplary embodiments of the present invention and is not intended to limit the scope of the invention, and all equivalent structural changes made by the present invention or direct/indirect application in other related technical fields are included in the scope of the present invention.
Claims (9)
1. The preparation process of the heavy metal adsorbent for river deep treatment is characterized by comprising the following steps of:
s1: mixing sulfhydrylation solid waste powder, composite biomass carbon, modified sodium alginate, expanded perlite, sodium silicate and deionized water, and granulating to obtain a blank;
s2: maintaining the blank to obtain a heavy metal adsorbent for river deep treatment;
the green body comprises the following raw materials in parts by weight: 22-26 parts of sulfhydrylation solid waste powder, 28-32 parts of composite biomass carbon, 1-3 parts of modified sodium alginate, 3-7 parts of expanded perlite, 1-2 parts of sodium silicate and 1-3 parts of deionized water.
2. The process for preparing the heavy metal adsorbent for river deep treatment according to claim 1, wherein the working conditions of maintenance are as follows: standing for 5-6h, heating to 60deg.C, and maintaining at 80% humidity for 1-2h; heating to 90deg.C, humidity of 90%, holding for 2-3 hr, heating to 120deg.C, humidity of 80%, and holding for 1-2 hr; cooling to 18-25deg.C.
3. The process for preparing the heavy metal adsorbent for river deep treatment according to claim 1, wherein the preparation of the sulfhydrylation solid waste powder comprises the following steps: soaking the solid waste powder in sodium hydroxide for 10-12h, taking out, drying, adding deionized water, carbodiimide hydrochloride, N-hydroxysuccinimide and L-cysteine, mixing, heating to 90-100 ℃ and preserving heat for 2-4h to obtain the sulfhydrylation solid waste powder.
4. The preparation process of the heavy metal adsorbent for river deep treatment according to claim 3, wherein the solid waste powder comprises the following components in percentage by mass: 2: and 3, compounding to obtain the product.
5. The process for preparing heavy metal adsorbent for river deep treatment according to claim 4, wherein the particle size of fly ash is 20-30 μm, the particle size of red mud is 10-15 μm, and the particle size of garbage incinerator slag is 5-10 μm.
6. The process for preparing the heavy metal adsorbent for river depth treatment according to claim 1, wherein the preparation of the composite biomass carbon comprises the following steps:
1) Under nitrogen atmosphere, heating the biomass raw material to 240 ℃ and preserving heat for 2 hours, grinding, and sieving with a 100-150 mesh sieve to obtain biomass carbon;
2) Mixing biomass carbon, ferric sulfate heptahydrate, ferric chloride hexahydrate and deionized water, adding sodium hydroxide to enable the pH of the solution to be 9.8-10.2, stirring for 40-50min, washing, filtering, drying, transferring into a mixed solution of zinc nitrate hexahydrate and aluminum nitrate nonahydrate, and performing ultrasonic dispersion for 1-2h to obtain magnetic composite biomass carbon;
3) Mixing tannic acid, ultrapure water and sodium hydroxide solution, adding mixed solution of benzalkonium chloride and ultrapure water, centrifuging, washing, and freeze-drying to obtain modified tannic acid;
4) Mixing magnetic composite biomass carbon, modified tannic acid and methanol, adding a mixed solution of zinc nitrate, 2-methylimidazole and anhydrous methanol, and preserving the temperature at 100 ℃ for 10-12 hours to obtain the composite biomass carbon.
7. The process for preparing the heavy metal adsorbent for river deep treatment according to claim 6, wherein the biomass raw material is one or a mixture of more of wheat straw, corn straw, soybean straw, peanut shell and bagasse fiber.
8. The preparation process of the heavy metal adsorbent for river deep treatment according to claim 1, wherein the preparation of the modified sodium alginate comprises the following steps:
heating chloridized-1-butyl-3-methylimidazole to 80 ℃ in nitrogen atmosphere, adding sodium alginate and potassium persulfate, stirring, adding methacryloxyethyl trimethyl ammonium chloride, acrylamide and 2-acrylamido-2-methyl-1-propane sulfonic acid, preserving heat for 2-3 hours at 75-80 ℃, cooling, soaking in absolute ethyl alcohol for 4 hours, centrifuging, washing, dialyzing with deionized water for 36 hours, and drying to obtain modified sodium alginate.
9. A heavy metal adsorbent for river depth treatment, which is characterized by being prepared by the preparation process of any one of claims 1-8.
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