CN112094039A - Electroplating sewage sludge dewatering curing agent and preparation method thereof - Google Patents
Electroplating sewage sludge dewatering curing agent and preparation method thereof Download PDFInfo
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- CN112094039A CN112094039A CN202010979343.2A CN202010979343A CN112094039A CN 112094039 A CN112094039 A CN 112094039A CN 202010979343 A CN202010979343 A CN 202010979343A CN 112094039 A CN112094039 A CN 112094039A
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- polyethyleneimine
- molecular polymer
- amino
- sulfonated
- curing agent
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 54
- 238000009713 electroplating Methods 0.000 title claims abstract description 43
- 239000010801 sewage sludge Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 134
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 103
- 229920000642 polymer Polymers 0.000 claims abstract description 73
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 59
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 37
- 239000002114 nanocomposite Substances 0.000 claims abstract description 24
- 239000002131 composite material Substances 0.000 claims abstract description 22
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 20
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 20
- 239000004571 lime Substances 0.000 claims abstract description 20
- 239000011575 calcium Substances 0.000 claims abstract description 19
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 19
- 239000010881 fly ash Substances 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000004568 cement Substances 0.000 claims abstract description 14
- 229920000805 Polyaspartic acid Polymers 0.000 claims abstract description 13
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims abstract description 13
- 108010064470 polyaspartate Proteins 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 78
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 75
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 67
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 45
- 239000002041 carbon nanotube Substances 0.000 claims description 45
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 45
- 238000002156 mixing Methods 0.000 claims description 37
- 238000003756 stirring Methods 0.000 claims description 33
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- 239000004695 Polyether sulfone Substances 0.000 claims description 26
- 238000004140 cleaning Methods 0.000 claims description 26
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 26
- 229920006393 polyether sulfone Polymers 0.000 claims description 26
- 229920000090 poly(aryl ether) Polymers 0.000 claims description 25
- 102000004157 Hydrolases Human genes 0.000 claims description 24
- 108090000604 Hydrolases Proteins 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 239000012528 membrane Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000012153 distilled water Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 16
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 15
- 239000002105 nanoparticle Substances 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
- 238000002791 soaking Methods 0.000 claims description 15
- 239000011398 Portland cement Substances 0.000 claims description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 11
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 230000010355 oscillation Effects 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 108010029541 Laccase Proteins 0.000 claims description 9
- 241000222355 Trametes versicolor Species 0.000 claims description 9
- 125000003172 aldehyde group Chemical group 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 6
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 6
- 229910017912 NH2OH Inorganic materials 0.000 claims description 6
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 6
- 239000002122 magnetic nanoparticle Substances 0.000 claims description 6
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- 230000003750 conditioning effect Effects 0.000 claims description 5
- 238000007334 copolymerization reaction Methods 0.000 claims description 5
- 238000007872 degassing Methods 0.000 claims description 5
- 229920001519 homopolymer Polymers 0.000 claims description 5
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- 229910006297 γ-Fe2O3 Inorganic materials 0.000 claims description 5
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 4
- 102000004190 Enzymes Human genes 0.000 claims description 4
- 108090000790 Enzymes Proteins 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 3
- CIJQGPVMMRXSQW-UHFFFAOYSA-M sodium;2-aminoacetic acid;hydroxide Chemical compound O.[Na+].NCC([O-])=O CIJQGPVMMRXSQW-UHFFFAOYSA-M 0.000 claims description 3
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 2
- AEOCXXJPGCBFJA-UHFFFAOYSA-N ethionamide Chemical compound CCC1=CC(C(N)=S)=CC=N1 AEOCXXJPGCBFJA-UHFFFAOYSA-N 0.000 claims description 2
- 229920002530 polyetherether ketone Polymers 0.000 claims description 2
- -1 7-azabenzotriazole-1-yl Chemical group 0.000 claims 2
- 102000045595 Phosphoprotein Phosphatases Human genes 0.000 claims 1
- 108700019535 Phosphoprotein Phosphatases Proteins 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- 239000010802 sludge Substances 0.000 abstract description 58
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 12
- 239000002689 soil Substances 0.000 abstract description 11
- 150000002500 ions Chemical class 0.000 abstract description 10
- 208000005156 Dehydration Diseases 0.000 abstract description 8
- 230000018044 dehydration Effects 0.000 abstract description 8
- 238000006297 dehydration reaction Methods 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 7
- 239000004566 building material Substances 0.000 abstract description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000292 calcium oxide Substances 0.000 abstract description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000378 calcium silicate Substances 0.000 abstract description 2
- 229910052918 calcium silicate Inorganic materials 0.000 abstract description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 231100000481 chemical toxicant Toxicity 0.000 abstract 1
- 238000009396 hybridization Methods 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 239000003440 toxic substance Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 230000001965 increasing effect Effects 0.000 description 9
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 8
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000010865 sewage Substances 0.000 description 6
- 238000007711 solidification Methods 0.000 description 6
- 230000008023 solidification Effects 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 4
- 229910003145 α-Fe2O3 Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 239000011449 brick Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000003337 fertilizer Substances 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 235000015097 nutrients Nutrition 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 230000008635 plant growth Effects 0.000 description 3
- 108010012464 thiocyanate hydrolase Proteins 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
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- 239000011573 trace mineral Substances 0.000 description 2
- 235000013619 trace mineral Nutrition 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 108700023418 Amidases Proteins 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 241001464837 Viridiplantae Species 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 102000005922 amidase Human genes 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent 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
- OKTJSMMVPCPJKN-YPZZEJLDSA-N carbon-10 atom Chemical group [10C] OKTJSMMVPCPJKN-YPZZEJLDSA-N 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
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- 230000002708 enhancing effect Effects 0.000 description 1
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- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
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- 230000005389 magnetism Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
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- 239000000178 monomer Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 235000008935 nutritious Nutrition 0.000 description 1
- 239000003895 organic fertilizer Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
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- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/14—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents
- C02F11/148—Combined use of inorganic and organic substances, being added in the same treatment step
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/008—Sludge treatment by fixation or solidification
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
Abstract
The invention provides an electroplating sewage sludge dehydration curing agent and a preparation method thereof, wherein the curing agent comprises composite cement, lime, fly ash, aluminum sulfate, amino-functionalized magnetic multi-walled carbon nanotubes [ amino oximation-polyethyleneimine/sulfonated high-molecular polymer reinforced polyacrylonitrile ] immobilized hydrolase hybridization nano-composites, nano-calcium materials and polyaspartic acid. The optimal proportion exists between several substances in the curing agent and the amount of the composite cement, a certain amount of calcium oxide is contained in the fly ash and the lime, the volume of the cured sludge generates certain expansion in the curing process, the strength of the cured soil can be promoted when the expansion amount is proper, and the formed cementation effect of hydrated calcium silicate among the sludge is destroyed when the expansion effect is too large, and the strength is reduced on the contrary; the curing agent provided by the invention can remove organic toxic chemical substances in sludge, and solidify and retain heavy metal ions to obtain a building material with good mechanical property and capable of recycling waste.
Description
Technical Field
The invention belongs to the technical field of water treatment sludge curing agents, and particularly relates to an electroplating sewage sludge dehydration curing agent and a preparation method thereof.
Background
The electroplating sewage sludge has complex components and contains a large amount of microorganisms, pathogens, heavy metals, organic pollutants and the like. The sludge mass usually accounts for 0.3-0.5% of the sewage amount, and the sludge amount can be increased by 0.5-1 time in advanced treatment. At present, the electroplating sewage treatment plant in China discharges 30 x 104 tons of dry sludge every year, and the dry sludge is increased by about 10% every year. Because of small particles, difficult dehydration, low bearing capacity, high organic matter content, high fluidity and the like, the sludge or the sludge cannot be directly used as engineering filling in sea filling engineering, embankment engineering and road engineering. The sludge is utilized as a geotechnical material by a solidification treatment technology or used as a pretreatment means of landfill disposal, so that a series of problems in sludge treatment can be solved. The development of efficient sludge curing agents is the key to the treatment process.
The conventional method at home and abroad is to add a large amount of fillers such as sandy soil and the like in the sludge landfill process, but the sludge landfill cost is greatly increased, and the effective utilization rate of a landfill site is reduced. In recent years, researches show that the mechanical property of the landfill soil can be better improved by adding composite cement, fly ash and lime into the electroplating sewage sludge, and after solidification pretreatment of the electroplating sewage sludge, the electroplating sewage sludge can be landfilled after a period of time of maintenance, so that the safety of the landfill treatment can be greatly improved.
For the solidification treatment of sludge and silt, cement, lime and the like are generally adopted as a curing agent at present, for example, in chinese patent 201510874164.1. The ordinary cement and the lime are slow in setting and hardening, the ordinary cement and the lime partially settle before being set under the condition of high water-to-solid ratio, the sludge has high organic matter content, hydration reaction of the cement is hindered, and the setting effect is poor or even impossible. In addition, cement is incorporated in high amounts as a curing agent.
Disclosure of Invention
Aiming at the defects, the invention provides a curing agent which has strong permeability, high speed, small dosage, fast hardening and early strength of the formed curing agent, good curing effect, no reduction of later strength and capability of removing sludge odor; an electroplating sewage sludge dehydration curing agent for reducing the release of heavy metal and nitrogen and phosphorus to the environment and a preparation method thereof.
The invention provides the following technical scheme: the electroplating sewage sludge dewatering curing agent comprises, by mass, 1 (0.222-0.556), 0.444-0.778, 0.111-0.333, 0.022-0.111, 0.007-0.022, 0.0002-0.0009, lime, fly ash, aluminum sulfate, an amino-functionalized magnetic multi-walled carbon nanotube [ amino oximation-polyethyleneimine/sulfonated high-molecular polymer reinforced polyacrylonitrile ] immobilized hydrolase hybrid nano-composite, a nano-calcium material and polyaspartic acid, wherein the amino-functionalized magnetic multi-walled carbon nanotube [ amino-oximation-polyethyleneimine/sulfonated high-molecular polymer reinforced polyacrylonitrile ] immobilized hydrolase hybrid nano-composite comprises the following components in parts by weight:
the preparation method of the amino-functionalized magnetic multi-walled carbon nanotube [ amino oximation-polyethyleneimine/sulfonated high-molecular polymer reinforced polyacrylonitrile ] immobilized hydrolase hybrid nano compound comprises the following steps:
s1: mixing the polyethyleneimine/sulfonated high-molecular polymer reinforced polyacrylonitrile, the benzoyl peroxide and the xylene, uniformly stirring at the rotating speed of 30-60 rpm at the temperature of 28-35 ℃, standing at the temperature of 25-27 ℃ for 30-40 min, then adding 100-200 parts of deionized water, carrying out further graft copolymerization on the polyethyleneimine/sulfonated high-molecular polymer reinforced polyacrylonitrile in a water bath at the temperature of 80-85 ℃ for 0.5-1 h, then cleaning with distilled water for 1-2 times, and soaking with dimethylformamide for 2-3 h to remove impurity homopolymers to obtain a polyethyleneimine/sulfonated high-molecular polymer reinforced polyacrylonitrile copolymer;
s2: mixing said weight components of NH2OH & HCl is dissolved in deionized water to form NH with the concentration of 30 g/L-50 g/L2OH HCl solution with 0.1M Na2CO3Solution conditioning of the NH2The initial pH value of the OH & HCl solution is 6.5-7.5, and the initial pH value of the polyethyleneimine/sulfonated high molecular polymer reinforced polyacrylonitrile copolymer obtained in the step S1 is 6.5-7.5 NH2Performing ultrasonic vibration on OH & HCl solution at the frequency of 50 Hz-100 Hz for 5 min-10 min, and heating in water bath at the rotating speed of 200 rpm-250 rpm for 40 min-50 min at the temperature of 70-80 ℃ to obtain an aminooximation-polyethyleneimine/sulfonated high-molecular polymer reinforced polyacrylonitrile prepolymer;
s3: washing the amino oximation-sulfonated high molecular polymer reinforced polyacrylonitrile prepolymer obtained in the step S2 by deionized water until the pH value is 7, and drying under vacuum at 50-60 ℃ to obtain the amino oximation-polyethyleneimine/sulfonated high molecular polymer reinforced polyacrylonitrile copolymer;
s4: mixing the amino-functionalized magnetic multi-walled carbon nano-tube with the weight components, the amino-oximation-polyethyleneimine/sulfonated high molecular polymer reinforced polyacrylonitrile copolymer obtained in the step S3 and glutaraldehyde with the weight components, heating and dissolving the mixture for 1.5 to 1.8 hours at 40 to 50 ℃ by ultrasonic waves, continuously adding the O- (7-azabenzotriazole-1-yl) -N, N, N ', N' -tetramethylurea hexafluorophosphate serving as the weight component in the dissolving process, cleaning by adopting a Tris-HCl solution with the pH of 7-8 and the concentration of 40-50 mM or a glycine-sodium hydroxide solution with the pH of 9-10 at the temperature of 60-70 ℃, determining the optimal pH value of immobilization to form a magnetic multi-walled carbon nanotube [ amino oximation-polyethyleneimine/sulfonated high molecular polymer reinforced polyacrylonitrile ] solution of an aldehyde group activated end;
s5: and (2) mixing the hydrolase with the weight components with the solution of the magnetic multi-walled carbon nanotube at the aldehyde group activated end obtained in the step S4, slightly oscillating for 1h at the rotating speed of 30-50 rpm, then alternately cleaning for 3 times by using ethanol and distilled water, and filtering to obtain the amino-functionalized magnetic multi-walled carbon nanotube [ amino oximation-polyethyleneimine/sulfonated high-molecular polymer reinforced polyacrylonitrile ] immobilized hydrolase hybrid nano-composite.
Further, the hydrolase is one or more of coriolus versicolor laccase, thiocyanic acid hydrolase, biphenyl hydrolase, phosphatase and thioamide enzyme.
Further, the polyethyleneimine/sulfonated high molecular polymer reinforced polyacrylonitrile comprises the following components in parts by weight:
further, the sulfonated high molecular polymer is one or more of sulfonated polyether sulfone, sulfonated polystyrene, sulfonated polyarylether benzonitrile or sulfonated polyether ether ketone.
Further, the preparation method of the polyethyleneimine/sulfonated high molecular polymer reinforced polyacrylonitrile comprises the following steps:
a1: mixing the polyethylene glycol of the weight component with the dimethylformamide of the weight component to form a high molecular polymer solvent;
a2: mixing the polyacrylonitrile and the high molecular polymer solvent obtained in the step A1, stirring at the rotating speed of 500-600 rpm for 1.5-1.8 h at the temperature of 65-85 ℃, and degassing at the temperature of 25-27 ℃ for 3-4 h;
a3: mixing the mixture obtained in the step A2 with the sulfonated high molecular polymer, uniformly stirring at 50-70 ℃, forming a reticular film at 28-30 ℃, soaking the reticular film into isopropanol and deionized water with a volume ratio of 1:1 at 25 ℃, standing and solidifying to form the sulfonated high molecular polymer reinforced polyacrylonitrile reticular film;
a4: soaking the sulfonated high molecular polymer reinforced polyacrylonitrile reticular film obtained in the step A3 into LiOH solution with the concentration of 1.0M at the temperature of 40-45 ℃ to hydrolyze the sulfonated high molecular polymer reinforced polyacrylonitrile reticular film for 0.5-1 h, and forming the surface functionalized sulfonated high molecular polymer reinforced polyacrylonitrile reticular film with negative charge carboxyl;
a5: dissolving the weight component of trimesoyl chloride in the weight component of n-hexane to form a trimesoyl chloride solution; dissolving the polyethyleneimine according to the weight components in 50-100 parts of distilled water to form a polyethyleneimine solution with positive surface charge, immersing the carboxyl sulfonated high molecular polymer reinforced polyacrylonitrile reticular membrane with the surface functionalized and negative charge obtained in the step A4 in the polyethyleneimine solution with positive surface charge for 2-4 min, and immersing in the trimesoyl chloride solution for 1-3 min to obtain polyethyleneimine/sulfonated high molecular polymer reinforced polyacrylonitrile.
Further, the amino-functionalized magnetic multi-wall carbon nanotube comprises the following components in parts by weight:
15-22.5 parts of magnetic nanoparticles;
60-90 parts of carbon nanotubes;
50-60 parts of ethylenediamine. Amino acidification, amination
Further, the magnetic nano particles are magnetic alpha-Fe2O3Nanoparticle, magnetic gamma-Fe2O3Nanoparticles or magnetic Fe3O4Nanoparticles.
Further, the preparation method of the amino-functionalized magnetic multi-wall carbon nanotube comprises the following steps:
b1: immersing the carbon nano tubes in the weight components in 100ml of mixed acid solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 3:1, and refluxing for 20min to 30min at the temperature of 125 ℃ to 140 ℃ to form carbon nano tube suspension solution;
b2: b1, filtering the carbon nano tube suspension solution obtained in the step B at 25-27 ℃ in vacuum by using a filter membrane with the aperture of 0.20-0.25 μm, cleaning the carbon nano tube obtained by filtering to be neutral by using distilled water, and drying at 90-100 ℃ to obtain a dried oxidized carbon nano tube;
b3: dissolving the magnetic nano particles and the oxidized carbon nano tube obtained in the step B2 in a mixed solution of ethanol and water with the volume ratio of 1:1, performing ultrasonic oscillation for 0.5 to 0.8h at the temperature of 45 to 55 ℃ at 30 to 40MHz, then stirring for 24 to 48h at the temperature of 25 to 27 ℃ and the speed of 300 to 500rpm, then filtering by adopting a filter membrane with the aperture of 0.20 to 0.25 mu m, and performing summer drying for 3 to 5h at the temperature of 70 to 75 ℃ in vacuum to obtain the magnetic carbon nano tube;
b4: and B3, dissolving the magnetic carbon nano tube obtained in the step B in ethylenediamine with the weight components, performing ultrasonic oscillation for 0.3 to 0.5h at the temperature of between 45 and 55 ℃ at the frequency of between 35 and 45MHz, cleaning for 2 to 3 times by using formaldehyde, and drying for 0.3 to 0.5h at the temperature of between 60 and 70 ℃ in vacuum to obtain the amino functionalized magnetic multi-walled carbon nano tube.
Further, the composite cement is composite portland cement, and the particle size of the nano calcium material is smaller than 200 meshes.
The invention also provides a preparation method of the electroplating sewage sludge dehydration curing agent, which comprises the steps of mixing the composite cement, lime, fly ash, aluminum sulfate, amino-functionalized magnetic multi-walled carbon nanotubes [ amino oximation-polyethyleneimine/sulfonated high-molecular polymer reinforced polyacrylonitrile ] immobilized hydrolase hybrid nano-composite, nano-calcium material and polyaspartic acid in the mass ratio at room temperature, uniformly stirring, completing the oxidative polymerization reaction among raw materials, and grinding until the particle size is smaller than 200 meshes to obtain the electroplating sewage sludge dehydration curing agent.
The invention has the beneficial effects that:
1. in the polyethyleneimine/sulfonated high molecular polymer reinforced polyacrylonitrile in the amino-functionalized magnetic multi-walled carbon nanotube [ aminooximation-polyethyleneimine/sulfonated high molecular polymer reinforced polyacrylonitrile ] immobilized hydrolase hybrid nano compound, the sulfonated high molecular polymer is added, and the sulfonated high molecular polymer has unique surface migration effect and porous structure and shares the same-CN group with the surface of the polyacrylonitrile, so that the structure of the substrate is changed, the polyacrylonitrile substrate has smoother and hydrophilic effect, the porosity in the polypropylene substrate is further increased, the polypropylene substrate with smaller pore diameter can be obtained, and the porous structure can intercept and adsorb heavy metal ions, thereby reducing heavy metal residues in sludge;
in the interfacial polymerization process of using sulfonated high molecular polymer to reinforce polyacrylonitrile, negatively charged-SO exists on the sulfonated high molecular polymer chain3-The surface of the sulfonated high molecular polymer reinforced polyacrylonitrile can be modified by a layer of polyethyleneimine through the electrostatic adsorption action force of positive and negative charges, so that the surface of the polyethyleneimine/sulfonated high molecular polymer reinforced polyacrylonitrile is smoother and denser, bacteria in sewage are prevented from invading, the formed reticular film is damaged, and the interception and adsorption removal efficiency of heavy metal ions are avoided;
presence of negatively charged-SO in sulfonated high molecular weight polymer chain3-The groups enable the reinforced polyacrylonitrile reticular film to have better hydrophilicity, stability within a wider pH range, higher water permeability and lower pollution tendency.
2. Grafting and copolymerizing polyethyleneimine/sulfonated high-molecular polymer reinforced polyacrylonitrile to form polyethyleneimine/sulfonated high-molecular polymer reinforced polyacrylonitrile copolymer with more monomers, and then adopting NH2OH & HCl is dissolved in deionized water to form NH with the concentration of 30 g/L-50 g/L2OH & HCl solution, stretching-C.ident.N of polyacrylonitrile molecule, and reacting-OH and-NH2Grafted to the surface of polyacrylonitrile molecule, and makes amino oximation on the surface of polyacrylonitrile molecule so as to form HO-C [ identical to ] N-NH2When the curing agent is added to the electroplating sewage sludge, HO-C.ident.N-NH2O.and-NH in-OH in the terminal of (1)2Wherein N.is deprotonated, and the terminal forms- (HO-C.ident.N-NH)2) Structure of-formed O in-OH-2-and-NH2N of (A-C)2-Respectively with Cu2+、Pb2+、Hg2+、Ni2+And Zn2+The divalent heavy metal ions are subjected to complexation/chelation, so that the heavy metal ions are further chelated, fixed and intercepted, and are prevented from dissociating.
3. The sulfonated high molecular polymer is used for enhancing the interception of the sulfonated high molecular polymer in the polyacrylonitrile to heavy metal ions, and after the amino oximation of the polyacrylonitrile molecule surface, the O group is used for2And N is a group N2-The complexing/chelating action of heavy metal ions can retain most of heavy metal ions on the surface of a reticular film formed by [ amino oximation-polyethyleneimine/sulfonated high-molecular polymer reinforced polyacrylonitrile, so that the sludge solidified by the curing agent has stronger mechanical property and good leaching property, on one hand, the dissociation of the heavy metal ions in the sludge in the nature is avoided, the mechanical property of the finally solidified sludge as a building material is improved while the solidification action is achieved, and the environmental-friendly waste utilization of the electroplating sewage sludge is simultaneously carried out, thereby playing a role in three timesThe technical effect is obtained.
4. Will use magnetic alpha-Fe2O3Nanoparticle, magnetic gamma-Fe2O3Nanoparticles or magnetic Fe3O4The magnetic multi-wall carbon nano-tube prepared from the nano-particles has-NH after amino functionalization2The end can be further formed into the compound with-NH-CH through the action of glutaraldehyde and coupling agent O- (7-azabenzotriazole-1-yl) -N, N, N ', N' -tetramethylurea hexafluorophosphate2-CH2-CH2The end of aldehyde group of CHO, and then can decompose the phosphatase with organic chemical substance COD, BOD in the electroplating effluent of enzyme decomposition and release nitrogen phosphorus element with nutritious green plant, thiocyanic acid hydrolase and sulfenamidase of decomposing cyanide, biphenyl hydrolase and coriolus versicolor laccase of decomposing benzene organic matter such as phenol, can carry on the immobilization to the enzyme after decomposing organic chemical substance in the effluent, can carry on the magnetism to retrieve and purify, reuse, the magnetic multiwalled carbon nanotube used can increase the thermal insulation performance and heat conductivity of the building material after using this firming agent, and then can carry on the latent heat to the temperature in the building and store, release when having played energy conservation and needing.
5. The components of the curing agent are not required to be dissolved in advance before being added, and the powder is directly added and mechanically stirred to be uniformly mixed with the sludge. The curing agent of the invention applies the compounding synergistic principle, fully exerts the functions of the curing agent, the adsorbent, the binding agent and the conditioner, and ensures that the sludge is rapidly cured to achieve the aim of improving the environment.
When the composite portland cement is used for sludge solidification treatment, the aluminosilico-based vitreous body in the composite portland cement is subjected to lattice rearrangement or recrystallization under the excitation of a proper alkaline condition, namely, volcanic ash reaction, so that the strength is remarkably improved, the active inorganic material fly ash can form crystalline particles and a space net rack, the active inorganic material fly ash is used as a channel in the early stage and is favorable for removing moisture in sludge, and the active inorganic material fly ash is used as a framework in the later stage and is favorable for improving the strength of a solidification body.
The effect of lime is as follows: the calcium oxide is combined with part of water to form calcium hydroxide, and can also react with qualitative silicic acid or aluminum oxide. The pH value of the sludge is increased under the action of alkaline substances; the temperature of the sludge is increased by the exothermic reaction; free water is combined in the reaction product, and part of heat generated by the reaction can be evaporated; the temperature and pH value are increased to sterilize and passivate heavy metal ions.
The nano calcium material is a porous material, has huge specific surface area, high chemical activity and strong adsorption capacity, and has extremely strong adsorption and treatment capacity on phosphorus in the sludge; the nano material has strong diffusivity and quick permeation, so that the agent disclosed by the invention is quickly diffused into sludge, and the curing effect is good; the nano calcium can effectively control and change the key conditions of anaerobic odor generation, change the oxidation-reduction potential of the nano calcium, control the growth of anaerobic microorganisms and eliminate the source of the odor generation.
The polyaspartic acid is a green environment-friendly chemical, can chelate polyvalent metal ions such as calcium, magnesium, copper, iron and the like, can enrich nitrogen and phosphorus, and reduces the release of heavy metals and nitrogen and phosphorus nutrient elements in sludge to the environment. In addition, polyaspartic acid as a high polymer has stronger water absorption performance after being compounded with other components of a curing agent.
6. An optimal ratio exists between the quantity of the curing agent and the quantity of the composite cement, because the fly ash and the lime contain certain calcium oxide which can cause certain expansion of the volume of the cured sludge in the curing process and can promote the strength of the cured soil when the expansion quantity is proper. However, when the swelling effect is too large, the cementation effect formed between the sludge by the hydrated calcium silicate is destroyed, and the strength is reduced, so that the excessive swelling is avoided.
7. The composite sludge curing agent has the following advantages: the permeability is strong, the speed is fast, and the dosage of the medicament is less; the formed condensate is fast and early in hardening and good in curing effect, and meanwhile, the later strength is not reduced; the odor of the sludge can be removed; reducing the release of heavy metal and nitrogen and phosphorus to the environment.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The electroplating sewage sludge dewatering curing agent provided by the embodiment comprises composite portland cement, lime, fly ash, aluminum sulfate, an amino-functionalized magnetic multi-wall carbon nanotube [ amino-oximation-polyethyleneimine/sulfonated polyether sulfone reinforced polyacrylonitrile ] fixed coriolus versicolor laccase hybrid nano-composite, a nano calcium material with the particle size of 150 meshes and polyaspartic acid, wherein the composite portland cement, lime, fly ash, aluminum sulfate, the amino-functionalized magnetic multi-wall carbon nanotube [ amino-oximation-polyethyleneimine/sulfonated polyether sulfone reinforced polyacrylonitrile ] fixed coriolus versicolor laccase hybrid nano-composite comprises the following components in parts by weight:
the preparation method of the amino-functionalized magnetic multi-walled carbon nanotube [ amino oximation-polyethyleneimine/sulfonated polyether sulfone reinforced polyacrylonitrile ] fixed coriolus versicolor laccase hybrid nano-composite comprises the following steps:
s1: mixing 25 parts of polyethyleneimine/sulfonated polyether sulfone reinforced polyacrylonitrile, 8 parts of benzoyl peroxide and 3 parts of xylene, uniformly stirring at the rotating speed of 30rpm at the temperature of 28 ℃, standing for 30min at the temperature of 25 ℃, then adding 100 parts of deionized water, carrying out further graft copolymerization on the polyethyleneimine/sulfonated polyether sulfone reinforced polyacrylonitrile in a water bath at the temperature of 80 ℃ for 0.5h, then cleaning for 1 time by using distilled water, and then soaking for 2h by using dimethylformamide to remove impurity homopolymers to obtain a polyethyleneimine/sulfonated polyether sulfone reinforced polyacrylonitrile copolymer;
s2: 30 portions of NH2OH & HCl was dissolved in deionized water to form NH at a concentration of 30g/L2OH HCl solution with 0.1M Na2CO3Solution conditioning of NH2Of OH & HCl solutionThe initial pH value is 6.5, and the initial pH value of the polyethyleneimine/sulfonated polyether sulfone reinforced polyacrylonitrile copolymer obtained in the step S1 is NH of 6.52Ultrasonically vibrating OH & HCl solution at 50Hz for 10min, and heating in water bath at the rotation speed of 250rpm for 40min at 70 ℃ to obtain aminooximation-polyethyleneimine/sulfonated polyether sulfone reinforced polyacrylonitrile prepolymer;
s3: cleaning the aminooximation-sulfonated polyether sulfone reinforced polyacrylonitrile prepolymer obtained in the step S2 by using deionized water until the pH value is 7, and drying the washed aminooximation-sulfonated polyether sulfone reinforced polyacrylonitrile prepolymer at 50 ℃ in vacuum to obtain an aminooximation-polyethyleneimine/sulfonated polyether sulfone reinforced polyacrylonitrile copolymer;
s4: mixing 25 parts of amino-functionalized magnetic multi-walled carbon nanotubes and 10 parts of glutaraldehyde with the amino oximation-polyethyleneimine/sulfonated polyether sulfone reinforced polyacrylonitrile copolymer obtained in the step S3, heating and dissolving the mixture for 1.5 hours at 40 ℃ by ultrasonic waves, continuously adding 3 parts of O- (7-azabenzotriazole-1-yl) -N, N, N ', N' -tetramethylurea hexafluorophosphate in the dissolving process, and cleaning the mixture by adopting a Tris-HCl solution with the pH of 7 and the concentration of 40mM to determine the optimal pH value of immobilization to be 7.5 so as to form a magnetic multi-walled carbon nanotube [ amino oximation-polyethyleneimine/sulfonated polyether sulfone reinforced polyacrylonitrile ] solution with an aldehyde group activated end;
s5: mixing 10 parts of trametes versicolor laccase with the magnetic multi-wall carbon nanotube solution at the aldehyde group activation end obtained in the step S4, slightly oscillating for 1h at the rotating speed of 30rpm, then alternately cleaning for 3 times by using ethanol and distilled water, and filtering to obtain the amino-functionalized magnetic multi-wall carbon nanotube [ amino oximation-polyethyleneimine/sulfonated polyether sulfone reinforced polyacrylonitrile ] immobilized trametes versicolor laccase hybrid nano-composite.
The polyethyleneimine/sulfonated polyether sulfone reinforced polyacrylonitrile comprises the following components in parts by weight:
the preparation method of the polyethyleneimine/sulfonated polyether sulfone reinforced polyacrylonitrile comprises the following steps:
a1: mixing 15 parts of polyethylene glycol and 60 parts of dimethylformamide to form a high-molecular polymer solvent;
a2: mixing 30 parts of polyacrylonitrile and the high molecular polymer solvent obtained in the step A1, stirring at the rotating speed of 500rpm for 1.5h at the temperature of 65 ℃, and degassing for 3h at the temperature of 25 ℃;
a3: mixing the mixture obtained in the step A2 with 15 parts of sulfonated polyether sulfone, uniformly stirring at 50 ℃, forming a reticular film at 28, soaking the reticular film into isopropanol and deionized water with the volume ratio of 1:1 at 25 ℃, standing and solidifying to form the sulfonated polyether sulfone reinforced polyacrylonitrile reticular film;
a4: soaking the sulfonated polyether sulfone reinforced polyacrylonitrile reticular membrane obtained in the step A3 into LiOH solution with the concentration of 1.0M at the temperature of 40-45 ℃ to hydrolyze the sulfonated polyether sulfone reinforced polyacrylonitrile reticular membrane for 0.5h to form a sulfonated polyether sulfone reinforced polyacrylonitrile reticular membrane with surface functionalized and negatively charged carboxyl;
a5: dissolving 10 parts of trimesoyl chloride in 5 parts of normal hexane to form trimesoyl chloride solution; and B, dissolving 10 parts of polyethyleneimine in 50-100 parts of distilled water to form polyethyleneimine solution with positive surface charge, immersing the surface functionalized carboxyl sulfonated polyether sulfone polyacrylonitrile reticular membrane with negative charge obtained in the step A4 in the polyethyleneimine solution with positive surface charge for 2min, and then immersing in the trimesoyl chloride solution for 1-3 min to obtain the polyethyleneimine/sulfonated polyether sulfone reinforced polyacrylonitrile.
The amino-functionalized magnetic multi-wall carbon nanotube comprises the following components in parts by weight:
magnetic alpha-Fe2O315 parts of nano particles;
60 parts of carbon nanotubes;
and 50 parts of ethylenediamine.
The preparation method of the amino-functionalized magnetic multi-wall carbon nanotube comprises the following steps:
b1: immersing 60 parts of carbon nano tube in 100ml of mixed acid solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 3:1, and refluxing for 20min at 125 ℃ to form carbon nano tube suspension solution;
b2: b1, filtering the carbon nano tube suspension solution obtained in the step B by adopting a filter membrane with the aperture of 0.20 mu m in vacuum at 25 ℃, then cleaning the carbon nano tube obtained by filtering to be neutral by adopting distilled water, and drying at 90 ℃ to obtain a dried oxidized carbon nano tube;
b3: 15 parts of magnetic alpha-Fe2O3Dissolving the nano particles and the oxidized carbon nano tube obtained in the step B2 in a mixed solution of ethanol and water with the volume ratio of 1:1, performing ultrasonic oscillation for 0.5h at 30MHz and 45 ℃, then stirring for 24h at 25 ℃ and 300rpm, then filtering by using a filter membrane with the aperture of 0.20 mu m, and drying for 3h in vacuum and 70 summer to obtain the magnetic carbon nano tube;
b4: and B3, dissolving the magnetic carbon nanotube obtained in the step B in 50 parts of ethylenediamine, performing ultrasonic oscillation for 0.3h at 35MHz and 45 ℃, cleaning for 2 times by using formaldehyde, and drying for 0.3h at 60 ℃ in vacuum to obtain the amino-functionalized magnetic multi-walled carbon nanotube.
The embodiment also provides a preparation method of the electroplating sewage sludge dewatering curing agent, which comprises the steps of mixing the composite portland cement, lime, fly ash, aluminum sulfate and amino-functionalized magnetic multi-walled carbon nanotubes [ amino oximation-polyethyleneimine/sulfonated polyether sulfone reinforced polyacrylonitrile ], the fixed coriolus versicolor laccase hybrid nano-composite, the nano-calcium material with the particle size of 150 meshes and polyaspartic acid according to the mass ratio of 1:0.222:0.444:0.111:0.022:0.007:0.0002 at room temperature, uniformly stirring, completing the oxidative polymerization reaction among raw materials, and grinding the mixture until the particle size is smaller than 200 meshes to obtain the electroplating sewage sludge dewatering curing agent.
And removing impurities such as lumps in the sludge from the electroplating sewage plant. The water content of the sludge was measured to be 45.7%. Adding 500g of sludge into a stirrer, adding 25g of curing agent, mechanically stirring to uniformly mix the sludge and the curing agent, stirring for about 2 minutes to gradually harden the sludge, and stopping stirring. After 2 days of granulation, the water content is reduced to 20.8%, and the strength is 585KN/m by an axial compression tester2The solidified sludge has no odor, can meet the requirements of landfill and building filling, and can also be made into bricks with various shapes by utilizing grinding tools for buildings. The crushed solidified sludge contains rich organic matters, nutrient elements such as nitrogen, phosphorus and potassium, and trace elements such as calcium, magnesium, copper, iron and zinc, can play roles in changing soil structure, increasing soil fertility and promoting plant growth, can be used as a fertilizer for garden greenbelts, and realizes resource utilization of sludge.
Example 2
The electroplating sewage sludge dewatering curing agent provided by the embodiment comprises, by mass, 1:0.40:0.60:0.222:0.067:0.01:0.0005 composite portland cement, lime, fly ash, aluminum sulfate, an amino-functionalized magnetic multi-walled carbon nanotube [ amino-oximated-polyethyleneimine/sulfonated polyarylether benzonitrile enhanced polyacrylonitrile ] immobilized thiocyanate hydrolase/phosphatase hybrid nano-composite, a nano calcium material with a particle size of 100 meshes and polyaspartic acid, and the amino-functionalized magnetic multi-walled carbon nanotube [ amino-oximated-polyethyleneimine/sulfonated polyarylether benzonitrile enhanced polyacrylonitrile ] immobilized thiocyanate hydrolase/phosphatase hybrid nano-composite comprises the following components in parts by weight:
the preparation method of the amino-functionalized magnetic multi-walled carbon nanotube [ amino oximation-polyethyleneimine/sulfonated polyarylether benzonitrile enhanced polyacrylonitrile ] immobilized thiocyanate hydrolase/phosphatase hybrid nano-composite comprises the following steps:
s1: mixing 30 parts of polyethyleneimine/sulfonated polyarylether benzonitrile enhanced polyacrylonitrile, 9 parts of benzoyl peroxide and 4 parts of xylene, stirring uniformly at the rotating speed of 45rpm at the temperature of 32 ℃, standing for 35min at the temperature of 26 ℃, then adding 150 parts of deionized water, carrying out further graft copolymerization on the polyethyleneimine/sulfonated polyarylether benzonitrile enhanced polyacrylonitrile in a water bath at the temperature of 82 ℃ for 0.75h, then washing for 2 times by using distilled water, and then soaking for 2.5h by using dimethylformamide to remove impurity homopolymers, thus obtaining a polyethyleneimine/sulfonated polyarylether benzonitrile enhanced polyacrylonitrile copolymer;
s2: 40 parts of NH2OH & HCl dissolved in deionized water to form 40g/L NH2OH HCl solution with 0.1M Na2CO3Solution conditioning of NH2The initial pH value of the OH & HCl solution is 7, and the initial pH value of the polyethyleneimine/sulfonated polyarylether benzonitrile reinforced polyacrylonitrile copolymer obtained in the step S1 is NH of 72Ultrasonically vibrating OH & HCl solution at 75Hz for 7min, and heating in water bath at the rotation speed of 225rpm at 75 ℃ for 45min to obtain aminooximation-polyethyleneimine/sulfonated polyarylether benzonitrile reinforced polyacrylonitrile prepolymer;
s3: washing the amino oximation-sulfonated polyarylether benzonitrile enhanced polyacrylonitrile prepolymer obtained in the step S2 by deionized water until the pH value is 7, and drying under vacuum at 55 ℃ to obtain an amino oximation-polyethyleneimine/sulfonated polyarylether benzonitrile enhanced polyacrylonitrile copolymer;
s4: mixing 27 parts of amino-functionalized magnetic multi-walled carbon nanotubes and the amino oximation-polyethyleneimine/sulfonated polyarylether benzonitrile reinforced polyacrylonitrile copolymer obtained in the step S3 with 15 parts of glutaraldehyde, heating and dissolving for 1.65 hours at 45 ℃ by ultrasonic waves, continuously adding 4 parts of O- (7-azabenzotriazole-1-yl) -N, N, N ', N' -tetramethylurea hexafluorophosphate in the dissolving process, and cleaning at 65 ℃ by adopting a glycine-sodium hydroxide solution with the pH of 9 to determine that the immobilized optimal pH value is 9, so as to form a magnetic multi-walled carbon nanotube [ amino oximation-polyethyleneimine/sulfonated polyarylether benzonitrile reinforced polyacrylonitrile ] solution with an aldehyde group activated end;
s5: mixing 6 parts of thiocyanic acid hydrolase and 7 parts of phosphatase with the magnetic multi-walled carbon nanotube solution at the aldehyde activated end obtained in the step S4, slightly oscillating for 1h at the rotating speed of 40rpm, then alternately cleaning for 3 times by using ethanol and distilled water, and filtering to obtain the amino-functionalized magnetic multi-walled carbon nanotube [ amino oximation-polyethyleneimine/sulfonated polyarylether benzonitrile enhanced polyacrylonitrile ] immobilized thiocyanic acid hydrolase/phosphatase hybrid nano-composite.
The polyethyleneimine/sulfonated polyarylether benzonitrile reinforced polyacrylonitrile comprises the following components in parts by weight:
the preparation method of the polyethyleneimine/sulfonated polyarylether benzonitrile reinforced polyacrylonitrile comprises the following steps:
a1: mixing 17.5 parts of polyethylene glycol with 65 parts of dimethylformamide to form a high-molecular polymer solvent;
a2: mixing 35 parts of polyacrylonitrile and the high molecular polymer solvent obtained in the step A1, stirring at the rotation speed of 550rpm for 1.65h at the temperature of 75 ℃, and degassing at the temperature of 26 ℃ for 3.5 h;
a3: mixing the mixture obtained in the step A2 with 17.5 parts of sulfonated polyarylether benzonitrile, stirring uniformly at 60 ℃, forming a reticular film at 39 ℃, soaking the reticular film into isopropanol and deionized water with the volume ratio of 1:1 at 25 ℃, standing and solidifying to form the sulfonated polyarylether benzonitrile reinforced polyacrylonitrile reticular film;
a4: soaking the sulfonated polyarylether benzonitrile reinforced polyacrylonitrile reticular film obtained in the step A3 into a LiOH solution with the concentration of 1.0M at 42 ℃ to hydrolyze/sulfonate the polyarylether benzonitrile reinforced polyacrylonitrile reticular film for 0.75h to form a surface functionalized/sulfonated polyarylether benzonitrile reinforced polyacrylonitrile reticular film with negative charge carboxyl;
a5: dissolving 12 parts of trimesoyl chloride in 7.5 parts of n-hexane to form a trimesoyl chloride solution; dissolving polyethyleneimine of the weight components in 75 parts of distilled water to form a polyethyleneimine solution with a positive surface charge, immersing the carboxyl sulfonated polyarylether benzonitrile reinforced polyacrylonitrile reticular membrane with a negative surface charge obtained in the step A4 in the polyethyleneimine solution with a positive surface charge for 3min, and then immersing in the trimesoyl chloride solution for 2min to obtain the polyethyleneimine/sulfonated polyarylether benzonitrile reinforced polyacrylonitrile.
The amino-functionalized magnetic multi-wall carbon nanotube comprises the following components in parts by weight:
magnetic gamma-Fe2O318.75 parts of nano particles;
75 parts of carbon nano tubes;
and 55 parts of ethylenediamine.
The preparation method of the amino-functionalized magnetic multi-wall carbon nanotube comprises the following steps:
b1: immersing 75 parts of carbon nano tube in 100ml of mixed acid solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 3:1, and refluxing for 25min at 130 ℃ to form carbon nano tube suspension solution;
b2: vacuum-filtering the carbon nano tube suspension solution obtained in the step B1 by using a filter membrane with the aperture of 0.22 mu m at the temperature of 26 ℃, then cleaning the carbon nano tube obtained by filtering to be neutral by using distilled water, and drying at the temperature of 95 ℃ to obtain a dried oxidized carbon nano tube;
b3: 18.75 parts of magnetic gamma-Fe2O3Dissolving the nano particles and the oxidized carbon nano tube obtained in the step B2 in a mixed solution of ethanol and water with the volume ratio of 1:1, performing ultrasonic oscillation for 0.65h at the temperature of 50 ℃ at 35MHz, then stirring for 36h at the temperature of 26 ℃ and the rpm of 400, then filtering by adopting a filter membrane with the aperture of 0.22 mu m, and performing summer drying for 4h at the temperature of 72 ℃ in vacuum to obtain a magnetic carbon nano tube;
b4: and B3, dissolving the magnetic carbon nanotube obtained in the step B in 55 parts of ethylenediamine, performing ultrasonic oscillation for 0.4h at the temperature of 50 ℃ at 40MHz, then cleaning for 3 times by using formaldehyde, and drying for 0.4h at the temperature of 65 ℃ in vacuum to obtain the amino-functionalized magnetic multi-walled carbon nanotube.
The preparation method of the dewatering curing agent for electroplating sewage sludge provided in this embodiment includes mixing, at room temperature, composite portland cement, lime, fly ash, aluminum sulfate, an amino-functionalized magnetic multi-walled carbon nanotube [ amino-oximated-polyethyleneimine/sulfonated polyarylether benzonitrile-enhanced polyacrylonitrile ], an immobilized thiocyanic acid hydrolase/phosphatase hybrid nano-composite, a nano-calcium material with a particle size of 100 meshes, and polyaspartic acid in a mass ratio of 1:0.40:0.60:0.222:0.067:0.01:0.0005, stirring uniformly, completing an oxidative polymerization reaction between raw materials, and grinding to a particle size of less than 200 meshes to obtain the dewatering curing agent for electroplating sewage sludge.
And removing impurities such as lumps in the sludge from the electroplating sewage plant. The water content of the sludge was measured to be 46.5%. 500g of sludge is put into a stirrer, 25g of curing agent is added, the mixture is stirred mechanically to be mixed uniformly, the sludge is gradually hardened after stirring for about 2 minutes, and the stirring is stopped. After 2 days of granulation, the water content was reduced to 21.3%, and the strength was measured by an axial compression tester to be 610KN/m2The sludge is equivalent to the third type of engineering soil, has no odor, can be used as building filling soil, and can also be made into bricks with various shapes by utilizing grinding tools for buildings. The sludge is rich in organic matters required by plant growth, is a valuable organic fertilizer, is suitable as a fertilizer for garden greenbelts, and can also be used for replacing base soil for building greenbelts.
Example 3
The electroplating sewage sludge dewatering curing agent provided by the embodiment comprises composite portland cement, lime, fly ash, aluminum sulfate, an amino-functionalized magnetic multi-walled carbon nanotube [ amino-oximation-polyethyleneimine/sulfonated polystyrene enhanced polyacrylonitrile ] fixed thioamidoase hybrid nano-composite, a nano calcium material with a particle size of 80 meshes and polyaspartic acid, wherein the composite portland cement, the lime, the fly ash, the aluminum sulfate, the amino-functionalized magnetic multi-walled carbon nanotube [ amino-oximation-polyethyleneimine/sulfonated polystyrene enhanced polyacrylonitrile ] fixed thioamidoase hybrid nano-composite comprises the following components in parts by weight:
the preparation method of the amino-functionalized magnetic multi-walled carbon nanotube [ amino oximation-polyethyleneimine/sulfonated polystyrene reinforced polyacrylonitrile ] immobilized sulfenyl amidase hybrid nano-composite comprises the following steps:
s1: mixing 45 parts of polyethyleneimine/sulfonated polystyrene reinforced polyacrylonitrile, 10 parts of benzoyl peroxide and 5 parts of xylene, uniformly stirring at the rotating speed of 60rpm at 35 ℃, standing at 27 ℃ for 40min, then adding 200 parts of deionized water, carrying out further graft copolymerization on the polyethyleneimine/sulfonated polystyrene reinforced polyacrylonitrile in a water bath at 85 ℃ for 1h, then cleaning for 1 time by using distilled water, and then soaking for 3h by using dimethylformamide to remove impurity homopolymers to obtain a polyethyleneimine/sulfonated polystyrene reinforced polyacrylonitrile copolymer;
s2: 50 portions of NH2OH & HCl dissolved in deionized water to form NH with a concentration of 50g/L2OH HCl solution with 0.1M Na2CO3Solution conditioning of NH2The initial pH value of the OH & HCl solution is 7.5, and the initial pH value of the polyethyleneimine/sulfonated polystyrene reinforced polyacrylonitrile copolymer obtained in the step S1 is 7.5 NH2Ultrasonically vibrating OH & HCl solution at 100Hz for 5min, and heating in water bath at 80 deg.C and 200rpm for 50min to obtain aminooximation-polyethyleneimine/sulfonated polystyrene reinforced polyacrylonitrile prepolymer;
s3: cleaning the aminooximation-sulfonated polystyrene reinforced polyacrylonitrile prepolymer obtained in the step S2 by using deionized water until the pH value is 7, and drying the washed aminooximation-sulfonated polystyrene reinforced polyacrylonitrile prepolymer at the temperature of 60 ℃ in vacuum to obtain an aminooximation-polyethyleneimine/sulfonated polystyrene reinforced polyacrylonitrile copolymer;
s4: mixing 30 parts of amino-functionalized magnetic multi-walled carbon nanotubes and the amino oximation-polyethyleneimine/sulfonated polystyrene reinforced polyacrylonitrile copolymer obtained in the step S3 with 20 parts of glutaraldehyde, heating and dissolving the mixture for 1.8 hours at 50 ℃ by ultrasonic waves, continuously adding 5 parts of O- (7-azabenzotriazole-1-yl) -N, N, N ', N' -tetramethylurea hexafluorophosphate in the dissolving process, and cleaning the mixture at 70 ℃ by adopting a Tris-HCl solution with the pH of 8 and the concentration of 50mM to determine the optimal pH value of immobilization to be 8 so as to form a magnetic multi-walled carbon nanotube [ amino oximation-polyethyleneimine/sulfonated polystyrene reinforced polyacrylonitrile ] solution with an aldehyde group activated end;
s5: mixing 15 parts of thioamidase with the magnetic multi-walled carbon nanotube solution at the aldehyde activated end obtained in the step S4, slightly oscillating for 1h at the rotating speed of 50rpm, then alternately cleaning for 3 times by using ethanol and distilled water, and filtering to obtain the amino-functionalized magnetic multi-walled carbon nanotube [ amino oximation-polyethyleneimine/sulfonated polystyrene enhanced polyacrylonitrile ] immobilized thioamidase hybrid nano-composite.
The polyethylene imine/sulfonated polystyrene reinforced polyacrylonitrile comprises the following components in parts by weight:
the preparation method of the polyethyleneimine/sulfonated polystyrene reinforced polyacrylonitrile comprises the following steps:
a1: mixing 20 parts of polyethylene glycol and 70 parts of dimethylformamide to form a high-molecular polymer solvent;
a2: mixing 40 parts of polyacrylonitrile with the high molecular polymer solvent obtained in the step A1, stirring at the rotating speed of 600rpm for 1.8h at the temperature of 85 ℃, and degassing for 3 h-4 h at the temperature of 27 ℃;
a3: mixing the mixture obtained in the step A2 with 20 parts of sulfonated polystyrene, uniformly stirring at 70 ℃, forming a reticular film at 30 ℃, soaking the reticular film in isopropanol and deionized water with the volume ratio of 1:1 at 25 ℃, standing and solidifying to form the sulfonated polystyrene reinforced polyacrylonitrile reticular film;
a4: soaking the sulfonated polystyrene reinforced polyacrylonitrile reticular membrane obtained in the step A3 in LiOH solution with the concentration of 1.0M at the temperature of 45 ℃ to hydrolyze the sulfonated polystyrene reinforced polyacrylonitrile reticular membrane for 1h to form a surface functionalized sulfonated polystyrene reinforced polyacrylonitrile reticular membrane with negative charge carboxyl;
a5: dissolving 13 parts of trimesoyl chloride in n-hexane according to weight components to form trimesoyl chloride solution; and B, dissolving 15 parts of polyethyleneimine in 100 parts of distilled water to form polyethyleneimine solution with positive surface charge, immersing the carboxyl sulfonated polystyrene reinforced polyacrylonitrile reticular membrane with surface functionalization and negative charge obtained in the step A4 in the polyethyleneimine solution with positive surface charge for 4min, and then immersing in the trimesoyl chloride solution for 3min to obtain polyethyleneimine/sulfonated polystyrene reinforced polyacrylonitrile.
The amino-functionalized magnetic multi-wall carbon nanotube comprises the following components in parts by weight:
magnetic Fe3O422.5 parts of nano particles;
90 parts of carbon nano tubes;
60 parts of ethylenediamine.
The preparation method of the amino-functionalized magnetic multi-wall carbon nanotube comprises the following steps:
b1: immersing 90 parts of carbon nano tube in 100ml of mixed acid solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 3:1, and refluxing for 30min at 140 ℃ to form carbon nano tube suspension solution;
b2: b1, filtering the carbon nano tube suspension solution obtained in the step B at 27 ℃ in vacuum by using a filter membrane with the aperture of 0.25 mu m, cleaning the carbon nano tube obtained by filtering to be neutral by using distilled water, and drying at 100 ℃ to obtain a dried oxidized carbon nano tube;
b3: 22.5 parts of magnetic Fe3O4Dissolving the nano particles and the oxidized carbon nano tube obtained in the step B2 in a mixed solution of ethanol and water with the volume ratio of 1:1, performing ultrasonic oscillation for 0.8h at 40MHz and 55 ℃, then stirring for 48h at 27 ℃ and 500rpm, then filtering by using a filter membrane with the aperture of 0.25 mu m, and performing summer drying for 5h at 75 ℃ in vacuum to obtain a magnetic carbon nano tube;
b4: and B3, dissolving the magnetic carbon nanotube obtained in the step B in 60 parts of ethylenediamine, performing ultrasonic oscillation for 0.5h at the temperature of 55 ℃ at 45MHz, then cleaning for 3 times by using formaldehyde, and drying for 0.5h at 70 ℃ in vacuum to obtain the amino-functionalized magnetic multi-walled carbon nanotube.
The embodiment also provides a preparation method of the electroplating sewage sludge dehydration curing agent, which comprises the steps of mixing the composite portland cement, lime, fly ash, aluminum sulfate, amino-functionalized magnetic multi-walled carbon nanotubes [ amino oximation-polyethyleneimine/sulfonated polystyrene reinforced polyacrylonitrile ] fixed thioamidoenzyme hybrid nano-composite, the nano-calcium material with the particle size of 80 meshes and polyaspartic acid according to the mass ratio of 1:0.556:0.778:0.333:0.111:0.022:0.0009 at room temperature, uniformly stirring, completing the oxidative polymerization reaction among raw materials, and grinding the mixture until the particle size is smaller than 200 meshes to obtain the electroplating sewage sludge dehydration curing agent.
The water content of the dewatered sludge of a certain electroplating sewage treatment plant is 80.35 percent. Adding 500g of sludge into a stirrer, adding 50g of curing agent, mechanically stirring to uniformly mix the sludge and the curing agent, stirring for about 2 minutes to gradually harden the sludge, and stopping stirring. After 2 days of granulation, the water content of the sludge is reduced to 28.3 percent, and the strength is 724KN/m by testing with an axial compression tester2The sludge has no odor, can meet the requirements of landfill and building filling, and can also be made into bricks for building. The crushed solidified sludge contains rich organic matters, nutrient elements such as nitrogen, phosphorus and potassium, and trace elements such as calcium, magnesium, copper, iron and zinc, can play roles in changing soil structure, increasing soil fertility and promoting plant growth, can be used as a fertilizer for garden greenbelts, and realizes resource utilization of sludge.
Comparative example 1
The electroplating sewage sludge dewatering curing agent prepared in the embodiments 1 to 3 and the embodiment 1 of the Chinese patent 201510874164.1 is adopted to treat the electroplating sewage sludge with the same source, and the heavy metal interception curing rate, the COD removal rate and the cyanide removal rate are measured. The results are shown in Table 1.
TABLE 1
Comparative example 2
The same source of electroplating sewage sludge was treated with the electroplating sewage sludge dewatering curing agent prepared in examples 1 to 3 and example 1 of chinese patent 201510874164.1, the treated sludge was made into a building material, and the mechanical properties (compressive strength), thermal insulation properties (thermal conductivity) and leaching properties (swelling ratio) were measured, and the results are shown in table 2.
TABLE 2
While the invention has been described with reference to a preferred embodiment, various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention. It is intended that the invention not be limited to the particular embodiments disclosed, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (10)
1. The electroplating sewage sludge dewatering curing agent is characterized by comprising, by mass, 1 (0.222-0.556), (0.444-0.778), (0.111-0.333), (0.022-0.111), (0.007-0.022) and (0.0002-0.0009) of composite cement, lime, fly ash, aluminum sulfate, an amino-functionalized magnetic multi-walled carbon nanotube [ amino-oximation-polyethyleneimine/sulfonated high-molecular polymer reinforced polyacrylonitrile ] immobilized hydrolase hybrid nano-composite, a nano-calcium material and polyaspartic acid, wherein the amino-functionalized magnetic multi-walled carbon nanotube [ amino-oximation-polyethyleneimine/sulfonated high-molecular polymer reinforced polyacrylonitrile ] immobilized hydrolase hybrid nano-composite comprises the following components in parts by weight:
3-5 parts of O- (7-azabenzotriazole-1-yl) -N, N, N ', N' -tetramethylurea hexafluorophosphate;
the preparation method of the amino-functionalized magnetic multi-walled carbon nanotube [ amino oximation-polyethyleneimine/sulfonated high-molecular polymer reinforced polyacrylonitrile ] immobilized hydrolase hybrid nano compound comprises the following steps:
s1: mixing the polyethyleneimine/sulfonated high-molecular polymer reinforced polyacrylonitrile, the benzoyl peroxide and the xylene, uniformly stirring at the rotating speed of 30-60 rpm at the temperature of 28-35 ℃, standing at the temperature of 25-27 ℃ for 30-40 min, then adding 100-200 parts of deionized water, carrying out further graft copolymerization on the polyethyleneimine/sulfonated high-molecular polymer reinforced polyacrylonitrile in a water bath at the temperature of 80-85 ℃ for 0.5-1 h, then cleaning with distilled water for 1-2 times, and soaking with dimethylformamide for 2-3 h to remove impurity homopolymers to obtain a polyethyleneimine/sulfonated high-molecular polymer reinforced polyacrylonitrile copolymer;
s2: mixing said weight components of NH2OH & HCl is dissolved in deionized water to form NH with the concentration of 30 g/L-50 g/L2OH HCl solution with 0.1M Na2CO3Solution conditioning of the NH2The initial pH value of the OH & HCl solution is 6.5-7.5, and the initial pH value of the polyethyleneimine/sulfonated high molecular polymer reinforced polyacrylonitrile copolymer obtained in the step S1 is 6.5-7.5 NH2Performing ultrasonic vibration on OH & HCl solution at the frequency of 50 Hz-100 Hz for 5 min-10 min, and heating in water bath at the rotating speed of 200 rpm-250 rpm for 40 min-50 min at the temperature of 70-80 ℃ to obtain an aminooximation-polyethyleneimine/sulfonated high-molecular polymer reinforced polyacrylonitrile prepolymer;
s3: washing the amino oximation-sulfonated high molecular polymer reinforced polyacrylonitrile prepolymer obtained in the step S2 by deionized water until the pH value is 7, and drying under vacuum at 50-60 ℃ to obtain the amino oximation-polyethyleneimine/sulfonated high molecular polymer reinforced polyacrylonitrile copolymer;
s4: mixing the amino-functionalized magnetic multi-walled carbon nano-tube with the weight components, the amino-oximation-polyethyleneimine/sulfonated high molecular polymer reinforced polyacrylonitrile copolymer obtained in the step S3 and glutaraldehyde with the weight components, heating and dissolving the mixture for 1.5 to 1.8 hours at 40 to 50 ℃ by ultrasonic waves, continuously adding the O- (7-azabenzotriazole-1-yl) -N, N, N ', N' -tetramethylurea hexafluorophosphate serving as the weight component in the dissolving process, cleaning by adopting a Tris-HCl solution with the pH of 7-8 and the concentration of 40-50 mM or a glycine-sodium hydroxide solution with the pH of 9-10 at the temperature of 60-70 ℃, determining the optimal pH value of immobilization to form a magnetic multi-walled carbon nanotube [ amino oximation-polyethyleneimine/sulfonated high molecular polymer reinforced polyacrylonitrile ] solution of an aldehyde group activated end;
s5: and (2) mixing the hydrolase with the weight components with the solution of the magnetic multi-walled carbon nanotube at the aldehyde group activated end obtained in the step S4, slightly oscillating for 1h at the rotating speed of 30-50 rpm, then alternately cleaning for 3 times by using ethanol and distilled water, and filtering to obtain the amino-functionalized magnetic multi-walled carbon nanotube [ amino oximation-polyethyleneimine/sulfonated high-molecular polymer reinforced polyacrylonitrile ] immobilized hydrolase hybrid nano-composite.
2. The electroplating sewage sludge dewatering curing agent as claimed in claim 1, wherein the hydrolase is one or more of coriolus versicolor laccase, thiocyanic acid hydrolase, biphenyl hydrolase, phosphatase, and thioamide enzyme.
3. The curing agent for dewatering of electroplating sewage sludge according to claim 1, wherein the polyethyleneimine/sulfonated high molecular polymer reinforced polyacrylonitrile comprises the following components by weight:
4. the electroplating sewage sludge dewatering curing agent according to claim 3, wherein the sulfonated high molecular polymer is one or more of sulfonated polyether sulfone, sulfonated polystyrene, sulfonated polyarylether benzonitrile or sulfonated polyether ether ketone.
5. The electroplating sewage sludge dewatering curing agent as claimed in claim 3, wherein the preparation method of the polyethyleneimine/sulfonated high molecular polymer reinforced polyacrylonitrile comprises the following steps:
a1: mixing the polyethylene glycol of the weight component with the dimethylformamide of the weight component to form a high molecular polymer solvent;
a2: mixing the polyacrylonitrile and the high molecular polymer solvent obtained in the step A1, stirring at the rotating speed of 500-600 rpm for 1.5-1.8 h at the temperature of 65-85 ℃, and degassing at the temperature of 25-27 ℃ for 3-4 h;
a3: mixing the mixture obtained in the step A2 with the sulfonated high molecular polymer, uniformly stirring at 50-70 ℃, forming a reticular film at 28-30 ℃, soaking the reticular film into isopropanol and deionized water with a volume ratio of 1:1 at 25 ℃, standing and solidifying to form the sulfonated high molecular polymer reinforced polyacrylonitrile reticular film;
a4: soaking the sulfonated high molecular polymer reinforced polyacrylonitrile reticular film obtained in the step A3 into LiOH solution with the concentration of 1.0M at the temperature of 40-45 ℃ to hydrolyze the sulfonated high molecular polymer reinforced polyacrylonitrile reticular film for 0.5-1 h, and forming the surface functionalized sulfonated high molecular polymer reinforced polyacrylonitrile reticular film with negative charge carboxyl;
a5: dissolving the weight component of trimesoyl chloride in the weight component of n-hexane to form a trimesoyl chloride solution; dissolving the polyethyleneimine according to the weight components in 50-100 parts of distilled water to form a polyethyleneimine solution with positive surface charge, immersing the carboxyl sulfonated high molecular polymer reinforced polyacrylonitrile reticular membrane with the surface functionalized and negative charge obtained in the step A4 in the polyethyleneimine solution with positive surface charge for 2-4 min, and immersing in the trimesoyl chloride solution for 1-3 min to obtain polyethyleneimine/sulfonated high molecular polymer reinforced polyacrylonitrile.
6. The electroplating sewage sludge dewatering curing agent as claimed in claim 1, wherein the amino-functionalized magnetic multi-walled carbon nanotube comprises the following components by weight:
15-22.5 parts of magnetic nanoparticles;
60-90 parts of carbon nanotubes;
50-60 parts of ethylenediamine.
7. The electroplating sewage sludge dewatering curing agent as claimed in claim 6, wherein the magnetic nanoparticles are magnetic α -Fe2O3Nanoparticle, magnetic gamma-Fe2O3Nanoparticles or magnetic Fe3O4Nanoparticles.
8. The electroplating sewage sludge dewatering curing agent as claimed in claim 6, wherein the preparation method of the amino-functionalized magnetic multi-walled carbon nanotube comprises the following steps:
b1: immersing the carbon nano tubes in the weight components in 100ml of mixed acid solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 3:1, and refluxing for 20min to 30min at the temperature of 125 ℃ to 140 ℃ to form carbon nano tube suspension solution;
b2: b1, filtering the carbon nano tube suspension solution obtained in the step B at 25-27 ℃ in vacuum by using a filter membrane with the aperture of 0.20-0.25 μm, cleaning the carbon nano tube obtained by filtering to be neutral by using distilled water, and drying at 90-100 ℃ to obtain a dried oxidized carbon nano tube;
b3: dissolving the magnetic nano particles and the oxidized carbon nano tube obtained in the step B2 in a mixed solution of ethanol and water with the volume ratio of 1:1, performing ultrasonic oscillation for 0.5 to 0.8h at the temperature of 45 to 55 ℃ at 30 to 40MHz, then stirring for 24 to 48h at the temperature of 25 to 27 ℃ and the speed of 300 to 500rpm, then filtering by adopting a filter membrane with the aperture of 0.20 to 0.25 mu m, and performing summer drying for 3 to 5h at the temperature of 70 to 75 ℃ in vacuum to obtain the magnetic carbon nano tube;
b4: and B3, dissolving the magnetic carbon nano tube obtained in the step B in ethylenediamine with the weight components, performing ultrasonic oscillation for 0.3 to 0.5h at the temperature of between 45 and 55 ℃ at the frequency of between 35 and 45MHz, cleaning for 2 to 3 times by using formaldehyde, and drying for 0.3 to 0.5h at the temperature of between 60 and 70 ℃ in vacuum to obtain the amino functionalized magnetic multi-walled carbon nano tube.
9. The electroplating sewage sludge dewatering curing agent as claimed in claim 1, wherein the composite cement is composite portland cement, and the nano calcium material has a particle size of less than 200 meshes.
10. The preparation method of the electroplating sewage sludge dewatering curing agent according to any one of claims 1 to 9, wherein the electroplating sewage sludge dewatering curing agent is obtained by mixing the composite cement, lime, fly ash, aluminum sulfate, amino-functionalized magnetic multi-walled carbon nanotube [ amino oximation-polyethyleneimine/sulfonated high-molecular polymer reinforced polyacrylonitrile ] immobilized hydrolase hybrid nano-composite, nano-calcium material and polyaspartic acid in the mass ratio at room temperature, stirring uniformly, completing the oxidative polymerization reaction between raw materials, and grinding to a particle size of less than 200 meshes.
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Application publication date: 20201218 |