CN117482920B - Preparation method and application of toughness-enhanced cobalt-zirconium resin composite material - Google Patents
Preparation method and application of toughness-enhanced cobalt-zirconium resin composite material Download PDFInfo
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- GNEMDYVJKXMKCS-UHFFFAOYSA-N cobalt zirconium Chemical compound [Co].[Zr] GNEMDYVJKXMKCS-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000000463 material Substances 0.000 title claims abstract description 64
- 239000000805 composite resin Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000011347 resin Substances 0.000 claims abstract description 42
- 229920005989 resin Polymers 0.000 claims abstract description 42
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 20
- 239000002351 wastewater Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims description 50
- 239000011259 mixed solution Substances 0.000 claims description 46
- 239000000243 solution Substances 0.000 claims description 39
- 229920000779 poly(divinylbenzene) Polymers 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 238000010438 heat treatment Methods 0.000 claims description 36
- 239000000839 emulsion Substances 0.000 claims description 34
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 24
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 23
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 22
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 20
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 20
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 238000004108 freeze drying Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000003607 modifier Substances 0.000 claims description 12
- 239000011859 microparticle Substances 0.000 claims description 11
- 230000001131 transforming effect Effects 0.000 claims description 11
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 10
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 10
- 238000000746 purification Methods 0.000 claims description 10
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 9
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 9
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 238000005530 etching Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 6
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims description 5
- 238000007334 copolymerization reaction Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000004945 emulsification Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 238000005191 phase separation Methods 0.000 claims description 5
- 150000003254 radicals Chemical class 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 28
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003729 cation exchange resin Substances 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 abstract description 2
- 230000001360 synchronised effect Effects 0.000 abstract description 2
- 210000003462 vein Anatomy 0.000 abstract description 2
- 239000010949 copper Substances 0.000 description 24
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 23
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 19
- 229910001431 copper ion Inorganic materials 0.000 description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 229910052802 copper Inorganic materials 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- 239000012528 membrane Substances 0.000 description 8
- 239000003463 adsorbent Substances 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 6
- 238000007865 diluting Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000011550 stock solution Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000012716 precipitator Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 1
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- VAOCPAMSLUNLGC-UHFFFAOYSA-N metronidazole Chemical compound CC1=NC=C([N+]([O-])=O)N1CCO VAOCPAMSLUNLGC-UHFFFAOYSA-N 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004094 preconcentration Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229940057950 sodium laureth sulfate Drugs 0.000 description 1
- SXHLENDCVBIJFO-UHFFFAOYSA-M sodium;2-[2-(2-dodecoxyethoxy)ethoxy]ethyl sulfate Chemical compound [Na+].CCCCCCCCCCCCOCCOCCOCCOS([O-])(=O)=O SXHLENDCVBIJFO-UHFFFAOYSA-M 0.000 description 1
- -1 sulfate radicals Chemical class 0.000 description 1
Abstract
The invention relates to the technical field of treatment of heavy metals in sewage, in particular to a preparation method and application of a toughness-enhanced cobalt-zirconium resin composite material; the preparation method is characterized in that nano cobalt zirconium hydrated oxide particles capable of being combined with sulfate radicals generated by peroxomonosulfate are compounded in cation exchange resin, and double-spherical SiO capable of effectively improving resin interface bonding strength through special-shaped structure 2 Preparing cobalt-zirconium resin composite material with high stability by using particles; when the cobalt-zirconium resin composite material is used together with PMS, the design purpose of synchronous oxidation and vein breaking and adsorption removal of complex heavy metals in wastewater can be realized while the self structure is stable; moreover, the cobalt-zirconium resin composite material has large specific surface area, large pore volume and high strength, and shows ideal adsorptivity and reusability in practical application.
Description
Technical Field
The invention relates to the technical field of treatment of heavy metals in sewage, in particular to a preparation method and application of a toughness-enhanced cobalt-zirconium resin composite material.
Background
Peroxymonosulfate (PMS) has a remarkable effect on degrading organic pollutants, but it is difficult to achieve the same degradation effect on the treatment of heavy metal complexes in water.
The macroporous cation exchange resin is used as a high-quality metal oxide carrier. The porous resin has the characteristics of stable property and wear resistance, and the macroporous structure ensures good hydraulic performance, and more importantly, the cation exchange groups fixed on the surfaces of the porous resin also have the effect similar to the pre-enrichment effect of a Donnan membrane, namely, the target heavy metal cations can be concentrated into the porous resin from the solution, so that the concentration of the heavy metal cations near the solid-supported object sites is improved.
Based on the above teaching, as disclosed in the patent publication No. CN112958040A, a Co-MOF-D113-6 nanocomposite resin is disclosed, and the cobalt ions with spherical metal frames are compounded in the cation exchange resin, so that the composite material has a good adsorption effect on methylene blue in wastewater.
The scheme provides a method for improving the organic matters in the water treated by the cation exchange resin, but the scheme does not consider the problem that the strength of the resin is low because the interface difference between the modified matters and the resin is large in the compounding process, so that the strength of a resin finished product is low; therefore, when the design product is used together with PMS to remove the HEDP-Cu and other heavy metal complexes in the wastewater, the final treatment effect does not reach theoretical expectation due to low structural stability.
Disclosure of Invention
In order to solve the problems, the invention designs a preparation method of a toughness-enhanced cobalt-zirconium resin composite material, which is characterized in that nano cobalt-zirconium hydrated oxide particles capable of combining sulfate radicals generated by combining peroxomonosulfate and double-sphere SiO capable of effectively improving the interfacial bonding strength of the resin through a special-shaped structure are compounded into cation exchange resin 2 Preparing cobalt-zirconium resin composite material with high stability by using particles; when the cobalt-zirconium resin composite material is used together with PMS, the design purpose of synchronous oxidation and vein breaking and complex state heavy metal adsorption removal in wastewater can be realized while the self structure stability is ensured, and the scheme is as follows:
s1, preparing cobalt zirconium ion solution;
firstly adding CoCl into a mixed solution of ethanol and concentrated hydrochloric acid with the mass fraction of 37 percent 2 ·6H 2 O, fully and uniformly stirring at 0-5 ℃ to obtain a first mixed solution; zrOCl is then added to the first mixture 2 ·8H 2 O and pure water are fully stirred to obtain cobalt-zirconium ion solution;
let n be the multiplying factor andthen CoCl 2 ·6H 2 The addition amount of O was 44n g, and the addition amount of ethanol was [250n,280n ]]mL, 37% by mass concentrationThe addition amount of the hydrochloric acid is [15n,17n ]] mL，ZrOCl 2 ·8H 2 The addition amount of O is [60n,66n ]]g, the addition amount of pure water is [20n,22n ]] mL；
S2, preparing modified resin; synthesizing carboxylic acid group acrylic acid copolymer, namely modified resin, by a free radical copolymerization method;
s3, preparing double-sphere SiO by a phase separation method 2 Microparticles: putting the etched PDVB hollow spheres and the modifier into ethylbenzene, uniformly mixing, and reacting under gradient heating; after the reaction is finished, the double-sphere SiO is obtained through centrifugation, washing and freeze drying 2 Particles;
s4, preparing cobalt-zirconium resin composite material
S4-1, adding cobalt zirconium ion solution in S1 and double-sphere SiO in S3 into the modified resin in S2 2 Fully and uniformly stirring the particles and pure water to obtain a second mixed solution;
s4-2, firstly adding a precipitant and a transforming agent into the second mixed solution in the S4-1, and stirring for 20-24 hours at the temperature of 30-50 ℃; filtering to obtain filter residues, and washing the filter residues to be neutral; finally, drying at 120 ℃ for 1-1.5 h to obtain a cobalt-zirconium resin composite material;
let n be the multiplying factor andthe addition amount of the modified resin was 15n,20n]g, the addition amount of the cobalt-zirconium ion solution is [200n,250n ]]mL, double sphere SiO 2 The addition amount of the particles was [6n,8n ]]g, the addition amount of pure water is [50n,100n ]]mL, the addition amount of the precipitant is [10n,12n ]]g, the addition amount of the transforming agent is [10n,12n ]] g。
Further, the step of preparing the modified resin in S2 is:
s2-1, firstly purifying methyl methacrylate and butyl acrylate, then adding the purified methyl methacrylate, the purified butyl acrylate and methacrylic acid into DMF together, and fully mixing to obtain a third mixed solution;
s2-2, adding AIBN into the third mixed solution, and stirring and reacting for 2-2.5 hours at the temperature of 60-70 ℃ to obtain a fourth mixed solution;
let n be the multiplying powerCoefficient ofThe amount of methacrylic acid added was 3n mol, the amount of methyl methacrylate added was 5n mol, the amount of butyl acrylate added was 2n mol, and the amount of DMF added was [100n,110n ]]mL, AIBN addition was 0.02n,0.025n] g；
S2-3, separating, purifying and washing the fourth mixed solution to obtain the modified resin.
Description: the modified resin designed by the invention is an acrylic copolymer with a macroporous structure and a carboxylic acid group, and can be attached to the surface of modified particles through the actions of ionic bonds, hydrogen bonds, van der Waals force and the like, thereby providing basic performance for resin modification.
Further, the steps of purifying Methyl Methacrylate (MMA) and Butyl Acrylate (BA) in S2-1 are as follows:
purification of methyl methacrylate: under 10.8 kPa, carrying out pressurized distillation at 40-42 ℃;
purification of butyl acrylate: and (3) carrying out pressurized distillation at the temperature of 60-62 ℃ under the pressure of 10.8 kPa.
Further, the preparation steps of the PDVB hollow sphere in the S3 are as follows:
S3-A1, placing the HP433 hollow sphere into pure water, and stirring for 30-40 min at 30-35 ℃ to obtain a first emulsion; then, performing ultrasonic emulsification on AIBN, divinylbenzene, sodium dodecyl polyoxyethylene ether sulfate and pure water for 10-15 min to obtain a second emulsion;
in the first emulsion, the mass concentration of the HP433 hollow sphere is 0.1-0.13 g/mL;
let n be the multiplying factor andthe AIBN is added in the second emulsion in an amount of 0.01n g and divinylbenzene in an amount of 0.1n,0.2n]g, the adding amount of the sodium dodecyl polyoxyethylene ether sulfate is [0.2n,0.22n ]]g, the addition amount of pure water is [20n,25n ]] mL；
S3-A2, adding the second emulsion into the first emulsion, stirring for 10-11 hours at the temperature of 30-35 ℃, then heating to 70-75 ℃ at the speed of 10-15 ℃/min, and reacting at constant temperature for 10-12 hours to obtain a reaction product;
the volume ratio of the second emulsion to the first emulsion is 1.2-1.4: 1, a step of;
S3-A3, washing and freeze-drying the reaction product in the S3-3 to obtain the PDVB hollow spheres.
Further, double spherical SiO in S3 2 The preparation steps of the particles are as follows:
S3-B1, etching the PDVB hollow sphere: dispersing the PDVB hollow spheres in a 10% NaOH solution, heating to 70 ℃ at a rate of 8-10 ℃ and continuously stirring for reacting for 1-1.5 h; obtaining etched PDVB hollow spheres;
S3-B2, putting the PDVB hollow spheres etched by the S3-B1 and the modifier into ethylbenzene, uniformly mixing, and reacting under gradient heating;
the modifier consists of 3- (methacryloyloxy) propyl trimethoxy silane, diethylenetriamine and 1% of K by mass 2 S 2 O 8 An aqueous solution;
let n be the multiplying factor andthe addition amount of the PDVB hollow sphere after etching treatment is 1n g, and the addition amount of the 3- (methacryloyloxy) propyl trimethoxysilane is [5n,5.5n ]]g, the addition amount of the diethylenetriamine is [4n,4.5n ]]g, 1% by mass of K 2 S 2 O 8 The addition amount of the aqueous solution is [3n,4n ]]mL, ethylbenzene addition was [40n,45n ]] mL；
Gradient heating is as follows: firstly, heating from 20 ℃ to 30 ℃ at a speed of 5-6 ℃/min, and preserving heat for 5-6 min; then heating from 30 ℃ to 100 ℃ at a speed of 10-14 ℃/min, and preserving heat for 20-30 min; then heating from 100 ℃ to 2000 ℃ at a speed of 20-22 ℃/min, and preserving heat for 3-4 hours;
S3-B3, centrifuging, washing and freeze-drying after the reaction is finished to obtain double-sphere SiO 2 Microparticles.
Description: the invention designs double spherical SiO 2 The microparticles have two clearly different space microspheres and anisotropies, so when the neck of the double sphere is positioned at the resin composite interface, the resin can be locked, and the crack in the crack resin is blockedThe grain expansion has the toughening and reinforcing effects.
Further, the precipitant in S4-2 is sodium hydroxide and the transforming agent is sodium chloride.
Further, the diameter of the cobalt-zirconium resin composite material is 1.10-1.22 mm, and the total load ratio of cobalt and zirconium is 8.8-10.6%.
The invention also provides application of the toughness reinforced cobalt-zirconium resin composite material, and the preparation method of the toughness reinforced cobalt-zirconium resin composite material is based on the fact that the cobalt-zirconium resin composite material and the PMS are combined to act together to remove heavy metal complexes in wastewater.
Compared with the existing treatment agent for heavy metal complex in wastewater, the invention has the beneficial effects that:
(1) The existing two-step method for removing complex heavy metals has the defects of oxidation, channel breaking and adsorption, long reaction period and low treatment efficiency; the cobalt-zirconium resin composite material designed by the invention can synchronously realize the oxidative degradation of the organic ligand and the adsorption removal of heavy metals, and greatly shortens the treatment time.
(2) The cobalt-zirconium resin composite material designed by the invention has large specific surface area, large pore volume and high strength, and shows excellent stability and reusability in practical application, so that the problem that the traditional Fenton-like reaction is limited by external energy activation, the problem that transition metal ions may cause secondary pollution in the activation process, and the problem that the transition metal ions are limited by recycling can be avoided.
(3) The cobalt-zirconium resin composite material designed by the invention couples the preconcentration effect of the polymer matrix, the catalytic oxidation performance of nano hydrated cobalt oxide, the adsorption selectivity performance of zirconium and the interface locking performance of double-ball particles together, can efficiently and selectively synchronously oxidize and break collaterals and adsorb and remove pollutants, and avoids the problems of large sludge yield in a chemical precipitation method, high cost of a membrane separation method, an electrochemical deposition method and the like and complex operation.
Drawings
FIG. 1 is a macroscopic appearance of the cobalt zirconium resin composite prepared in example 2 of the present invention;
FIG. 2 is a graph showing the relationship between the removal rate of copper ions and the PMS amount in experimental example 1;
FIG. 3 is a graph showing the relationship between the degradation rate of organic phosphorus and the removal rate of copper ions and the equilibrium pH in Experimental example 2;
FIG. 4 is a graph showing the relationship between the adsorption capacity of copper ions and the initial copper ion concentration in Experimental example 3; in the figure, A is a cobalt-zirconium resin composite material used in combination with PMS, and B is a cobalt-zirconium resin composite material used alone;
FIG. 5 shows the removal rate of copper ions and NO in Experimental example 4 3 - A concentration graph; in the figure, A is a cobalt-zirconium resin composite material used alone, B is a cobalt-zirconium D001 composite material used alone, C is a cobalt-zirconium resin composite material used in combination with PMS, and D is a cobalt-zirconium D001 composite material used in combination with PMS;
FIG. 6 is a graph showing the relationship between the removal rate of copper ions and the concentration of competing ions in Experimental example 5;
FIG. 7 is a graph showing the relationship between the removal rate of copper ions, the loss rate of cobalt and the number of cycles in Experimental example 6; in the figure, A is the combined use of the cobalt-zirconium resin composite material and PMS, and B is the separate use of the cobalt-zirconium resin composite material.
Detailed Description
In order to further illustrate the manner in which the invention is made and the effects obtained, a clear and complete description of the technical solution of the invention will be provided in connection with experiments.
Example 1: the embodiment describes a preparation method of a toughness-enhanced cobalt-zirconium resin composite material.
S1, preparing cobalt zirconium ion solution;
firstly adding CoCl into a mixed solution of ethanol and concentrated hydrochloric acid with the mass fraction of 37 percent 2 ·6H 2 O, fully and uniformly stirring at 0 ℃ to obtain a first mixed solution; zrOCl is then added to the first mixture 2 ·8H 2 O and pure water are fully stirred to obtain cobalt-zirconium ion solution;
when CoCl 2 ·6H 2 When the addition amount of O was 44 and g, the addition amount of ethanol was 250 and mL, the addition amount of concentrated hydrochloric acid with a mass fraction of 37% was 15 mL, zrOCl 2 ·8H 2 The addition amount of O is 60 g,the addition amount of pure water was 20 mL;
s2, preparing modified resin; synthesizing carboxylic acid group acrylic acid copolymer, namely modified resin, by a free radical copolymerization method;
s2-1, firstly purifying methyl methacrylate and butyl acrylate, then adding the purified methyl methacrylate, the purified butyl acrylate and methacrylic acid into DMF together, and fully mixing to obtain a third mixed solution;
purification of methyl methacrylate: pressure distillation at 40℃under 10.8 kPa;
purification of butyl acrylate: pressure distillation at 60℃under 10.8 kPa;
s2-2, adding AIBN into the third mixed solution, and stirring at 60 ℃ to react 2 h to obtain a fourth mixed solution;
when the amount of methacrylic acid added was 3 mol, the amount of methyl methacrylate added was 5 mol, the amount of butyl acrylate added was 2 mol, the amount of DMF added was 100 mL, and the amount of AIBN added was 0.02g;
s2-3, separating, purifying and washing the fourth mixed solution to obtain modified resin;
s3, preparing double-sphere SiO by a phase separation method 2 Microparticles:
first, PDVB hollow spheres were prepared:
S3-A1, placing HP433 hollow spheres into pure water, and stirring for 30 min at 30 ℃ to obtain a first emulsion; then, performing ultrasonic emulsification on AIBN, divinylbenzene, sodium dodecyl polyoxyethylene ether sulfate and pure water for 10 min to obtain a second emulsion;
in the first emulsion, the mass concentration of the HP433 hollow sphere is 0.1 g/mL;
in the second emulsion, the addition amount of AIBN was 0.01 g, the addition amount of divinylbenzene was 0.1g, the addition amount of sodium dodecyl polyoxyethylene ether sulfate was 0.2 g, and the addition amount of pure water was 20 mL;
S3-A2, adding the 120 mL second emulsion into the 100 mL first emulsion, stirring for 10 hours at 30 ℃, then heating to 70 ℃ at the speed of 10 ℃/min, and reacting at constant temperature for 10h to obtain a reaction product;
S3-A3, washing and freeze-drying the reaction product in the S3-3 to obtain the PDVB hollow spheres;
then, a double sphere SiO was prepared 2 Microparticles:
S3-B1, etching the PDVB hollow sphere: dispersing 5g of PDVB hollow spheres in a NaOH solution with the mass fraction of 10% of 20 mL, heating to 70 ℃ at the rate of 8 ℃ and continuously stirring for reaction of 1 h; obtaining etched PDVB hollow spheres;
S3-B2, putting the PDVB hollow spheres etched by the S3-B1 and the modifier into ethylbenzene, uniformly mixing, and reacting under gradient heating;
the modifier consists of 3- (methacryloyloxy) propyl trimethoxy silane, diethylenetriamine and 1% of K by mass 2 S 2 O 8 An aqueous solution;
when the addition amount of the etched PDVB hollow sphere is 1g, the addition amount of 3- (methacryloyloxy) propyl trimethoxysilane is 5g, the addition amount of diethylenetriamine is 4 g, and the mass fraction of K is 1% 2 S 2 O 8 The addition amount of the aqueous solution is 3mL; the addition amount of ethylbenzene was 40 mL;
gradient heating is as follows: firstly, heating from 20 ℃ to 30 ℃ at a speed of 5 ℃/min, and preserving heat for 5 min; then heating from 30 ℃ to 100 ℃ at a speed of 10 ℃/min, and preserving heat for 20 min; then heating from 100 ℃ to 2000 ℃ at a speed of 20 ℃/min, and preserving heat for 3 h;
S3-B3, centrifuging, washing and freeze-drying after the reaction is finished to obtain double-sphere SiO 2 Particles;
s4, preparing cobalt-zirconium resin composite material
S4-1, adding cobalt zirconium ion solution in S1 and double-sphere SiO in S3 into the modified resin in S2 2 Fully and uniformly stirring the particles and pure water to obtain a second mixed solution;
s4-2, firstly adding a precipitator and a transforming agent into the second mixed solution in the S4-1, and stirring at 30 ℃ for 20 h; filtering to obtain filter residues, and washing the filter residues to be neutral; finally, drying 1h at 120 ℃ to obtain a cobalt-zirconium resin composite material;
the addition amount of the modified resin is 15 g, and the addition amount of the cobalt-zirconium ion solution is 200mL, double sphere SiO 2 The amount of fine particles added was 6 g, the amount of pure water added was 50 mL, the amount of precipitant added was 10 g, and the amount of transforming agent added was 10 g.
Example 2: the embodiment describes a preparation method of a toughness-enhanced cobalt-zirconium resin composite material.
S1, preparing cobalt zirconium ion solution;
firstly adding CoCl into a mixed solution of ethanol and concentrated hydrochloric acid with the mass fraction of 37 percent 2 ·6H 2 O, fully and uniformly stirring at 5 ℃ to obtain a first mixed solution; zrOCl is then added to the first mixture 2 ·8H 2 O and pure water are fully stirred to obtain cobalt-zirconium ion solution;
when CoCl 2 ·6H 2 When the addition amount of O was 44 and g, the addition amount of ethanol was 280 and mL, the addition amount of concentrated hydrochloric acid with a mass fraction of 37% was 17 mL, zrOCl 2 ·8H 2 The addition amount of O is 66 g, and the addition amount of pure water is 22 mL;
s2, preparing modified resin; synthesizing carboxylic acid group acrylic acid copolymer, namely modified resin, by a free radical copolymerization method;
s2-1, firstly purifying methyl methacrylate and butyl acrylate, then adding the purified methyl methacrylate, the purified butyl acrylate and methacrylic acid into DMF together, and fully mixing to obtain a third mixed solution;
purification of methyl methacrylate: pressure distillation at 42℃under 10.8 kPa;
purification of butyl acrylate: pressure distillation at 62℃under 10.8 kPa;
s2-2, adding AIBN into the third mixed solution, and stirring at 0 ℃ to react for 2.5 h to obtain a fourth mixed solution;
when the amount of methacrylic acid added was 3 mol, the amount of methyl methacrylate added was 5 mol, the amount of butyl acrylate added was 2 mol, the amount of DMF added was 110 mL, and the amount of AIBN added was 0.025g;
s2-3, separating, purifying and washing the fourth mixed solution to obtain modified resin;
s3, preparing double by a phase separation methodSpherical SiO 2 Microparticles:
first, PDVB hollow spheres were prepared:
S3-A1, putting the HP433 hollow sphere into pure water, and stirring for 40 min at 35 ℃ to obtain a first emulsion; then, performing ultrasonic emulsification on AIBN, divinylbenzene, sodium dodecyl polyoxyethylene ether sulfate and pure water for 15 min to obtain a second emulsion;
in the first emulsion, the mass concentration of the HP433 hollow sphere is 0.13 g/mL;
in the second emulsion, the addition amount of AIBN was 0.01 g, the addition amount of divinylbenzene was 0.2 g, the addition amount of sodium dodecyl polyoxyethylene ether sulfate was 0.22 g, and the addition amount of pure water was 25 mL;
S3-A2, adding the 140-mL second emulsion into the 100-mL first emulsion, stirring for 11 hours at 35 ℃, then heating to 75 ℃ at a speed of 15 ℃/min, and reacting at constant temperature for 12-h to obtain a reaction product;
S3-A3, washing and freeze-drying the reaction product in the S3-3 to obtain the PDVB hollow spheres;
then, a double sphere SiO was prepared 2 Microparticles:
S3-B1, etching the PDVB hollow sphere: dispersing 6 g of PDVB hollow spheres in a NaOH solution with the mass fraction of 10% of 20 mL, heating to 70 ℃ at the rate of 10 ℃ and continuously stirring for reaction of 1.5h; obtaining etched PDVB hollow spheres;
S3-B2, putting the PDVB hollow spheres etched by the S3-B1 and the modifier into ethylbenzene, uniformly mixing, and reacting under gradient heating;
the modifier consists of 3- (methacryloyloxy) propyl trimethoxy silane, diethylenetriamine and 1% of K by mass 2 S 2 O 8 An aqueous solution;
when the addition amount of the etched PDVB hollow sphere is 1g, the addition amount of 3- (methacryloyloxy) propyl trimethoxysilane is 5.5 g, the addition amount of diethylenetriamine is 4.5 g, and the mass fraction of K is 1% 2 S 2 O 8 The addition amount of the aqueous solution was 4 mL; the addition amount of ethylbenzene is 45 mL;
gradient heating is as follows: firstly, heating from 20 ℃ to 30 ℃ at a speed of 6 ℃/min, and preserving heat for 6min; then heating from 30 ℃ to 100 ℃ at a speed of 14 ℃/min, and preserving heat for 30 min; then heating from 100 ℃ to 2000 ℃ at a speed of 22 ℃/min, and preserving heat for 4h;
S3-B3, centrifuging, washing and freeze-drying after the reaction is finished to obtain double-sphere SiO 2 Particles;
s4, preparing cobalt-zirconium resin composite material
S4-1, adding cobalt zirconium ion solution in S1 and double-sphere SiO in S3 into the modified resin in S2 2 Fully and uniformly stirring the particles and pure water to obtain a second mixed solution;
s4-2, firstly adding a precipitator and a transforming agent into the second mixed solution in the S4-1, and stirring at 50 ℃ for 24h; filtering to obtain filter residues, and washing the filter residues to be neutral; finally, drying at 120 ℃ for 1.5 hours to obtain a cobalt-zirconium resin composite material;
the addition amount of the modified resin is 20 g, the addition amount of the cobalt-zirconium ion solution is 250 mL, and the double spherical SiO is prepared 2 The addition amount of the fine particles was 8 g, the addition amount of pure water was 100 mL, the addition amount of the precipitant was 12 g, and the addition amount of the transforming agent was 12 g.
Example 3: the description of this example is based on the scheme described in example 2, except that the resin was a D001 resin, and a cobalt zirconium D001 composite material was produced, with the remainder being the same.
Example 4: the embodiment describes a preparation method of a toughness-enhanced cobalt-zirconium resin composite material.
S1, preparing cobalt zirconium ion solution;
firstly adding CoCl into a mixed solution of ethanol and concentrated hydrochloric acid with the mass fraction of 37 percent 2 ·6H 2 O, fully and uniformly stirring at 5 ℃ to obtain a first mixed solution; zrOCl is then added to the first mixture 2 ·8H 2 O and pure water are fully stirred to obtain cobalt-zirconium ion solution;
when CoCl 2 ·6H 2 When the addition amount of O was 88 g, the addition amount of ethanol was 560 mL, the addition amount of concentrated hydrochloric acid with a mass fraction of 37% was 34 mL, zrOCl 2 ·8H 2 The addition amount of O is 132 g, and the addition amount of pure water is 44 mL;
s2, preparing modified resin; synthesizing carboxylic acid group acrylic acid copolymer, namely modified resin, by a free radical copolymerization method;
s2-1, firstly purifying methyl methacrylate and butyl acrylate, then adding the purified methyl methacrylate, the purified butyl acrylate and methacrylic acid into DMF together, and fully mixing to obtain a third mixed solution;
purification of methyl methacrylate: pressure distillation at 42℃under 10.8 kPa;
purification of butyl acrylate: pressure distillation at 62℃under 10.8 kPa;
s2-2, adding AIBN into the third mixed solution, and stirring at 0 ℃ to react for 2.5 h to obtain a fourth mixed solution;
when the amount of methacrylic acid added was 6 mol, the amount of methyl methacrylate added was 10 mol, the amount of butyl acrylate added was 4 mol, the amount of DMF added was 220 mL, and the amount of AIBN added was 0.05 g;
s2-3, separating, purifying and washing the fourth mixed solution to obtain modified resin;
s3, preparing double-sphere SiO by a phase separation method 2 Microparticles:
first, PDVB hollow spheres were prepared:
S3-A1, putting the HP433 hollow sphere into pure water, and stirring for 40 min at 35 ℃ to obtain a first emulsion; then, performing ultrasonic emulsification on AIBN, divinylbenzene, sodium dodecyl polyoxyethylene ether sulfate and pure water for 15 min to obtain a second emulsion;
in the first emulsion, the mass concentration of the HP433 hollow sphere is 0.13 g/mL;
in the second emulsion, the addition amount of AIBN was 0.02g, divinylbenzene was 0.4 g, sodium laureth sulfate was 0.44 g and pure water was 50 mL;
S3-A2, adding the 280 mL second emulsion into the 200 mL first emulsion, stirring for 11 hours at 35 ℃, then heating to 75 ℃ at a speed of 15 ℃/min, and reacting at constant temperature for 12 h to obtain a reaction product;
S3-A3, washing and freeze-drying the reaction product in the S3-3 to obtain the PDVB hollow spheres;
then, a double sphere SiO was prepared 2 Microparticles:
S3-B1, etching the PDVB hollow sphere: dispersing 10 g of PDVB hollow spheres in 40 mL mass percent 10% NaOH solution, heating to 70 ℃ at a rate of 10 ℃ and continuously stirring for reaction for 1.5h; obtaining etched PDVB hollow spheres;
S3-B2, putting the PDVB hollow spheres etched by the S3-B1 and the modifier into ethylbenzene, uniformly mixing, and reacting under gradient heating;
the modifier consists of 3- (methacryloyloxy) propyl trimethoxy silane, diethylenetriamine and 1% of K by mass 2 S 2 O 8 An aqueous solution;
when the addition amount of the etched PDVB hollow sphere is 2g, the addition amount of 3- (methacryloyloxy) propyl trimethoxysilane is 11 g, the addition amount of diethylenetriamine is 9 g, and the mass fraction of K is 1% 2 S 2 O 8 The addition amount of the aqueous solution is 8 mL; the addition amount of ethylbenzene was 90 mL;
gradient heating is as follows: firstly, heating from 20 ℃ to 30 ℃ at a speed of 6 ℃/min, and preserving heat for 6min; then heating from 30 ℃ to 100 ℃ at a speed of 14 ℃/min, and preserving heat for 30 min; then heating from 100 ℃ to 2000 ℃ at a speed of 22 ℃/min, and preserving heat for 4h;
S3-B3, centrifuging, washing and freeze-drying after the reaction is finished to obtain double-sphere SiO 2 Particles;
s4, preparing cobalt-zirconium resin composite material
S4-1, adding cobalt zirconium ion solution in S1 and double-sphere SiO in S3 into the modified resin in S2 2 Fully and uniformly stirring the particles and pure water to obtain a second mixed solution;
s4-2, firstly adding a precipitator and a transforming agent into the second mixed solution in the S4-1, and stirring at 50 ℃ for 24h; filtering to obtain filter residues, and washing the filter residues to be neutral; finally, drying at 120 ℃ for 1.5 hours to obtain a cobalt-zirconium resin composite material;
the addition amount of the modified resin is 40 g, the addition amount of the cobalt-zirconium ion solution is 500 mL, and the double spherical SiO is prepared 2 The amount of fine particles added was 16 g, the amount of pure water added was 200 mL, the amount of precipitant added was 24 g, and the amount of transforming agent added was 24 g.
Experimental example 1: the description of this experimental example is that the cobalt-zirconium resin composite material prepared in example 2 was used for removal of complex heavy metals.
1) Taking CA-Cu, HEDP-Cu and EDTA-Cu stock solution, and diluting in a volumetric flask until marked lines are prepared into a solution containing 15mgL of copper ions;
2) Five groups of 50 mL centrifuge tubes are used for comparing the adsorption performance of the cobalt-zirconium resin composite material prepared by the invention under different PMS concentrations, and each group of reactors is respectively added with 0.02g adsorption material;
3) The concentration of PMS added in each group is respectively 0 mM, 1 mM, 2 mM, 3 mM and 4 mM, five groups of reactors are placed in a constant temperature stirrer, the stirring temperature is set to be 25 ℃, the stirring speed is set to be 180rpm, and the vibration is started to enable the adsorbent to fully contact with the adsorption liquid;
4) After 24. 24h, all centrifuge tubes were taken out, left for 10 minutes, the mixed solution was extracted using a syringe, and the solution was filtered with a 0.45 μm filter membrane, and the copper ion content of each sample was measured.
As shown in FIG. 2, the amount of PMS used was 2 mM for the highest removal of the three complex heavy metals.
Experimental example 2: this experimental example describes the use of the cobalt zirconium resin composite material prepared in example 3 for the removal of heavy metal contaminants from HEDP copper plating wastewater.
1) Diluting HEDP-Cu stock solution in a volumetric flask until marked lines are used for preparing a solution containing 15mgL of copper ions;
2) Ten groups of 50 mL centrifuge tubes are used for comparing the adsorption performance of the cobalt-zirconium resin composite material prepared by the invention under different pH values, and each group of reactors is respectively added with 0.02g adsorption material and 2 mM PMS;
3) Each group of pH is 2, 3, 4, 5, 6, 7, 8, 9, 10 and 11 respectively, ten groups of reactors are put into a constant temperature stirrer, the stirring temperature is set to be 25 ℃, the stirring speed is set to be 180rpm, and the stirring is started to oscillate so that the adsorbent is fully contacted with the adsorption liquid;
4) After 24. 24h, all centrifuge tubes were taken out, and after 10 min of standing, the mixed solution was extracted using a syringe and filtered through a 0.45 μm filter membrane, and the equilibrium pH, copper ion content and orthophosphoric acid group content of each sample were determined.
As shown in FIG. 3, the balanced pH is basically distributed between 6 and 8, the degradation rate of HEDP oxidized and decomposed into orthophosphate is highest between 7 and 8, and the copper removal rate is also highest.
Experimental example 3: this experimental example describes the use of the cobalt zirconium resin composite material prepared in example 2 for the removal of heavy metal contaminants from HEDP copper plating wastewater.
1) Respectively diluting HEDP-Cu stock solution to marked lines in a volumetric flask to prepare HEDP-Cu solutions containing 15mgL, 30 mgL, 45 mgL, 60 mgL and 75 mgL of copper ions;
2) Two groups of 50 mL centrifuge tubes are used for comparing the adsorption capacity of the cobalt-zirconium resin composite material prepared by the method, and each group of reactors is respectively added with 0.02g adsorption material;
3) One group of the reactors is added with 2 mM PMS, the two groups of the reactors are placed in a constant temperature stirrer, the stirring temperature is set to be 25 ℃, the stirring speed is set to be 180rpm, and the stirring is started to oscillate so that the adsorbent and the adsorption liquid are fully contacted;
4) After 24. 24h, all centrifuge tubes were taken out, left for 10 minutes, the mixed solution was extracted using a syringe, and the solution was filtered with a 0.45 μm filter membrane, and the copper ion content of each sample was measured.
As shown in fig. 4, the adsorption capacity of the cobalt zirconium resin composite material added with PMS was much higher for copper than for the group without PMS, indicating that PMS degradation complex plays an important role in copper removal.
Experimental example 4: this experimental example describes the use of the cobalt-zirconium resin composite materials prepared in examples 2 and 3 for the removal of heavy metals from HEDP copper plating wastewater, while exploringInfluence of ions on adsorption experiments.
1) Diluting HEDP-Cu stock solution in a volumetric flask until marked lines are used for preparing HEDP-Cu solution containing 15mgL of copper ions;
2) Four sets of 50 mL centrifuge tubes were used to compare the adsorption properties of two cobalt zirconium resin composites prepared according to the present invention:
the components in the first group are: 0.02g cobalt zirconium resin composite material;
the components in the second group are: 0.02g cobalt zirconium D001 composite material;
the components in the third group are: 0.02g cobalt zirconium resin composite, PMS of 2 mM;
the fourth group comprises the following components: 0.02g cobalt zirconium D001 composite, PMS of 2 mM;
controlling the first group, the second group, the third group and the fourth groupThe addition variables of the ions are: 0 mgL, 400 mgL, 800 mgL and 1200 mgL;
3) Placing the four groups of centrifugal tubes into a constant temperature stirrer, setting the stirring temperature to 25 ℃ and the stirring speed to 180rpm, and starting to oscillate to enable the adsorbent to fully contact with the adsorption liquid;
4) After 24. 24h, all centrifuge tubes were taken out, left for 10 minutes, the mixed solution was extracted using a syringe, and the solution was filtered with a 0.45 μm filter membrane, and the copper ion content of each sample was measured.
As shown in fig. 5, the adsorption effect of the cobalt-zirconium resin composite is stronger than that of the cobalt-zirconium D001 composite.
Experimental example 5: this experimental example describes the use of the cobalt-zirconium resin composite material prepared in example 2 for the removal of heavy metals from HEDP copper plating wastewater, and explores Zn 2+ 、Ca 2+ Influence of HA on adsorption experiments.
1) Diluting HEDP-Cu stock solution in a volumetric flask until marked lines are used for preparing HEDP-Cu solution containing 15mgL of copper ions;
2) Three groups of 50 mL centrifuge tubes are used for comparing the adsorption performance of the cobalt-zirconium resin composite material prepared by the invention under different competitive ion conditions, and each group of reactors is respectively added with 0.02g adsorption material and 2 mM PMS;
3) Zn is added into each group 2+ 、Ca 2+ The HA concentration is 0 mM, 0.5 mM, 1 mM, 2 mM and 4 mM respectively, three groups of reactors are placed in a constant temperature stirrer, the stirring temperature is set to be 25 ℃, the stirring speed is set to be 180rpm, and the vibration is started to enable the adsorbent to fully contact with the adsorption liquid;
4) After 24. 24h, all centrifuge tubes were taken out, left for 10 minutes, the mixed solution was extracted using a syringe, and the solution was filtered with a 0.45 μm filter membrane, and the copper ion content of each sample was measured.
As shown in fig. 6, the cobalt-zirconium resin composite material has little influence on the copper removal rate under different competitive ion conditions, which indicates that the adsorbent has better selectivity.
Experimental example 6: this experimental example describes the regeneration performance of the cobalt zirconium resin composite material prepared in example 2 when it was used for removing heavy metals from HEDP copper plating wastewater.
1) Diluting HEDP-Cu stock solution in a volumetric flask until marked lines are used for preparing HEDP-Cu solution containing 15mgL of copper ions;
2) Two groups of 50 mL centrifuge tubes are used for comparing the adsorption performance of the cobalt-zirconium resin composite material prepared by the invention under the condition of containing PMS, and each group of reactors is respectively added with 0.02g adsorption material;
3) One group of the reactors is added with 2 mM PMS, the two groups of the reactors are placed in a constant temperature stirrer, the stirring temperature is set to be 25 ℃, the stirring speed is set to be 180rpm, and the stirring is started to oscillate so that the adsorbent and the adsorption liquid are fully contacted;
4) Taking out all centrifuge tubes after 24 and h, standing for 10 min, extracting mixed solution in the centrifuge tubes by using a needle tube, filtering the solution by using a filter membrane with the diameter of 0.45 mu m, and measuring the copper ion content of each sample;
5) And (3) placing the filtered cobalt-zirconium resin composite material in NaCl-HCl solution with the pH value of 3 for desorption, filtering after 24h, repeating the step (3), and measuring the loss rate of cobalt and the removal rate of copper after five times of circulation.
As shown in fig. 7, the loss rate of cobalt after five cycles is less than 0.1%, and the influence on the removal rate of copper is small, which indicates that the regeneration performance of the modified material is better.
Claims (6)
1. The preparation method of the toughness-enhanced cobalt-zirconium resin composite material is characterized by comprising the following steps of:
s1, preparing cobalt zirconium ion solution:
firstly adding CoCl into a mixed solution of ethanol and concentrated hydrochloric acid with the mass fraction of 37 percent 2 ·6H 2 O, fully and uniformly stirring at 0-5 ℃ to obtain a first mixed solution; zrOCl is then added to the first mixed liquor 2 ·8H 2 O and pure water are fully stirred to obtain cobalt-zirconium ion solution;
let n be the multiplying factor andthen the CoCl 2 ·6H 2 The addition amount of O was 44n g, and the addition amount of ethanol was [250n,280n ]]The addition amount of the concentrated hydrochloric acid with the mass fraction of 37 percent of mL is [15n,17n ]] mL，ZrOCl 2 ·8H 2 The addition amount of O is [60n,66n ]]g, the addition amount of pure water is [20n,22n ]] mL；
S2, preparing modified resin: synthesizing carboxylic acid group acrylic acid copolymer, namely modified resin, by a free radical copolymerization method;
s3, preparing double-sphere SiO by a phase separation method 2 Microparticles: putting the etched PDVB hollow spheres and the modifier into ethylbenzene, uniformly mixing, and reacting under gradient heating; after the reaction is finished, the double-sphere SiO is obtained through centrifugation, washing and freeze drying 2 Particles;
the modifier consists of 3- (methacryloxy) propyl trimethoxy silane, diethylenetriamine and 1% by mass of K 2 S 2 O 8 An aqueous solution;
let n be the multiplying factor andthe addition amount of the PDVB hollow sphere after etching treatment is 1n g, and the addition amount of the 3- (methacryloyloxy) propyl trimethoxysilane is [5n,5.5n ]]g, the addition amount of the diethylenetriamine is [4n,4.5n ]]g, 1% by mass of K 2 S 2 O 8 The addition amount of the aqueous solution is [3n,4n ]]mL, ethylbenzene addition was[40n,45n] mL；
The gradient temperature rise is as follows: firstly, heating from 20 ℃ to 30 ℃ at a speed of 5-6 ℃/min, and preserving heat for 5-6 min; then heating from 30 ℃ to 100 ℃ at a speed of 10-14 ℃/min, and preserving heat for 20-30 min; then heating from 100 ℃ to 2000 ℃ at a speed of 20-22 ℃/min, and preserving heat for 3-4 hours;
s4, preparing a cobalt-zirconium resin composite material:
s4-1, adding cobalt zirconium ion solution in S1 and double-sphere SiO in S3 into the modified resin in S2 2 Fully and uniformly stirring the particles and pure water to obtain a second mixed solution;
s4-2, firstly adding a precipitant and a transforming agent into the second mixed solution in the S4-1, and stirring for 20-24 hours at the temperature of 30-50 ℃; filtering to obtain filter residues, and washing the filter residues to be neutral; finally, drying at 120 ℃ for 1-1.5 h to obtain a cobalt-zirconium resin composite material;
let n be the multiplying factor andthe addition amount of the modified resin is 15n,20n]g, the addition amount of the cobalt-zirconium ion solution is [200n,250n ]]mL, double sphere SiO 2 The addition amount of the particles was [6n,8n ]]g, the addition amount of pure water is [50n,100n ]]mL, the addition amount of the precipitant is [10n,12n ]]g, the addition amount of the transforming agent is [10n,12n ]] g。
2. The method for preparing the toughness reinforced cobalt-zirconium resin composite material according to claim 1, wherein the step of preparing the modified resin in S2 is as follows:
s2-1, firstly purifying methyl methacrylate and butyl acrylate, then adding the purified methyl methacrylate, the purified butyl acrylate and methacrylic acid into DMF together, and fully mixing to obtain a third mixed solution;
s2-2, adding AIBN into the third mixed solution, and stirring and reacting for 2-2.5 hours at the temperature of 60-70 ℃ to obtain a fourth mixed solution;
let n be the multiplying factor andthe amount of methacrylic acid added was 3n mol, the amount of methyl methacrylate added was 5n mol, the amount of butyl acrylate added was 2n mol, and the amount of DMF added was [100n,110n ]]mL, AIBN addition was 0.02n,0.025n] g；
S2-3, separating, purifying and washing the fourth mixed solution to obtain the modified resin.
3. The method for preparing the toughness reinforced cobalt-zirconium resin composite material according to claim 2, wherein the step of purifying methyl methacrylate and butyl acrylate in S2-1 is as follows:
purification of methyl methacrylate: under 10.8 kPa, carrying out pressurized distillation at 40-42 ℃;
purification of butyl acrylate: and (3) carrying out pressurized distillation at the temperature of 60-62 ℃ under the pressure of 10.8 kPa.
4. The method for preparing the toughness reinforced cobalt-zirconium resin composite material according to claim 1, wherein the step of preparing the PDVB hollow sphere in S3 is as follows:
S3-A1, placing the HP433 hollow sphere into pure water, and stirring for 30-40 min at 30-35 ℃ to obtain a first emulsion; then, performing ultrasonic emulsification on AIBN, divinylbenzene, sodium dodecyl polyoxyethylene ether sulfate and pure water for 10-15 min to obtain a second emulsion;
the mass concentration of the HP433 hollow spheres in the first emulsion is 0.1-0.13 g/mL;
let n be the multiplying factor andthe AIBN in the second emulsion is added in an amount of 0.01n g and divinylbenzene in an amount of 0.1n,0.2n]g, the adding amount of the sodium dodecyl polyoxyethylene ether sulfate is [0.2n,0.22n ]]g, the addition amount of pure water is [20n,25n ]] mL；
S3-A2, adding the second emulsion into the first emulsion, stirring for 10-11 hours at the temperature of 30-35 ℃, then heating to 70-75 ℃ at the speed of 10-15 ℃/min, and reacting at constant temperature for 10-12 hours to obtain a reaction product;
the volume ratio of the second emulsion to the first emulsion is 1.2-1.4: 1, a step of;
S3-A3, washing and freeze-drying the reaction product in the S3-3 to obtain the PDVB hollow spheres.
5. The method for preparing a toughness reinforced cobalt-zirconium resin composite material according to claim 1, wherein the double sphere SiO in S3 is 2 The preparation steps of the particles are as follows:
S3-B1, etching the PDVB hollow sphere: dispersing the PDVB hollow spheres in a NaOH solution with the mass fraction of 10%, heating to 70 ℃ at the rate of 8-10 ℃ and continuously stirring for reacting for 1-1.5 hours to obtain etched PDVB hollow spheres;
S3-B2, putting the PDVB hollow spheres etched by the S3-B1 and the modifier into ethylbenzene, uniformly mixing, and reacting under gradient heating;
S3-B3, centrifuging, washing and freeze-drying after the reaction is finished to obtain double-sphere SiO 2 Microparticles.
6. Use of the toughness reinforced cobalt zirconium resin composite material prepared by the preparation method according to claim 1, wherein the cobalt zirconium resin composite material and the PMS are combined to remove heavy metal complexes in wastewater.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110170316A (en) * | 2019-06-20 | 2019-08-27 | 南京大学 | A kind of resin-base nano composite material, preparation method and its depth go copper-citric acid method in water removal |
| CN113694899A (en) * | 2021-09-02 | 2021-11-26 | 南京大学 | Lanthanum-zirconium bimetallic resin-based nanocomposite and preparation method and application thereof |
| CN117181202A (en) * | 2023-09-20 | 2023-12-08 | 南京信息工程大学 | Anionic resin-based nano cerium-manganese oxide composite material and preparation method and application thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110170316A (en) * | 2019-06-20 | 2019-08-27 | 南京大学 | A kind of resin-base nano composite material, preparation method and its depth go copper-citric acid method in water removal |
| CN113694899A (en) * | 2021-09-02 | 2021-11-26 | 南京大学 | Lanthanum-zirconium bimetallic resin-based nanocomposite and preparation method and application thereof |
| CN117181202A (en) * | 2023-09-20 | 2023-12-08 | 南京信息工程大学 | Anionic resin-based nano cerium-manganese oxide composite material and preparation method and application thereof |
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