CN116589053A - Core-shell structure CCoS magnetic flocculant with chromium removal function, and green synthesis method and application thereof - Google Patents
Core-shell structure CCoS magnetic flocculant with chromium removal function, and green synthesis method and application thereof Download PDFInfo
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- CN116589053A CN116589053A CN202310724878.9A CN202310724878A CN116589053A CN 116589053 A CN116589053 A CN 116589053A CN 202310724878 A CN202310724878 A CN 202310724878A CN 116589053 A CN116589053 A CN 116589053A
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 26
- 239000011651 chromium Substances 0.000 title claims abstract description 26
- 239000011258 core-shell material Substances 0.000 title claims abstract description 15
- 238000001308 synthesis method Methods 0.000 title claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 4
- 239000010840 domestic wastewater Substances 0.000 claims abstract description 3
- 229910003321 CoFe Inorganic materials 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- -1 iron ion Chemical class 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- 239000010935 stainless steel Substances 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 5
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 4
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 208000023445 Congenital pulmonary airway malformation Diseases 0.000 claims 2
- 229910017052 cobalt Inorganic materials 0.000 abstract description 13
- 239000010941 cobalt Substances 0.000 abstract description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 13
- 229910000859 α-Fe Inorganic materials 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 9
- 238000002360 preparation method Methods 0.000 abstract description 9
- 239000000839 emulsion Substances 0.000 abstract description 8
- 239000006249 magnetic particle Substances 0.000 abstract description 4
- 125000003277 amino group Chemical group 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 24
- 239000000047 product Substances 0.000 description 12
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005189 flocculation Methods 0.000 description 4
- 230000016615 flocculation Effects 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- PZNOBXVHZYGUEX-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine;hydrochloride Chemical compound Cl.C=CCNCC=C PZNOBXVHZYGUEX-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- 229910020647 Co-O Inorganic materials 0.000 description 2
- 229910020704 Co—O Inorganic materials 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000413 hydrolysate Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002122 magnetic nanoparticle Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
- C02F1/488—Treatment of water, waste water, or sewage with magnetic or electric fields for separation of magnetic materials, e.g. magnetic flocculation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
A core-shell structure CCoS magnetic flocculant with a chromium removal function, and a green synthesis method and application thereof. The application belongs to the field of magnetic flocculant preparation. The application aims to solve the technical problems of single function and unstable emulsion of the traditional magnetic flocculant. The application prepares magnetic nano cobalt ferrite particles by a hydrothermal/high-temperature calcination method, then combines hydroxyl groups on the surface of cobalt ferrite with a plurality of hydrolyzed SCA molecules to form nano magnetic particles with amino groups at the end groups, further generates amino free radicals under the ultraviolet light catalysis effect, and then initiates AM and DMD to copolymerize on the surfaces of the magnetic particles, thereby successfully preparing the core-shell structure CCoS magnetic flocculant with the chromium removal function. The method is simple and easy to operate, is suitable for industrial production, and meanwhile, the obtained CCoS magnetic flocculant has good stability and a certain chromium removal function, and overcomes the defect of single function of the existing magnetic flocculant. Can be applied to the field of chromium-containing domestic wastewater treatment.
Description
Technical Field
The application belongs to the field of preparation of magnetic flocculant, and particularly relates to a core-shell structure CCoS magnetic flocculant with a chromium removal function, and a green synthesis method and application thereof.
Background
The magnetic flocculant is a functional material commonly used for water treatment, but the preparation process is relatively complex, and the magnetic flocculant can achieve proper quality and use effect through processing of multiple procedures. Specifically, the preparation process of the flocculant comprises the following steps: first, a cationic polymer polyacrylamide (CPAM) colloid was prepared by an aqueous solution polymerization method. And then, granulating, drying, grinding, screening and other processing technologies are carried out on the CPAM colloid, so that CPAM dry powder with uniform particles and reliable quality is obtained. Next, preparing CPAM dry powder into a water solution with a certain concentration, and adding a certain proportion of modified Fe into the water solution 3 O 4 The composite flocculant product with magnetic property is obtained by means of rapid stirring and the like.
However, this preparation process has a certain problem: (1) The preparation process is complex, a large amount of time and energy are consumed, and meanwhile, the problems of high cost, unstable product performance and the like exist: (2) Due to Fe 3 O 4 The product is easy to precipitate at the flocculation bottom, and the application effect of the product can be influenced; (3) Fe is used in flocculant 3 O 4 The magnetic nano particles only improve the turbidity removing effect of the product, have single function and are suitable for some heavy metal ionsThe wastewater treatment effect is not ideal, so that the preparation process is further optimized and the functionality of the product is improved.
Disclosure of Invention
The application provides a core-shell structure CCoS magnetic flocculant with a chromium removal function, a green synthesis method and application thereof, and aims to solve the technical problems of single function and unstable emulsion of the existing magnetic flocculant.
The application aims to provide a green synthesis method of a core-shell structure CCoS magnetic flocculant with a chromium removal function, which comprises the following steps:
s1: nanometer CoFe prepared by hydrothermal/high-temperature calcination method 2 O 4 Particles;
s2: dissolving Silane Coupling Agent (SCA) in water, regulating pH value to 5-6, continuously stirring to hydrolyze, and nano CoFe 2 O 4 The particles are dispersed in the water by ultrasonic, then the water-heat reaction is carried out, and after the reaction is finished, the washing and the vacuum drying are carried out to obtain CoFe 2 O 4 -SCA particles;
s3: acrylamide (AM) was dissolved in water and then CoFe was added 2 O 4 The SCA particles are dispersed in the ultrasonic wave, then dimethyl diallyl ammonium chloride, ammonium sulfate, dispersing agent, sodium chloride and polyethylene glycol 400 are added, and N is introduced after stirring and dissolution 2 Deoxidizing, adding photoinitiator at 10deg.C, ultraviolet polymerizing, standing for a certain time to obtain CPAM/CoFe 2 O 4 SCA, i.e. a core-shell structure CCoS magnetic flocculant with chromium removal function.
Further defined, nano CoFe in S1 2 O 4 Preparation of the particles:
(1) Mixing cobalt ion aqueous solution and iron ion aqueous solution, adding Cetyl Trimethyl Ammonium Bromide (CTAB), continuously stirring for 60min, regulating the pH value of the solution to 8.5-10.5, continuously stirring for 30min, transferring to a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting for 15-20h at 160-190 ℃, cooling to room temperature, washing, and drying;
(2) Calcining in a muffle furnace at 600-800 ℃ for 3-5h to obtain nano CoFe 2 O 4 And (3) particles.
Further defined, the concentration of the aqueous SCA solution in S2 is 0.5-1.75wt%.
Further defined, nano CoFe in S2 2 O 4 The mass ratio of the particles to the SCA is (10-20): 1.
Further limited, the hydrothermal reaction temperature in S2 is 80-90 ℃ and the time is 40-50min.
Further defined, acrylamide (AM), coFe in S3 2 O 4 The SCA particles, the dimethyl diallyl ammonium chloride, the ammonium sulfate, the dispersing agent, the sodium chloride and the polyethylene glycol 400 respectively account for 6-8% of the total mass of the materials, 0.05-0.3%, 1.5-3.5%, 24-28%, 0.5-2%, 0.25-2.5%, 0.5-2% of the total mass of the materials, and the balance is water.
Further limited, the photoinitiator in S3 is photoinitiator V005, and the addition amount is 0.003-0.01 per mill of the total mass of the materials.
Further limited, the ultraviolet irradiation power in the step S3 is 6-20W, and the irradiation time is 3-5min.
Further limited, stirring reaction is continued for 5-7h after the irradiation in S3 is finished.
The second purpose of the application is to provide a core-shell structure CCoS magnetic flocculant with chromium removal function, which is prepared by the method, wherein the shell of the core-shell structure CCoS magnetic flocculant with chromium removal function is CPAM, and the magnetic core is CoFe 2 O 4 -SCA，CoFe 2 O 4 Covalently linked to the SCA.
The application further aims to provide an application of the core-shell structure CCoS magnetic flocculant with the chromium removal function in chromium-containing domestic wastewater.
Compared with the prior art, the application has the remarkable effects that:
(1) The application prepares magnetic nano cobalt ferrite particles by a hydrothermal/high-temperature calcination method, then combines hydroxyl groups on the surface of the cobalt ferrite with a plurality of hydrolyzed SCA molecules to form nano magnetic particles with amino groups at the end groups, further generates amino free radicals under the ultraviolet light catalysis effect, and then initiates Acrylamide (AM) and dimethyl diallyl ammonium chloride (DMD) to copolymerize on the surfaces of the magnetic particles, thus successfully preparing the core-shell structure CCoS magnetic flocculant with the chromium removal function.
(2) The method is simple and easy to operate, is suitable for industrial production, and meanwhile, the obtained CCoS magnetic flocculant has good stability and a certain chromium removal function, and overcomes the defect of single function of the existing magnetic flocculant.
Drawings
FIG. 1 is a graph showing the turbidity removal rate of a CCoS prepared by an embodiment of the present application;
FIG. 2 is a graph showing the chromium removal rate of CCoS produced by an embodiment of the present application;
FIG. 3 shows a magnetic nano CoFe in an embodiment of the application 2 O 4 Infrared spectrogram of the particles;
FIG. 4 is an infrared spectrum of a CCoS prepared by an embodiment of the present application;
FIG. 5 shows a TG spectrum of CCoS prepared by an embodiment of the present application.
Detailed Description
The present application will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present application more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application.
The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, methods and apparatus used, without any particular description, are those conventional in the art and are commercially available to those skilled in the art.
The terms "comprising," "including," "having," "containing," or any other variation thereof, as used in the following embodiments, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range. In the description and claims of the application, the range limitations may be combined and/or interchanged, if not otherwise specified, including all the sub-ranges subsumed therein.
The indefinite articles "a" and "an" preceding an element or component of the application are not limited to the requirement (i.e. the number of occurrences) of the element or component. Thus, the use of "a" or "an" should be interpreted as including one or at least one, and the singular reference of an element or component includes the plural reference unless the amount clearly dictates otherwise.
Reference to "one embodiment" or "an embodiment" of the present application means that a particular feature, structure, or characteristic may be included in at least one implementation of the present application. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
The endpoints of the ranges and any values disclosed in the application are not limited to the precise range or value, and the range or value should be understood to include values close to the range or value. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Examples
The green synthesis method of the core-shell structure CCoS magnetic flocculant with the chromium removal function comprises the following steps:
first step, preparing nano CoFe 2 O 4 And (3) particles:
(1) Accurately weigh 1.19g of CoCl 2 ·6H 2 The O solid particles are stirred in 20mL of deionized water until being completely dissolved, then transferred into a 50mL volumetric flask, and the volumetric flask is fixed to scale by the deionized water to obtain cobalt ion aqueous solution for standby;
(2) 2.705g of FeCl is accurately weighed 3 ·6H 2 Dissolving O solid in 25mL of deionized water, stirring until the O solid is completely dissolved, transferring the O solid into a 50mL volumetric flask, and fixing the volume to a scale by using the deionized water to obtain an iron ion aqueous solution for later use;
(3) 8mL each of the aqueous cobalt ion solution and the aqueous iron ion solution prepared in advance was pipetted with a 10mL pipette, added to a 50mL beaker, added with 0.03g of cetyltrimethylammonium bromide (CTAB), stirred continuously for 60min, and then stirred with NaOH and NaHCO 3 The pH value of the aqueous solution is adjusted to be within the range of 8.5, and the mixed solution is continuously stirred for 30min. Then, the stirred solution is moved into a stainless steel reaction kettle with a polytetrafluoroethylene lining, the stainless steel reaction kettle is filled into a kettle with the polytetrafluoroethylene lining for 80 percent of the capacity of the reaction kettle, the stainless steel reaction kettle is screwed up, sealing is made, the stainless steel reaction kettle is moved into a baking oven for reaction for 19h at 180 ℃, heating is closed, cooling is carried out to room temperature, products in the reaction kettle are taken out, the stainless steel reaction kettle is ultrasonically cleaned by absolute ethyl alcohol and then filtered by a 0.45um filter membrane, the stainless steel reaction kettle is repeatedly cleaned for 4 times, the obtained precipitate is dried for 2h at 70 ℃, the products are transferred into a crucible, and the magnetic nano CoFe is obtained by placing the product into a muffle furnace for calcination for 4.5h at 800 DEG C 2 O 4 And (3) particles.
Second step, coFe is prepared 2 O 4 -SCA particles:
(4) Firstly preparing a silane coupling agent KH550 into a 1.5wt% aqueous solution, then regulating the pH value of the solution to 5 by using acetic acid, and continuously stirring for 15min to complete the hydrolysis process to obtain a hydrolysate;
(5) Magnetic nano CoFe obtained in the step (3) 2 O 4 Particles are ultrasonically dispersed in the hydrolysate (CoFe 2 O 4 The mass ratio of the SCA to the SCA is 10:1), after continuous ultrasonic treatment for 30min, stirring for 45min in a constant-temperature water bath at 85 ℃, and cooling to room temperature; after centrifugation, the supernatant was decanted off and usedWashing nano CoFe with absolute ethyl alcohol 2 O 4 Continuously centrifugally separating SCA with unmodified surface, washing with ethanol for 4 times, and finally obtaining modified nano CoFe 2 O 4 Drying in a vacuum drying oven at 60deg.C for 4 hr to obtain CoFe 2 O 4 -SCA particles.
Thirdly, preparing a magnetic flocculant:
(6) Firstly, a transparent glass reaction kettle with a circulating water bath jacket is installed, 238g of deionized water is added, 30g of Acrylamide (AM) is dissolved in the reaction kettle, and then 1g of CoFe is added 2 O 4 SCA particles, after being uniformly dispersed, adding 10g of dimethyl diallyl ammonium chloride, 108g of ammonium sulfate, 6g of dispersing agent, 4g of sodium chloride and 3g of polyethylene glycol 400, installing a polytetrafluoroethylene stirring rod, stirring for 15min to completely dissolve at 400r/min, introducing nitrogen for 30min, removing dissolved oxygen in the solution, simultaneously opening a circulating water bath, reducing the temperature of the reaction solution to 10 ℃, when the nitrogen blowing time and the solution temperature are both satisfied, starting to add 0.0016g of photoinitiator V005, irradiating for 4min under 12W by using ultraviolet light, and continuously reacting for 6h after the irradiation is finished to obtain CPAM coated CoFe 2 O 4 CPAM/CoFe of SCA 2 O 4 SCA (ccoS), i.e. a core-shell structure ccoS magnetic flocculant with chromium removal.
Flocculation performance test
CPAM/CoFe prepared in the above examples 2 O 4 The SCA emulsion is prepared into 0.05wt%,0.1wt%,0.2wt% and 0.5wt% water solution, flocculation experiments are carried out on chromium-containing simulated sewage (kaolin 1g/L, chromium ion concentration 0.5 mg/L), the turbidity removal rate results are shown in figure 1, when the mass fraction of the magnetic water-in-water emulsion is 0.05wt%,0.1wt%,0.2wt% and 0.5wt%, the turbidity removal rate shows a trend of increasing and decreasing with the increase of the dosage, the highest turbidity removal rate can reach 99.55% when the dosage of 0.05wt% is 50 mu L, and the time for achieving the optimal flocculation effect only needs 1-3min when a magnetic field acts.
(II) chromium removal Performance test
Selecting a magnetic emulsion flocculant with the concentration of 0.05wt% according to the turbidity removal rate to carry out chromium removal experimental study, and applying no work to the magnetic emulsion flocculantMagnetic nanoparticle CoFe 2 O 4 As shown in FIG. 2, the result shows that the chromium removal rate is 92.13% when the dosage is 50uL, the effect is best and is far higher than that of the common CPAM product.
(III) recovery of magnetic nanoparticles
Pouring out the flocculated clear liquid to leave a liquid 1cm away from the bottom, shearing and stirring the flocculate and the solution at a high speed to separate the flocculate from nano cobalt ferrite, and separating the flocculate after chromium removal by an external magnetic field. And (3) adsorbing or extracting the nano cobalt ferrite aggregate at the bottom by using a magnet, washing the nano cobalt ferrite aggregate for multiple times to remove impurities, and finally drying to obtain the recovered magnetic nano cobalt ferrite, wherein the recovery rate is 71.2%.
Characterization of infrared spectrum of CCoS products
FIG. 3 shows nano CoFe in the above embodiment 2 O 4 Particles and CoFe 2 O 4 -infra-red spectrogram of SCA particles, as shown, 591cm -1 Is a Co-O telescopic vibration peak in cobalt ferrite, and corresponds to 591cm in SCA modified nano cobalt ferrite -1 Also has characteristic peaks at CoFe 2 O 4 In the SCA infrared spectrogram, 3478cm -1 is-OH stretching vibration absorption peak, 1040cm -1 A telescopic vibration absorption peak of-Si-O bond of 1628cm -1 Characteristic absorption peak of C=C, which shows that the modification of cobalt ferrite is successful and is CoFe 2 O 4 -SCA。
FIG. 4 is an infrared spectrum of CPAM and CCoS in the above example, as shown, wavenumber 3186cm -1 Is the-N-H telescopic vibration absorption peak in AM, wave number is 2863cm -1 is-NH-CH 2 -an absorption peak indicating-NH on the silane coupling agent 2 Free radicals are generated under the action of ultraviolet light, and polymerization reaction of C=C double bonds is initiated; wave number 2947cm -1 The wave number is 1662cm for the asymmetric absorption peak of methyl and methylene -1 is-NH in AM 2 With C=O group, wave number 1440cm -1 Corresponding to- (CH) in DMD 2 ) 2 N + (CH 3 ) 2 Symmetrical flexural vibration absorption peak, wavenumber 1104cm -1 The wave number is 964cm, which is the-C-N telescopic vibration absorption peak in the DMD -1 Is the bending vibration of = C-H in DMD. The infrared spectrogram of CPAM shows that the prepared cationic polyacrylamide water-in-water emulsion is CPAM/CoFe 2 O 4 611cm visible in the infrared spectrum of SCA -1 A strong peak is a Co-O stretching vibration peak in cobalt ferrite, and the success of the preparation of the magnetic cobalt ferrite water-in-water emulsion CCoS is proved.
Differential thermogravimetric characterization of (fifth) CCoS products
Fig. 5 shows TG spectra of the CPAM and CCoS in the above examples, and it can be seen that there are five main stages of thermal decomposition of the CPAM and CCoS. The weight loss ranges from 40 ℃ to 110 ℃ in the first stage are basically consistent, and the mass loss in the stage can be attributed to physical adsorption and evaporation of water adsorbed by hydrophilic groups.
The temperature ranges of the CPAM and the CCoS in the second stage are 110-211 ℃ and 110-200 ℃ respectively, and the CPAM/CoFe temperature ranges are respectively 2 O 4 The SCA's initial decomposition temperature at this stage is advanced compared to CPAM, and the mass loss at this stage corresponds to the decomposition and imidization of the amide groups and the cleavage of intermolecular hydrogen bonds formed by part of the amide groups.
The temperature ranges of the third stage are not greatly different, and the thermal weight loss of the third stage is mainly caused by the decomposition of quaternary ammonium salt groups; the thermal weight loss of CPAM and CCoS in the range of 200 ℃ to 427 ℃ is the decomposition of the polymer backbone.
The temperature difference between the fourth stage 427 deg.c and 589 deg.c is not great, both because the CPAM gradually approaches complete decomposition at this stage.
CPAM in the fifth stage is basically completely decomposed at 589-900 ℃, the residual mass of CPAM and CCoS after complete decomposition is 21.38% and 23.08% respectively, and the residual mass is due to undegradable CoFe in the system 2 O 4 Thus, coFe can also be described 2 O 4 The SCA is present in the form of a covalent bond in the CCoS.
In the foregoing, the present application is merely preferred embodiments, which are based on different implementations of the overall concept of the application, and the protection scope of the application is not limited thereto, and any changes or substitutions easily come within the technical scope of the present application as those skilled in the art should not fall within the protection scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.
Claims (10)
1. The green synthesis method of the core-shell structure CCoS magnetic flocculant with the chromium removal function is characterized by comprising the following steps of:
s1: nanometer CoFe prepared by hydrothermal/high-temperature calcination method 2 O 4 Particles;
s2: dissolving SCA in water, regulating pH to 5-6, stirring to hydrolyze, and adding nano CoFe 2 O 4 The particles are dispersed in the water by ultrasonic, then the water-heat reaction is carried out, and after the reaction is finished, the washing and the vacuum drying are carried out to obtain CoFe 2 O 4 -SCA particles;
s3: dissolving AM in water, then dissolving CoFe 2 O 4 The SCA particles are dispersed in the ultrasonic wave, then dimethyl diallyl ammonium chloride, ammonium sulfate, dispersing agent, sodium chloride and polyethylene glycol 400 are added, and N is introduced after stirring and dissolution 2 Deoxidizing, adding photoinitiator at 10deg.C, ultraviolet polymerizing, standing for a certain time to obtain CPAM/CoFe 2 O 4 -SCA。
2. The method according to claim 1, wherein S1 comprises the specific steps of:
(1) Mixing cobalt ion aqueous solution and iron ion aqueous solution, adding CTAB, continuously stirring for 60min, regulating the pH value of the solution to 8.5-10.5, continuously stirring for 30min, then transferring into a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting for 15-20h at 160-190 ℃, cooling to room temperature, washing and drying;
(2) Calcining in a muffle furnace at 600-800 ℃ for 3-5h to obtain nano CoFe 2 O 4 And (3) particles.
3. The method as claimed in claim 1, characterized in that the concentration of the aqueous SCA solution in S2 is 0.5-1.75 wt.%, nano CoFe 2 O 4 The mass ratio of the particles to the SCA is (10-20): 1.
4. The method according to claim 1, wherein the hydrothermal reaction temperature in S2 is 80-90 ℃ for 40-50min.
5. The method according to claim 1, wherein AM, coFe in S3 2 O 4 The SCA particles, the dimethyl diallyl ammonium chloride, the ammonium sulfate, the dispersing agent, the sodium chloride and the polyethylene glycol 400 respectively account for 6-8% of the total mass of the materials, 0.05-0.3%, 1.5-3.5%, 24-28%, 0.5-2%, 0.25-2.5%, 0.5-2% of the total mass of the materials, and the balance is water.
6. The method according to claim 1, wherein the photoinitiator in S3 is photoinitiator V005 added in an amount of 0.003-0.01% by weight of the total mass of the material.
7. The method according to claim 1, wherein the ultraviolet irradiation power in S3 is 6-20W and the irradiation time is 3-5min.
8. The method according to claim 1, wherein the stirring reaction is continued for 5-7 hours after the irradiation in S3 is completed.
9. The magnetic flocculant of any one of claims 1-8, wherein the shell is CPAM and the core is CoFe 2 O 4 -SCA，CoFe 2 O 4 Covalently linked to the SCA.
10. Use of a magnetic flocculant produced by the method of any one of claims 1-8 in chromium-containing domestic wastewater.
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