CN113019339A - Preparation method of magnetic nano material for printing and dyeing wastewater - Google Patents

Preparation method of magnetic nano material for printing and dyeing wastewater Download PDF

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CN113019339A
CN113019339A CN202110192295.7A CN202110192295A CN113019339A CN 113019339 A CN113019339 A CN 113019339A CN 202110192295 A CN202110192295 A CN 202110192295A CN 113019339 A CN113019339 A CN 113019339A
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printing
dyeing wastewater
opal shale
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CN113019339B (en
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丁俊杰
原晔
余金礼
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Wuhan Lvzhixing Environmental Protection Technology Co ltd
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28009—Magnetic properties
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/46—Materials comprising a mixture of inorganic and organic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Water Treatment By Sorption (AREA)
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Abstract

The invention relates to the technical field of wastewater treatment, in particular to a preparation method of a magnetic nano material for printing and dyeing wastewater. The preparation method of the magnetic nano material for printing and dyeing wastewater comprises three steps of opal shale surface treatment, opal shale surface modification and core-shell reaction. The modified opal shale has the advantages that the surface hydrophilic performance is improved, the capability of adsorbing dye and heavy metal is further improved, the opal shale can be better compatible with wastewater water body when being adsorbed, and the practicability is high.

Description

Preparation method of magnetic nano material for printing and dyeing wastewater
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a preparation method of a magnetic nano material for printing and dyeing wastewater.
Background
The printing and dyeing wastewater is wastewater discharged from printing and dyeing factories which mainly process cotton, hemp, chemical fibers and blended products thereof. The amount of the printing and dyeing wastewater is large, 100-200 tons of water are consumed for each 1 ton of textiles processed by printing and dyeing, and 80-90% of the water finally becomes wastewater. The textile printing and dyeing wastewater has the characteristics of high yield, high organic pollutant content and the like, contains a large amount of dye, auxiliary agent and heavy metal pollutants, and the pollutants are decomposed to generate various carcinogenic substances after flowing into rivers, slightly cause skin allergy and seriously cause tumors and cancers. In addition, the additives, the sizing agents and the like in the printing and dyeing wastewater are also doped with heavy metal ions, and the heavy metal ions are easily combined with organisms, are enriched into the body through a water body, and finally enter the human body through a food chain to influence the health of people.
The common treatment methods for printing and dyeing wastewater mainly comprise a membrane separation method, a chemical method, an oxidation-reduction method, a photocatalysis method, an adsorption method and the like. The membrane separation method cannot be used in a large scale at present due to its high cost. The chemical method mainly uses chemicals to precipitate substances in the wastewater, and then carries out solid-liquid separation, although the method has low cost, because a large amount of precipitant is required to be added when the wastewater is treated, the precipitant is difficult to recover, and secondary pollution is easily caused. The redox method is mainly to add an oxidant into the wastewater and remove pollutants through redox reaction with dyes, but the method needs to use a large amount of corrosion-resistant equipment, and has complex process flow and high cost. The photocatalytic method is a method in which a photocatalyst converts light energy into chemical energy under irradiation of visible light or ultraviolet rays, and destroys the molecular structure in dye molecules, thereby decomposing organic pollutants and converting the organic pollutants into harmless carbon dioxide and water. The adsorption method has certain advantages in printing and dyeing wastewater treatment by virtue of the advantages of low cost, reproducibility, no secondary pollution and the like, and the nano material is a suitable material for adsorbing pollutants in the printing and dyeing wastewater due to excellent surface property.
However, because the volume of the nano material is small, the nano material is difficult to separate after being added into waste water for adsorption, and secondary pollution to the environment is easy to cause. Therefore, in order to better recover the nano-adsorbent, researchers in various countries carry out magnetic modification on the nano-material, so that the problem of difficulty in recovering the nano-material is solved, and the nano-adsorbent is easily separated from the solution under an applied magnetic field, so that the waste of the material is avoided, and the pollution to the environment is reduced.
Chinese patent CN102527332A discloses a composite magnetic adsorption material and a preparation method and application thereof, wherein the composite magnetic adsorption material is prepared by embedding powdered activated carbon particles and nano Fe mixed with the surface or the interior of the powdered activated carbon particles3O4The magnetic adsorption material can be used for superconducting magnetic separation treatment of sewage, but because the surface hydrophilicity of the material is weak, the material is easy to float after being added into printing and dyeing wastewater for adsorption, and the efficiency for removing pollutants in the wastewater is poor.
Chinese patent CN109317089A discloses a magnetic adsorbing material for thallium-containing wastewater treatment, which is manganese dioxide loaded manganese ferrite, and although the external magnetic field can recover the adsorbing material well, the adsorbing material has general adsorbing capacity and adsorbing rate, which is not beneficial to rapid removal of industrial printing and dyeing wastewater pollutants.
Disclosure of Invention
In order to overcome the technical problems in the prior art, the invention provides a preparation method of a magnetic nano material for printing and dyeing wastewater.
The invention provides a magnetic nano material for printing and dyeing wastewater, and a preparation method of the magnetic nano material comprises the following steps:
s1, performing surface treatment on the opal shale: calcining the opal shale; dissolving in 1-2 mol/L acid, centrifuging, washing with water until the pH value of the supernatant is 6-7, and drying to obtain the surface-treated opal shale;
s2, modifying the surface of the opal shale: taking the opal shale subjected to the surface treatment in the step S1, dripping a silane coupling agent, adding a reflux solvent for refluxing, filtering, washing with ethanol, and drying to obtain the surface-modified opal shale;
s3, core-shell reaction: weighing the surface-modified opal shale obtained in the step S2, adding an alcohol solvent, performing ultrasonic dispersion, adding ferric trichloride hexahydrate, stirring for 3-5 hours, adding sodium acetate and anionic polyelectrolyte, stirring for 40-60 min, transferring to a polytetrafluoroethylene reactor, reacting, washing and drying.
Further, the preparation method of the magnetic nano material comprises the following steps:
s1, performing surface treatment on the opal shale: calcining the opal shale; dissolving in 1.5mol/L acid, centrifuging, washing with water until the pH of the supernatant is 6.5, and drying to obtain surface-treated opal shale;
s2, modifying the surface of the opal shale: taking the opal shale subjected to the surface treatment in the step S1, dripping a silane coupling agent, adding a reflux solvent for refluxing, filtering, washing with ethanol, and drying to obtain the surface-modified opal shale;
s3, core-shell reaction: weighing the surface-modified opal shale obtained in the step S2, adding an alcohol solvent, performing ultrasonic dispersion, adding ferric trichloride hexahydrate, stirring for 4 hours, adding sodium acetate and anionic polyelectrolyte, stirring for 50 minutes, transferring to a polytetrafluoroethylene reactor, reacting, washing and drying.
Further, the acid in step S1 is hydrochloric acid or phosphoric acid.
Further, the silane coupling agent described in step S2 is one or more of 3-aminopropyltriethoxysilane, diethylaminotrimethylsilane and N-aminoethyl-3-aminopropyltriethoxysilane.
Further, the silane coupling agent is prepared from 3-aminopropyltriethoxysilane and N-aminoethyl-3-aminopropyltriethoxysilane in a weight ratio of 1: 0.05-0.5 mass ratio.
Preferably, the silane coupling agent is prepared from 3-aminopropyltriethoxysilane and N-aminoethyl-3-aminopropyltriethoxysilane in a weight ratio of 1: 0.2 in mass ratio.
Further, the refluxing solvent in step S2 is toluene or xylene.
Further, the alcohol solvent in step S3 is one or more of ethanol, methanol, ethylene glycol, and glycerol.
Further, the anionic polyelectrolyte in step S3 is one or more of poly (4-styrenesulfonic acid-co-maleic acid) sodium salt, polystyrenesulfonic acid, polyacrylic acid, and polyvinyl alcohol.
Preferably, the anionic polyelectrolyte in step S3 is poly (4-styrenesulfonic acid-co-maleic acid) sodium salt
Further, in the step S1, the calcining temperature of the opal shale is 200-400 ℃, and the calcining time is 3-6 hours.
Preferably, the calcination temperature of the opal shale in the step S1 is 300 ℃, and the calcination time is 5 h.
Furthermore, the refluxing time in the step S2 is 8-16 h.
Preferably, the reflow time in step S2 is 10 h.
Further, the reaction temperature in the polytetrafluoroethylene reactor is 200-400 ℃, and the reaction time is 12-16 h.
Further, the reaction temperature in the polytetrafluoroethylene reactor is 300 ℃, and the reaction time is 15 h.
Compared with the prior art, the preparation method of the magnetic nano material for printing and dyeing wastewater provided by the invention has the following beneficial effects:
(1) according to the invention, the polyanionic electrolyte modified opal shale coated magnetic nano material is prepared, and the material has a good effect on adsorption of dye in printing and dyeing wastewater, and has excellent removal efficiency of heavy metal and dye in wastewater.
(2) The opal shale used in the invention is subjected to surface treatment and then surface modification, the number of surface hydroxyl groups of the opal shale powder after the surface treatment is increased, the hydrophilic property is increased, and then the surface hydroxyl groups are subjected to surface modification with a silane coupling agent with amino groups, so that the adsorption capacity of the opal shale after the surface modification is increased, the hydrophilic property is further improved, the opal shale can be better compatible with a wastewater body during adsorption, and the practicability is strong.
Detailed Description
The present invention is further described in the following description of the specific embodiments, which is not intended to limit the invention, but various modifications and improvements can be made by those skilled in the art based on the basic idea of the invention without departing from the scope of the invention. The reagents used are those not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
The preparation method of the magnetic nano material for printing and dyeing wastewater in the embodiment 1 comprises the following steps:
s1, performing surface treatment on the opal shale: calcining the opal shale at 200 ℃ for 6 h; dissolving in 1mol/L hydrochloric acid, centrifuging, washing with distilled water until the pH of the supernatant is 6, and drying to obtain the surface-treated opal shale;
s2, modifying the surface of the opal shale: taking the opal shale subjected to surface treatment in the step S1, dripping 3-aminopropyl triethoxysilane into the opal shale, adding toluene, refluxing for 8 hours, filtering, washing with ethanol, and drying to obtain the opal shale subjected to surface modification;
s3, core-shell reaction: weighing the surface-modified opal shale obtained in the step S2, adding an ethanol solvent, performing ultrasonic dispersion, adding ferric trichloride hexahydrate, stirring for 3 hours, adding sodium acetate and polystyrene sulfonic acid, stirring for 40min, transferring to a polytetrafluoroethylene reactor, reacting for 16 hours at 200 ℃, washing with ethanol, and drying.
Example 2
The preparation method of the magnetic nano material for printing and dyeing wastewater in the embodiment 2 comprises the following steps:
s1, performing surface treatment on the opal shale: calcining the opal shale at 400 ℃ for 3 h; dissolving in 2mol/L phosphoric acid, centrifuging, washing with distilled water until the pH of the supernatant is 7, and drying to obtain the surface-treated opal shale;
s2, modifying the surface of the opal shale: taking the opal shale subjected to the surface treatment in the step S1, dripping diethylaminotrimethylsilane into the opal shale, adding xylene into the opal shale, refluxing for 16 hours, filtering, washing with ethanol, and drying to obtain the surface-modified opal shale;
s3, core-shell reaction: weighing the surface-modified opal shale obtained in the step S2, adding a methanol solvent, performing ultrasonic dispersion, adding ferric trichloride hexahydrate, stirring for 5 hours, adding sodium acetate and polyacrylic acid, stirring for 60 minutes, transferring to a polytetrafluoroethylene reactor, reacting for 12 hours at 400 ℃, washing with ethanol, and drying.
Example 3
The preparation method of the magnetic nanomaterial for printing and dyeing wastewater of embodiment 3 comprises the following steps:
s1, performing surface treatment on the opal shale: calcining the opal shale at 300 ℃ for 5 hours; dissolving in 1.5mol/L phosphoric acid, centrifuging, washing with distilled water until the pH of the supernatant is 7, and drying to obtain the surface-treated opal shale;
s2, modifying the surface of the opal shale: taking the opal shale subjected to surface treatment in the step S1, dripping N-aminoethyl-3-aminopropyltriethoxysilane into the opal shale, adding xylene, refluxing for 10 hours, filtering, washing with ethanol, and drying to obtain the surface-modified opal shale;
s3, core-shell reaction: weighing the surface-modified opal shale obtained in the step S2, adding an ethylene glycol solvent, performing ultrasonic dispersion, adding ferric trichloride hexahydrate, stirring for 4 hours, adding sodium acetate and polyvinyl alcohol, stirring for 50min, transferring to a polytetrafluoroethylene reactor, reacting for 15 hours at 300 ℃, washing with ethanol, and drying.
Example 4
The preparation method of the magnetic nanomaterial for printing and dyeing wastewater of embodiment 4 comprises the following steps:
s1, performing surface treatment on the opal shale: calcining the opal shale at 300 ℃ for 4 h; dissolving in 1mol/L phosphoric acid, centrifuging, washing with distilled water until the pH of the supernatant is 7, and drying to obtain the surface-treated opal shale;
s2, modifying the surface of the opal shale: and (3) dripping a silane coupling agent into the opal shale subjected to surface treatment in the step S1, wherein the silane coupling agent is prepared by mixing 3-aminopropyltriethoxysilane and N-aminoethyl-3-aminopropyltriethoxysilane in a ratio of 1: 0.2, adding dimethylbenzene, refluxing for 10 hours, filtering, washing with ethanol, and drying to obtain the surface-modified opal shale;
s3, core-shell reaction: weighing the surface-modified opal shale obtained in the step S2, adding an ethylene glycol solvent, performing ultrasonic dispersion, adding ferric trichloride hexahydrate, stirring for 4 hours, adding sodium acetate and poly (4-styrenesulfonic acid-co-maleic acid) sodium salt, stirring for 50 minutes, transferring to a polytetrafluoroethylene reactor, reacting for 15 hours at 300 ℃, washing with ethanol, and drying.
Example 5
The preparation method of the magnetic nano material for printing and dyeing wastewater of the embodiment 5 comprises the following steps:
s1, performing surface treatment on the opal shale: calcining the opal shale at 400 ℃ for 4 h; dissolving in 2mol/L phosphoric acid, centrifuging, washing with distilled water until the pH of the supernatant is 6, and drying to obtain the surface-treated opal shale;
s2, modifying the surface of the opal shale: and (3) dripping a silane coupling agent into the opal shale subjected to surface treatment in the step S1, wherein the silane coupling agent is prepared by mixing 3-aminopropyltriethoxysilane and N-aminoethyl-3-aminopropyltriethoxysilane in a ratio of 1: 0.05, adding toluene, refluxing for 13 hours, filtering, washing with ethanol, and drying to obtain the surface-modified opal shale;
s3, core-shell reaction: weighing the surface-modified opal shale obtained in the step S2, adding an ethylene glycol solvent, performing ultrasonic dispersion, adding ferric trichloride hexahydrate, stirring for 4 hours, adding sodium acetate and poly (4-styrenesulfonic acid-co-maleic acid) sodium salt, stirring for 50 minutes, transferring to a polytetrafluoroethylene reactor, reacting for 14 hours at 350 ℃, washing with ethanol, and drying.
Comparative example 1
The opal shale in the method for preparing a magnetic nanomaterial for printing and dyeing wastewater of comparative example 1 is not subjected to the surface treatment step of step S1, the opal shale is directly subjected to the surface modification process of step S2, and the surface-modified opal shale is further subjected to the core-shell reaction of step S3, wherein steps S2 and S3 are the same as example 4.
Comparative example 2
The opal shale in the method for preparing a magnetic nanomaterial for printing and dyeing wastewater of comparative example 2 does not undergo the surface modification step of step S2, but only undergoes the steps S1 and S3, i.e., the opal shale after surface treatment is directly subjected to the core-shell reaction, wherein the steps S1 and S3 are the same as those of example 4.
Comparative example 3
In the method for preparing the magnetic nanomaterial for printing and dyeing wastewater of comparative example 3, poly (4-styrenesulfonic acid-co-maleic acid) sodium salt was not added in step S3, and the other steps and reaction materials were the same as those in example 4.
Comparative example 4
The preparation method of the magnetic nanomaterial for printing and dyeing wastewater of comparative example 4 does not use opal shale as the adsorbing material, uses titanium dioxide P25 powder as the adsorbing material, and has the same steps and reaction materials as those of example 4.
Comparative example 5
The opal shale of comparative example 5 was neither surface-treated nor surface-modified, and only subjected to the core-shell reaction of step S3, in which step S3 was the same as in example 4.
Experimental example 1 specific surface area and wettability test of opal shale in magnetic nanomaterial of the present invention
1g of opal shale powder for preparing the magnetic nano material in the embodiments 1-5, the comparative examples 1-2 and the comparative examples 4-5 is dispersed in 5mL of absolute ethyl alcohol, uniformly coated on a glass slide respectively and dried, 5 sample wafers are coated on each embodiment or comparative example respectively, deionized water is used as test liquid, a static water contact angle test of the surface of a sample is carried out by an optical contact angle measuring instrument at 20 ℃, the test data of the 5 sample wafers are calculated to be an average value, and the result is expressed by a unit degree.
Table 1 specific surface area and wettability testing of opal shale in magnetic nanomaterials of the invention
Figure BDA0002944964470000061
As shown in table 1, the contact angle of the modified opal shale prepared by the method of the present invention is also greatly reduced, wherein the contact angle of the modified opal shale prepared by the method of example 4 to water is only 27.5 °, which indicates that the hydrophilic property of the modified opal shale is greatly improved, and the material can be well compatible with the wastewater water body, does not float on the wastewater water body, and can further improve the adsorption efficiency.
Test example 2 adsorption capacity test of magnetic nanomaterial of the present invention
50mg of the magnetic nanomaterial for printing and dyeing wastewater prepared by the methods of examples 1 to 5 and comparative examples 1 to 5 are respectively put into a 50mL colorimetric tube with a cover, 5 samples to be tested are respectively prepared in each example or test example, 10mL of methylene blue solution with the concentration of 100mg/L and the pH value of 7.0 is respectively added, the colorimetric tube is covered and then put into a constant temperature water bath oscillator for shaking, the colorimetric tube is taken out after adsorption is carried out for 1min, 5min, 10min, 30min and 60min, magnetic separation is carried out, the absorbance of the supernatant is tested by an ultraviolet spectrophotometer, the concentration of the methylene blue solution after adsorption is calculated according to the absorbance and a standard working curve, and the adsorption capacity of the magnetic nanomaterial is calculated. The adsorption capacity is calculated as follows: qe＝[(C0-Ce)×V]M, wherein QeThe adsorption capacity is expressed in mg/g; c0、CeThe concentration of methylene blue solution before and after adsorption is expressed in mg/L; v is the volume of methylene blue solution, and the unit is mL; and m is the mass of the magnetic nano material and has the unit of mg.
Table 2 adsorption capacity test of magnetic nanomaterial of the present invention
Figure BDA0002944964470000071
The magnetic nano material for printing and dyeing wastewater prepared by the method can reach adsorption balance within 10min, wherein in example 4, the adsorption capacity reaches 60.4mg/g within 5 min. The opal shale in the method for preparing the magnetic nanomaterial for printing and dyeing wastewater of comparative example 1 does not undergo the surface treatment step of step S1, and other steps are the same as those of example 4, so that the adsorption capacity is greatly reduced, the adsorption equilibrium time is improved, and the adsorption equilibrium can be reached after 30 min; the opal shale in the method for preparing the magnetic nanomaterial for printing and dyeing wastewater of comparative example 2 does not undergo the surface modification step of step S2, and other steps are the same as those of the reaction substance and example 4, and the adsorption capacity is greatly reduced compared with example 4; the method for preparing the magnetic nanomaterial for printing and dyeing wastewater of the comparative example 3 does not add poly (4-styrenesulfonic acid-co-maleic acid) sodium salt, and other steps are consistent with those of the reaction substance and the example 4, and it can be seen that although the adsorption capacity of the magnetic nanomaterial finally differs from that of the example 4 by 59.4mg/g, the magnetic nanomaterial prepared by the method of the comparative example can reach adsorption equilibrium after 30min, and the time for reaching the adsorption equilibrium is much slower than that of the example 4, which shows that the poly (4-styrenesulfonic acid-co-maleic acid) sodium salt has the effect of enabling the prepared magnetic nanomaterial to quickly adsorb pollutants, probably because the poly (4-styrenesulfonic acid-co-maleic acid) sodium salt has a large amount of carboxyl groups and sulfonic groups, the existence of the carboxyl and the sulfonic group can enable the cationic pollutants to be better bonded electrostatically, and further greatly reduce the adsorption balance time. In addition, the opal shale of comparative example 5 is not subjected to surface treatment or surface modification, only the core-shell structure reaction shown in example 4 is performed, and the adsorption capacity is the worst of all the examples and comparative examples, which further illustrates that the modified opal shale can well improve the adsorption capacity for methylene blue, so as to achieve the purpose of removing pollutants.
Test example 3 test of removing effect of the magnetic nanomaterial of the present invention on harmful substances
And (3) testing the removal effect of the heavy metal harmful substances: 50mg of the magnetic nanomaterial for printing and dyeing wastewater prepared by the methods of example 4 and comparative examples 3 and 5 was placed in a 50mL colorimetric tube with a cover, 10mL of a mixed solution of copper ions and lead ions at a concentration of 50mg/L was added, the colorimetric tube was covered with the cover and then placed in a thermostatic waterbath oscillator to shake for 20min, the colorimetric tube was taken out, magnetic separation was performed, and the content of copper ions and lead ions in the supernatant was measured by ICP. The calculation formula of the removal rate of the heavy metal harmful substances is as follows: r1＝[(C1-C2)/C1]X 100%, wherein C1And C2The concentrations of heavy metal ions before and after adsorption, respectively, were obtained, and the final results were expressed in%.
And (3) testing the removing effect of harmful substances of the azo dye: : 50mg of the magnetic nanomaterial for printing and dyeing wastewater prepared by the methods of example 4 and comparative examples 3 and 5 were placed in 50mL colorimetric tubes with covers, and added10mL of disperse yellow 23 methanol solution with the concentration of 30mg/L, covering a cover of the colorimetric tube, putting the colorimetric tube into a constant-temperature water bath oscillator, shaking for 20min, taking out the colorimetric tube, carrying out magnetic separation, and measuring the content of the disperse yellow 23 solution in the supernatant after adsorption by using high performance liquid chromatography. The calculation formula of the removal rate of the harmful substances of the azo dye is as follows: r2＝[(C3-C4)/C1]X 100%, wherein C3And C4The concentrations of the azo dye harmful substance before and after adsorption are shown respectively, the final result is expressed in percent, and the test results are shown in Table 3:
table 3 test of removing effect of the magnetic nanomaterial of the present invention on the harmful substance
Figure BDA0002944964470000081
From the test results shown in table 3, the magnetic nanomaterial for printing and dyeing wastewater prepared in example 4 has better removal efficiency for heavy metal ions and azo dyes, the removal efficiency for copper ions and lead ions is 90.8% and 95.6%, respectively, and the removal efficiency for disperse yellow 23 azo dye can reach 87.4%. In the method for preparing the magnetic nanomaterial for printing and dyeing wastewater in the comparative example 3, no poly (4-styrenesulfonic acid-co-maleic acid) sodium salt is added, and other steps are consistent with those of the reaction substance and the example 4, so that the removal efficiency of copper ions and lead ions is greatly reduced, which shows that the magnetic nanomaterial prepared by adding the poly (4-styrenesulfonic acid-co-maleic acid) sodium salt can better adsorb heavy metal ions in wastewater.
According to the invention, the magnetic nano material for printing and dyeing wastewater is prepared through the steps of opal shale surface treatment, opal shale surface modification and core-shell reaction, and the prepared magnetic nano material has good hydrophilic property and adsorption capacity, high dye and heavy metal removal efficiency and strong practicability.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed.

Claims (10)

1. A preparation method of a magnetic nano material for printing and dyeing wastewater is characterized by comprising the following steps: the method comprises the following steps:
s1, performing surface treatment on the opal shale: calcining the opal shale; dissolving in 1-2 mol/L acid, centrifuging, washing with water until the pH value of the supernatant is 6-7, and drying to obtain the surface-treated opal shale;
s2, modifying the surface of the opal shale: taking the surface-treated opal shale obtained in the step S1, dripping a silane coupling agent, adding a reflux solvent for refluxing, filtering, washing with ethanol, and drying to obtain surface-modified opal shale;
s3, core-shell reaction: weighing the surface-modified opal shale obtained in the step S2, adding an alcohol solvent, performing ultrasonic dispersion, adding ferric trichloride hexahydrate, stirring for 3-5 hours, adding sodium acetate and anionic polyelectrolyte, stirring for 40-60 min, transferring to a polytetrafluoroethylene reactor, reacting, washing and drying.
2. The method for preparing the magnetic nano material for printing and dyeing wastewater according to claim 1, which is characterized by comprising the following steps: the acid in step S1 is hydrochloric acid or phosphoric acid.
3. The method for preparing the magnetic nano material for printing and dyeing wastewater according to claim 1, which is characterized by comprising the following steps: the silane coupling agent in step S2 is one or more of 3-aminopropyltriethoxysilane, diethylaminotrimethylsilane, and N-aminoethyl-3-aminopropyltriethoxysilane.
4. The method for preparing the magnetic nano material for printing and dyeing wastewater according to claim 3, which is characterized by comprising the following steps: the silane coupling agent is prepared from 3-aminopropyltriethoxysilane and N-aminoethyl-3-aminopropyltriethoxysilane in a weight ratio of 1: 0.05-0.5 mass ratio.
5. The method for preparing the magnetic nano material for printing and dyeing wastewater according to claim 1, which is characterized by comprising the following steps: the refluxing solvent in step S2 is toluene or xylene.
6. The method for preparing the magnetic nano material for printing and dyeing wastewater according to claim 1, which is characterized by comprising the following steps: the alcohol solvent in step S3 is one or more of ethanol, methanol, ethylene glycol, and glycerol.
7. The method for preparing the magnetic nano material for printing and dyeing wastewater according to claim 1, which is characterized by comprising the following steps: the anionic polyelectrolyte in step S3 is one or more of poly (4-styrenesulfonic acid-co-maleic acid) sodium salt, polystyrenesulfonic acid, polyacrylic acid, and polyvinyl alcohol.
8. The method for preparing the magnetic nano material for printing and dyeing wastewater according to claim 1, which is characterized by comprising the following steps: in the step S1, the calcining temperature of the opal shale is 200-400 ℃, and the calcining time is 3-6 h.
9. The method for preparing the magnetic nano material for printing and dyeing wastewater according to claim 1, which is characterized by comprising the following steps: the refluxing time in the step S2 is 8-16 h.
10. The method for preparing the magnetic nano material for printing and dyeing wastewater according to claim 1, which is characterized by comprising the following steps: the reaction temperature in the polytetrafluoroethylene reactor is 200-400 ℃, and the reaction time is 12-16 h.
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CN104475040A (en) * 2014-12-31 2015-04-01 湖南大学 Modified magnetic nano adsorption material as well as preparation method and application thereof
CN104817064A (en) * 2015-05-08 2015-08-05 吉林大学 Opoka-base carbon composite material and preparation method thereof
CN105836925A (en) * 2016-05-19 2016-08-10 四川大学 Hexavalent chromium-wastewater treatment method integrating 'reduction, adsorption and magnetic removal'
CN106824288A (en) * 2017-02-07 2017-06-13 天津城建大学 Magnetic quinone amboceptor nano-functional material and its preparation method and application

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104475040A (en) * 2014-12-31 2015-04-01 湖南大学 Modified magnetic nano adsorption material as well as preparation method and application thereof
CN104817064A (en) * 2015-05-08 2015-08-05 吉林大学 Opoka-base carbon composite material and preparation method thereof
CN105836925A (en) * 2016-05-19 2016-08-10 四川大学 Hexavalent chromium-wastewater treatment method integrating 'reduction, adsorption and magnetic removal'
CN106824288A (en) * 2017-02-07 2017-06-13 天津城建大学 Magnetic quinone amboceptor nano-functional material and its preparation method and application

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