WO2020243996A1 - Manganese dioxide@polymetaphenylenediamine@ferroferric oxide composite material, preparation method therefor, and application thereof - Google Patents

Manganese dioxide@polymetaphenylenediamine@ferroferric oxide composite material, preparation method therefor, and application thereof Download PDF

Info

Publication number
WO2020243996A1
WO2020243996A1 PCT/CN2019/091977 CN2019091977W WO2020243996A1 WO 2020243996 A1 WO2020243996 A1 WO 2020243996A1 CN 2019091977 W CN2019091977 W CN 2019091977W WO 2020243996 A1 WO2020243996 A1 WO 2020243996A1
Authority
WO
WIPO (PCT)
Prior art keywords
composite material
manganese dioxide
phenylenediamine
ferroferric oxide
heavy metal
Prior art date
Application number
PCT/CN2019/091977
Other languages
French (fr)
Chinese (zh)
Inventor
袁兴中
熊婷
曹旭洋
杨羽茜
彭叶琼
曾光明
Original Assignee
湖南大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 湖南大学 filed Critical 湖南大学
Publication of WO2020243996A1 publication Critical patent/WO2020243996A1/en

Links

Images

Classifications

    • 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
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • 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
    • 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
    • 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
    • B01J20/28011—Other properties, e.g. density, crush strength
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • 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
    • 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
    • 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

Definitions

  • the invention belongs to the technical field of environmentally friendly adsorption materials, and relates to a manganese dioxide@polymetaphenylenediamine@tetraoxide three iron shell core structure composite material and a preparation method and application thereof.
  • Heavy metal pollution is very common. Heavy metal ions cannot be degraded through natural biological processes, posing a threat to the water environment and biological health. It can enter the aquatic environment through a variety of ways, including electroplating plants, mining industry, electronics manufacturing, inorganic pigment manufacturing, and waste water from the wood processing industry. Heavy metals have strong chemical stability and biodegradability, and can exist in water for a long time, causing damage to the nervous system, tissues and organs of organisms, and continuing to cause serious environmental and health problems.
  • Poly-m-phenylene diamine is often used in the treatment of polluted water bodies. As a typical amino conjugated polymer, it has dense amine groups and imine groups and exhibits strong adsorption capacity for many pollutants. However, according to previous studies, because poly-m-phenylene diamine has a small specific surface area and a positive surface charge, it has a low affinity for heavy metals and a poor adsorption effect. Manganese dioxide has attracted attention because of its large surface area, strong heavy metal adsorption capacity, easy synthesis, low cost, high environmental stability, etc., and more importantly, manganese dioxide can pass between carbon and potassium permanganate. A simple redox reaction is loaded on the surface of the organic material to form a multi-core shell-core composite material.
  • ferroferric oxide has inherent superparamagnetic properties. Using it as the core of the composite material allows the composite material to be easily magnetically separated from the solution.
  • Patent application 201610065134.0 synthesized manganese dioxide@polymetaphenyldiamine@tetraoxide three iron shell core structure composite material for arsenic adsorption, but the prior art has the following defects: 1. The amount of potassium permanganate in the synthesis process Higher, there is a waste of resources; 2. Too low synthesis temperature of poly-m-phenylene diamine will affect the synthesis yield, resulting in poor adsorption effect. 3. The pH in the synthesis process of poly-m-phenylenediamine is not adjusted, which affects the oxidation process of m-phenylenediamine, which affects the adsorption capacity.
  • the technical problem to be solved by the present invention is to overcome the shortcomings of the prior art, optimize the synthesis method of manganese dioxide@polymetaphenyldiamine@tetraoxide three iron shell core structure composite material, and provide a low cost and good adsorption performance
  • Manganese dioxide@polymeta-phenylenediamine@iron tetroxide composite adsorbent also provides a simple preparation process, simple operation, mild reaction conditions, low cost, high production efficiency, short production cycle, and high product yield.
  • the present invention adopts the following technical solutions:
  • a manganese dioxide@polymetaphenylenediamine@triiron tetroxide composite material which is characterized in that it comprises ferroferric oxide, manganese dioxide and poly-m-phenylene diamine.
  • the poly-m-phenylene diamine is supported on On the surface of tri-iron, manganese dioxide is supported on the surface of poly-m-phenylene diamine, and finally a ternary composite material with a double-layer core-shell structure is formed;
  • the mass ratio in the ferroferric oxide composite material is not higher than 40%.
  • the mass ratio of ferroferric oxide, polym-phenylene diamine, and manganese dioxide in the manganese dioxide@polym-phenylenediamine@ferric oxide composite material ranges from 1:1.1:0.9-1:2:0.1
  • the specific surface area of the manganese dioxide@polym-phenylenediamine@ferric oxide composite material is 150m 2 /g-220m 2 /g.
  • the ferroferric oxide has a spherical shape with a rough surface and a size of about 50-100 nm;
  • the poly-m-phenylene diamine has a spherical shape and a smooth surface;
  • the manganese dioxide@polym-phenylenediamine@tetrairon tetraoxide composite material is Sea urchin-like, rough surface. Compared with m-phenylenediamine, the sea urchin-like specific surface area will increase, which will improve the adsorption performance of the material.
  • the method for preparing the manganese dioxide@polymetaphenylenediamine@ferric oxide composite material is characterized in that it comprises the following steps:
  • step S3 mixing the dispersion of ferroferric oxide and m-phenylenediamine obtained in step S2 with an oxidizing agent for oxidative polymerization to obtain a polym-phenylene diamine@triiron tetraoxide composite material;
  • step S4 Disperse the poly-m-phenylenediamine@triiron tetraoxide composite material obtained in step S3 into water to obtain a colloidal dispersion, and add potassium permanganate solution to it to perform oxidation-reduction reaction to obtain manganese dioxide@polymetaphthalene Amine@Tri-iron tetraoxide shell core structure composite material.
  • the mass ratio of the ferroferric oxide, m-phenylenediamine, oxidant and potassium permanganate is 1:1.1:0.9-1:2:0.1;
  • the oxidant is ammonium persulfate and/or sodium persulfate.
  • Ferroferric oxide only provides magnetism, and the adsorption site is located on m-phenylenediamine. The higher the content of ferroferric oxide, the lower the adsorption capacity per unit mass. Therefore, it is necessary to control the content of ferroferric oxide in the composite material. During the preparation process, the amount of ferroferric oxide added is controlled.
  • the temperature of the ultrasonic dispersion is 15°C to 45°C; the time of the ultrasonic dispersion is 0.5h to 1h.
  • Ultrasound is to make m-phenylenediamine and ferroferric oxide disperse more uniformly in water, help the uniform combination of the two, and prevent the uneven combination of agglomerates, and the temperature is to keep consistent with subsequent reactions.
  • the time is the minimum ultrasound time that can achieve the effect.
  • step S3 lye is added during the oxidative polymerization reaction to maintain the pH value of the reaction system, and the yield of poly(m-phenylene diamine@ferric oxide) is increased by about 5%-10%.
  • 10% to 30% of the total volume of the reaction system is added in an amount of lye;
  • the alkaline solution is sodium hydroxide and / or potassium hydroxide solution;
  • the oxidative polymerization reaction is carried out under stirring conditions; the temperature of the oxidative polymerization reaction is 25° C. to 45° C., and the yield of poly-m-phenylene diamine@ferric oxide is increased by about 5%-15%.
  • the oxidative polymerization reaction time is 5h-10h.
  • step S4 an acid is added during the oxidation-reduction reaction process to maintain the pH value of the reaction system, the acid is a hydrochloric acid/nitric acid/sulfuric acid solution; the concentration of H + in the acid is 5M-15M; the oxidation
  • the reduction reaction is carried out under stirring conditions; the temperature of the redox reaction is 0°C to 5°C; the time of the redox reaction is 1h-12h.
  • the manganese dioxide@polymetaphenylenediamine@triiron tetraoxide composite material or the manganese dioxide@polymetaphenylenediamine@triiron tetraoxide composite material prepared by the preparation method is useful in the treatment of heavy metal wastewater application.
  • the application includes the following steps: mixing manganese dioxide@polymeta-phenylenediamine@tetrairon tetraoxide composite material and heavy metal wastewater for vibration adsorption to complete the treatment of heavy metal wastewater;
  • the addition amount of the amine@triiron tetraoxide composite material is 0.1g ⁇ 0.5g per liter of heavy metal wastewater.
  • the concentration of the heavy metal wastewater is 50 mg/L to 100 mg/L Cd and/or 50 mg/L to 200 mg/L Pb; the pH value of the heavy metal wastewater is 2 to 7;
  • the rotational speed of the oscillating adsorption is 100 rpm to 200 rpm; the temperature of the oscillating adsorption is 15° C. to 45° C.; the time of the oscillating adsorption is 1 min to 1440 min.
  • a manganese dioxide@polymetaphenylenediamine@triiron tetraoxide composite material includes triiron tetroxide, manganese dioxide and polymetaphenylene Diamine, the poly-m-phenylene diamine is supported on the surface of ferroferric oxide, and the manganese dioxide is supported on the surface of the poly-m-phenylene diamine.
  • the above-mentioned manganese dioxide@polymeta-phenylenediamine@triiron tetraoxide composite material is further improved.
  • the triiron tetroxide and polymeta The mass ratio of phenylenediamine and manganese dioxide is in the range of 1:1.1:0.9-1:2:0.1; the ferroferric oxide has a spherical shape with a rough surface and a small size; the poly-m-phenylenediamine is spherical, The surface is smooth; the manganese dioxide@polymetaphenylenediamine@triiron tetroxide composite material is sea urchin-like with a rough surface.
  • the present invention also provides a method for preparing the above-mentioned manganese dioxide@polymetaphenylenediamine@three iron composite material, which includes the following steps:
  • step S3 mixing the dispersion of ferroferric oxide and m-phenylenediamine obtained in step S2 with an oxidizing agent to perform an oxidative polymerization reaction to obtain a polym-phenylene diamine@triiron tetraoxide composite material.
  • step S4 Disperse the poly-m-phenylenediamine@triiron tetraoxide composite material obtained in step S3 into water to obtain a colloidal dispersion, and add potassium permanganate solution to it to perform oxidation-reduction reaction to obtain manganese dioxide@polymetaphthalene Amine@Tri-iron tetraoxide shell core structure composite material.
  • the above preparation method is further improved, and the mass ratio of the ferroferric oxide, m-phenylenediamine, oxidant and potassium permanganate is 1:1.1:0.9-1:2:0.1.
  • the above preparation method is further improved, and the oxidant is ammonium persulfate and/or sodium persulfate.
  • the temperature of the ultrasonic dispersion is 25° C. to 45° C.; the time of the ultrasonic dispersion is 0.5 h to 1 h;
  • the above preparation method is further improved.
  • lye is added to maintain the pH value of the reaction system; the added amount of lye is 10% to 30% of the total volume of the reaction system; the lye It is sodium hydroxide solution and/or potassium hydroxide solution; the concentration of OH @ in the lye is 1M ⁇ 3M; the oxidative polymerization reaction is carried out under stirring conditions; the temperature of the oxidative polymerization reaction is 15°C ⁇ 45 °C; the time of the oxidative polymerization reaction is 5h-10h.
  • step S4 an acid is added during the redox reaction to maintain the pH of the reaction system, the acid is a hydrochloric acid solution; the concentration of H + in the acid is 5M ⁇ 12M;
  • the redox reaction is carried out under stirring conditions; the temperature of the redox reaction is 0°C ⁇ 5°C; the time of the redox reaction is 4h ⁇ 12h
  • the present invention also provides a manganese dioxide@polymetaphenylenediamine@tetrairon tetraoxide composite material or manganese dioxide@polymetaphenylenediamine@ prepared by the above preparation method.
  • the above application is further improved and includes the following steps: mixing the manganese dioxide@polymetaphenylenediamine@triiron tetraoxide composite material with heavy metal wastewater for vibration adsorption to complete the treatment of the heavy metal wastewater; the manganese dioxide@ The addition amount of poly-m-phenylene diamine@triiron tetraoxide composite material is 0.25g ⁇ 0.5g per liter of heavy metal wastewater with manganese dioxide@polymeta-phenylene diamine@triiron tetraoxide composite material.
  • the above application is further improved.
  • the concentration of the heavy metal wastewater is 50 mg/L-100 mg/L Cd and/or 50 mg/L-200 mg/L Pb; the pH value of the heavy metal wastewater is 2-7.
  • the above application is further improved.
  • the rotational speed of the oscillating adsorption is 150 rpm to 200 rpm; the temperature of the oscillating adsorption is 15° C. to 45° C.; and the time of the oscillating adsorption is 1 min to 1440 min.
  • the present invention provides a manganese dioxide@polymetaphenylenediamine@triiron tetraoxide composite material, including triiron tetroxide, manganese dioxide and polymetaphenylene diamine, the polymetaphenylene diamine supporting On the surface of ferroferric oxide, manganese dioxide is supported on the surface of poly-m-phenylenediamine.
  • poly-m-phenylenediamine is a typical amino conjugated polymer that can be a variety of pollutants, has a large number of amine groups and imine groups, and can provide adsorption sites for pollutants.
  • manganese dioxide has a large surface area, has a strong affinity for pollutants, and has a good adsorption effect on heavy metal ions. It can pass through organic matter and permanganic acid.
  • the simple oxidation-reduction reaction between potassium loads the surface of organic matter.
  • the loading of manganese dioxide changes the electronegativity of the surface of the poly-m-phenylene diamine, and the composite material changes from positive to negative, which helps the material to adsorb positively charged organics (such as heavy metals) through electrostatic attraction.
  • the ferroferric oxide magnetic core allows the composite material to be easily magnetically separated from the solution, which is beneficial to its practical application.
  • the manganese dioxide@polymetaphenylenediamine@ferric oxide composite material of the present invention has the advantages of low cost, easy synthesis, good adsorption performance, easy separation, etc., can effectively adsorb heavy metals in wastewater, and has good use value and application prospect.
  • the triiron tetroxide and poly The mass ratio of m-phenylenediamine and manganese dioxide is in the range of 1:1.1:0.9-1:2:0.1, which can ensure that the material has sufficient adsorption sites, thereby improving the material's adsorption capacity for heavy metal pollutants, and thus has a better Good adsorption effect.
  • the ferroferric oxide is spherical, the surface is rough, and the size is small, making the spherical polymetaphenylene diamine with smooth surface easier to load To the surface of Fe3O4.
  • the rich functional groups of poly-m-phenylenediamine make it easy to graft manganese dioxide on its surface, and the resulting manganese dioxide@polym-phenylenediamine@triiron tetraoxide composite has more stable properties.
  • Manganese dioxide@polymetaphenylenediamine@ferric oxide composite material is sea urchin-like with rough surface, large surface area and a large number of heavy metal adsorption sites.
  • the present invention also provides a preparation method of manganese dioxide@polym-phenylenediamine@triiron tetroxide composite material.
  • ferric oxide is ultrasonically dispersed in water to make the binding sites on ferric oxide
  • m-phenylenediamine is added at this time, which makes it easier for the m-phenylenediamine to combine with the binding sites on ferroferric oxide, and it is dispersed by ultrasonic to form ferroferric oxide@meta-phenylenediamine, and then acts as an oxidizer
  • An oxidative polymerization reaction takes place under the condition that meta-phenylenediamine is converted into poly-m-phenylenediamine and loaded on the surface of ferroferric oxide.
  • the preparation method of the invention has the advantages of simple process, convenient operation, mild reaction conditions (preparation at room temperature), low cost, high production efficiency, short production cycle, high product yield, etc., is suitable for large-scale preparation and is beneficial to industrial application.
  • the present invention also provides an application of manganese dioxide@polymeta-phenylenediamine@triiron tetraoxide composite material in the treatment of heavy metal wastewater.
  • the mixing of materials and heavy metal wastewater can achieve effective adsorption of heavy metals in wastewater through vibration adsorption. It has the advantages of simple process, convenient operation, easy separation, low cost, high treatment efficiency, and good adsorption effect. It can be applied to treat heavy metal wastewater on a large scale. , Has high application value and commercial value.
  • the invention discloses a manganese dioxide@polymetaphenylenediamine@tetrairon tetraoxide shell-core structure composite material, and a preparation method and application thereof.
  • the manganese dioxide@polymetaphenylenediamine@tetrairon tetraoxide composite material includes Ferroferric oxide, manganese dioxide and poly-m-phenylenediamine, ferroferric oxide is used as the magnetic core, the poly-m-phenylene diamine is loaded on the surface of the ferro-ferric oxide, and the poly-m-phenylene diamine is wrapped with manganese dioxide@ ⁇ The ferroferric oxide compound finally forms the manganese dioxide@polymeta-phenylenediamine@tetraoxide ternary composite material.
  • the preparation method includes preparing a dispersion of ferroferric oxide; preparing a dispersion of ferroferric oxide and m-phenylenediamine; mixing the dispersion of ferroferric oxide and m-phenylenediamine with an oxidizing agent for oxidative polymerization;
  • the poly(m-phenylenediamine@tetraoxide) is prepared as a dispersion; the poly(m-phenylene diamine@tetraoxide) dispersion is mixed with the potassium permanganate solution to undergo redox reaction to generate manganese dioxide, so that the manganese dioxide is loaded to Material surface.
  • the manganese dioxide@polymetaphenylenediamine@triiron tetraoxide shell core structure composite material of the present invention has the advantages of low cost, easy synthesis, good adsorption performance, strong adaptability, easy separation, etc., and its preparation method has simple process and convenient operation , The advantages of mild reaction conditions, low cost, high production efficiency, short production cycle, high product yield, etc., are suitable for large-scale preparation and are conducive to practical industrial applications.
  • the composite material of the invention can be applied to the treatment of heavy metal polluted wastewater, has the advantages of simple process, convenient operation, low cost, high treatment efficiency, good adsorption effect, etc., and has high application value and commercial value.
  • Figure 1(a) is the TEM image of the poly-m-phenylene diamine prepared in Comparative Example 2;
  • Figure 1(b) is the TEM image of the poly-m-phenylene diamine@triiron tetraoxide composite material prepared in Comparative Example 1
  • Figure 1(c) is the TEM image of the manganese dioxide@polym-phenylenediamine@tetrairon tetraoxide composite material (FM150) prepared by adding 150mL of a solution containing 0.02M potassium permanganate in Example 1 of the present invention .
  • FM150 manganese dioxide@polym-phenylenediamine@tetrairon tetraoxide composite material
  • Figure 2 (a) is an X-ray photoelectron spectroscopy (xps) analysis diagram of FP and FM150 prepared in Example 1 of the present invention. (b) is the N Is energy spectrum analysis diagram, (c) is the 0 Is energy spectrum analysis diagram, and (d) is the C Is energy spectrum analysis diagram.
  • xps X-ray photoelectron spectroscopy
  • Figure 3 (a) is the thermogravimetric analysis diagram of FP and FM150 prepared in Example 1 of the present invention; Figure 1 (b) is the hysteresis loop diagram of FP and FM150; (b) is the hysteresis of FP and FM150 Loop graph.
  • Fig. 4 (a) is a comparison diagram of the adsorption amount of heavy metals Pb and Cd by 8 different materials in Example 2 of the present invention; (b) is a zeta potential diagram of 6 different materials.
  • Figure 5(a) shows the FP and FM synthesized in Example 1 of the present invention, the FP synthesized in Comparative Example 4 (corresponding to "FP without NaOH” in the figure), and the FP synthesized in Comparative Example 3 (corresponding to the figure in the figure).
  • “Comparative Example FP" and FM (corresponding to the “Comparative Example FM” in the figure) to compare the adsorption amount of lead ions;
  • (b) is the FM separated solution prepared in Example 1 and Comparative Example FM in Comparative Example 3. Comparison chart of potassium permanganate content in the separated solution.
  • Fig. 6 is a diagram showing the relationship between the amount of heavy metal adsorption by FM150 in Example 3 of the present invention over time.
  • Fig. 7 is a graph showing the relationship between the amount of heavy metals adsorbed by FM150 at different temperatures and the initial concentration in Example 4 of the present invention.
  • Fig. 8 is a diagram showing the relationship between the amount of heavy metal adsorption by FM150 and the change in pH in Example 5 of the present invention, and the corresponding change in Zeta potential.
  • Figure 9 is a graph showing the relationship between the amount of heavy metal adsorption by FM150 and the coexisting ions and humic acid in the sixth embodiment of the present invention.
  • This group of embodiments provides a composite material of manganese dioxide@polymetaphenylenediamine@triiron tetraoxide, which is characterized in that it includes ferroferric oxide, manganese dioxide and polymetaphenylene diamine.
  • the amine is supported on the surface of ferroferric oxide, and the manganese dioxide is supported on the surface of poly(metaphenylene diamine), and finally a ternary composite material with a double-layer core-shell structure is formed; the ferroferric oxide is on the manganese dioxide@ ⁇
  • the mass proportion of phenylenediamine@ferric oxide composite material is not more than 40%.
  • the mass ratio of ferroferric oxide, polym-phenylene diamine, and manganese dioxide in the manganese dioxide@polym-phenylenediamine@triiron tetraoxide composite material ranges from 1:1.1:0.9 -1:2:0.1; the specific surface area of the manganese dioxide@polym-phenylenediamine@ferric oxide composite material is 150m 2 /g-220m 2 /g.
  • This group of embodiments provides a method for preparing the manganese dioxide@polymetaphenylenediamine@triiron tetraoxide composite material described in any one of the first group of embodiments, which is characterized in that it comprises the following steps:
  • step S3 mixing the dispersion of ferroferric oxide and m-phenylenediamine obtained in step S2 with an oxidizing agent for oxidative polymerization to obtain a polym-phenylene diamine@triiron tetraoxide composite material;
  • step S4 Disperse the poly-m-phenylenediamine@triiron tetraoxide composite material obtained in step S3 into water to obtain a colloidal dispersion, and add potassium permanganate solution to it to perform oxidation-reduction reaction to obtain manganese dioxide@polymetaphthalene Amine@Tri-iron tetraoxide shell core structure composite material.
  • the mass ratio of the ferroferric oxide, m-phenylenediamine, oxidant and potassium permanganate is 1:1.1:0.9-1:2:0.1;
  • the temperature of the ultrasonic dispersion is 15° C. to 45° C.; the time of the ultrasonic dispersion is 0.5 h to 1 h.
  • Ultrasound is to make m-phenylenediamine and ferroferric oxide disperse more uniformly in water, help the uniform combination of the two, and prevent the uneven combination of agglomerates, and the temperature is to keep consistent with subsequent reactions.
  • the time is the minimum ultrasound time that can achieve the effect.
  • step S3 lye is added during the oxidative polymerization reaction to maintain the pH value of the reaction system, and the yield of poly(m-phenylene diamine@ferric oxide) is increased by about 5%-10 %.
  • 10% to 30% of the total volume of the reaction system is added in an amount of lye;
  • the alkaline solution is sodium hydroxide and / or potassium hydroxide solution;
  • the oxidative polymerization reaction is carried out under stirring conditions; the temperature of the oxidative polymerization reaction is 25° C. to 45° C., and the yield of poly-m-phenylene diamine@ferric oxide is increased by about 5%-15%.
  • the oxidative polymerization reaction time is 5h-10h.
  • an acid is added during the redox reaction to maintain the pH of the reaction system, the acid is a hydrochloric acid/nitric acid/sulfuric acid solution; the concentration of H + in the acid is 5M ⁇ 15M; the redox reaction is carried out under stirring conditions; the temperature of the redox reaction is 0°C to 5°C; the time of the redox reaction is 1h-12h.
  • This group of embodiments provides the manganese dioxide@polymetaphenylenediamine@tetrairon tetraoxide composite material described in any one of the first group of embodiments or the two prepared by the preparation method described in any one of the second group of embodiments The application of manganese oxide@polymetaphenylenediamine@ferric oxide composite material in the treatment of heavy metal wastewater.
  • the application includes the following steps: mixing manganese dioxide@polymeta-phenylenediamine@triiron tetraoxide composite material with heavy metal wastewater for vibration adsorption to complete the treatment of heavy metal wastewater;
  • the addition amount of manganese oxide@polym-phenylenediamine@triiron tetraoxide composite material is 0.1g ⁇ 0.5g per liter of heavy metal wastewater.
  • the concentration of the heavy metal wastewater is 50mg/L-100mg/L Cd and/or 50mg/L-200mg/L Pb; the pH value of the heavy metal wastewater is 2-7;
  • the rotational speed of the oscillation adsorption is 100 rpm to 200 rpm; the temperature of the oscillation adsorption is 15° C. to 45° C.; and the time of the oscillation adsorption is 1 min to 1440 min.
  • a manganese dioxide@polymetaphenylenediamine@triiron tetroxide composite material including ferroferric oxide, manganese dioxide and polymetaphenylene diamine, wherein the polymetaphenylene diamine is supported on the surface of ferroferric oxide, two Manganese oxide is supported on the surface of poly-m-phenylene diamine and chemically combined with poly-m-phenylene diamine.
  • the loading amount of poly-m-phenylene diamine is 44.6% of the mass of the composite material of manganese dioxide@polym-phenylenediamine@tetraoxide, and the loading amount of manganese dioxide is manganese dioxide@poly-p-phenylene two 24.4% of the mass of amine@ferroferric oxide composite material.
  • ferroferric oxide is spherical with a rough surface
  • poly-m-phenylene diamine is spherical with a smooth surface
  • the manganese dioxide@polym-phenylenediamine@triiron tetraoxide composite material is a sea urchin with rough surface .
  • the manganese dioxide@polym-phenylenediamine@ferric oxide composite material is a dark brown powder.
  • a method for preparing the manganese dioxide@polym-phenylenediamine@triiron tetraoxide composite material of the above embodiment includes the following steps:
  • the poly-m-phenylene diamine@triiron tetraoxide composite material was prepared.
  • a preparation method of poly-m-phenylene diamine comprising the following steps: mixing 2 g of m-phenylene diamine with 100 mL of water, and ultrasonically dispersing at 25° C. for 15 min, so that the m-phenylene diamine is fully mixed uniformly to obtain a m-phenylene diamine dispersion; Add 11 mL of an equimolar amount of ammonium persulfate solution to the resulting m-phenylenediamine dispersion, and then add 11 mL of a solution containing 2M sodium hydroxide (to maintain the pH of the reaction system), and stir at 25°C. The oxidative polymerization reaction was carried out for 5h under the conditions of, filtered, washed and dried to obtain poly-m-phenylenediamine.
  • the method for preparing Fe 3 O 4 poly-m-phenylenediamine MnO 2 magnetic core-shell structure nanocomposite material in the published patent 201610065134.0 includes the following steps:
  • Figure 1(b) is a TEM image of the poly(m-phenylenediamine@triiron tetraoxide) composite prepared in Comparative Example 1.
  • Figure 1(a) is a TEM image of the polym-phenylene diamine prepared in Comparative Example 2. It can be seen from Figure 1(a) that the microstructure of poly-m-phenylenediamine is spherical.
  • Figure 1(c) is a TEM image of manganese dioxide@polymetaphenylenediamine@triiron tetraoxide composite material FM150 prepared by adding 150 mL of a solution containing 0.02M potassium permanganate in Example 1 of the present invention. It can be seen from Figure 3 that the manganese dioxide@polymetaphenylenediamine@triiron tetraoxide composite material of the present invention becomes a sea urchin after being loaded with manganese dioxide.
  • Figure 2 is the XPS spectrum of the manganese dioxide@polymetaphenylenediamine@triiron tetraoxide composite prepared in Example 1 of the present invention.
  • the results of the broad spectrum X-ray photoelectron spectroscopy also show that the manganese, carbon, The presence of oxygen and nitrogen elements.
  • the pattern shown by O 1s also proves the presence of carboxyl groups in the complex.
  • Potassium permanganate which has strong oxidizing properties, also has a certain effect on the nitrogen-containing groups in FP.
  • N 1s spectrum of FM it can be seen that the content of benzene cyclic amines has dropped from 19.4% to 11.5%.
  • Figure 3(a) is a thermogravimetric analysis diagram of the manganese dioxide@polymetaphenylenediamine@triiron tetraoxide composite material prepared in Example 1 of the present invention.
  • the weight loss of poly-m-phenylenediamine@tetrairon tetraoxide at 200-630°C is about 44.6%, which includes the weight loss caused by the thermal decomposition of poly-m-phenylene diamine.
  • the loading of m-phenylenediamine is 44.6%. According to the TGA image, after loading manganese dioxide, the thermal stability of the composite material increases.
  • the loading amount of manganese dioxide in the composite material FM150 of manganese dioxide@polymetaphenyldiamine@tetraoxide is calculated to be 24.4% .
  • Figure 3(b) shows the hysteresis loop of the material.
  • the magnetic curves of polym-phenylene diamine@tetra ⁇ and manganese dioxide@polymeta-phenylenediamine@tetraoxide three iron shell core composites show at room temperature There is no remanence and coercivity, indicating the superparamagnetic properties of the material.
  • the magnetic saturation value of the condenser-phenylenediamine @ triiron tetroxide is 70.88emu g -1, manganese dioxide, although poly-m-phenylenediamine @ @ tetroxide steel nuclear magnetic saturation value of the magnetic composite material down to 59.07emu g - 1 , but it can still ensure that the manganese dioxide@polymeta-phenylenediamine@tetraoxide core-shell composite can be easily separated from the aqueous solution under the low magnetic field gradient.
  • the manganese dioxide@polymeta-phenylene diamine@tetrogen oxide after loading manganese dioxide increased to 214.72m 2 g -1 , indicating that the addition of manganese dioxide can increase the surface area of the material.
  • Example 1 Take the ferroferric oxide and manganese dioxide used in Comparative Example 1, the poly-m-phenylene diamine@tetra-iron composite material prepared in Comparative Example 1, and the poly-m-phenylene diamine prepared in Comparative Example 2.
  • the heavy metal wastewater with a Pb concentration of 100 mg/L, a Cd concentration of 50 mg/L and a pH of 5.3 is placed in a constant temperature water bath at 25° C. and 170 rpm for 24 hours to absorb and vibrate to complete the treatment of the heavy metal wastewater.
  • FIG. 4 shows the triiron tetroxide, polymetaphenylene diamine, polymetaphenylene diamine@tetrairon tetraoxide composite material obtained in Comparative Example 1, manganese dioxide and four manganese dioxides obtained in Example 2 of the present invention @Polym-phenylenediamine@Triiron tetroxide composite material to compare the amount of heavy metal adsorption.
  • the adsorption capacity of the material FM150 to Pb in the present invention is higher than the three monomers of ferroferric oxide, poly-m-phenylene diamine, manganese dioxide, poly-m-phenylene diamine@tetra-iron tetraoxide composite material and other three kinds of dioxide Manganese@polymeta-phenylenediamine@ferric oxide composite material.
  • Figure 5(a) shows that the FP of the present invention has a significantly higher adsorption capacity for lead than the FP synthesized in Comparative Example 4 without NaOH, which is about 1.2 times the adsorption effect synthesized in Comparative Example 4. It shows that the addition of NaOH will obviously promote the adsorption of FP to lead. The reason is because the hydroxyl group can promote the polymerization process of the polymer, and NaOH can increase the yield of poly-m-phenylenediamine. The yield of FP is increased by about 5%-10%. Therefore, the NaOH added in the present invention optimizes the synthesis of FP.
  • This experiment also studied the adsorption effect of FM150 in Comparative Example FM and Example 1 on trivalent arsenic. Treating arsenic with an initial concentration of 12.5 ppm, the removal rate of arsenic by the FM150 of the present invention is 39%, and the adsorption capacity is 20 mg/g. The arsenic removal rate of the comparative example FM is 16%, and the adsorption capacity is 8mg/g. It can be seen from the results that the adsorption capacity of the FM150 of the present invention is about 2.5 times that of the FM.
  • the removal efficiency of the material of the present invention for arsenic is very low, less than 40%, because the surface of the material is negatively charged, and arsenic is also present in the form of negatively charged arsenate in water. There will be electrostatic repulsion between the two, which will affect the adsorption of arsenic and cause poor adsorption. Therefore, it is not suitable for the treatment of arsenic-containing wastewater, and the material using positively charged heavy metals such as lead of the present invention can have a high adsorption capacity of about 438.6 mg/g due to electrostatic attraction.
  • the application of a manganese dioxide@polym-phenylenediamine@ferric oxide composite material in the treatment of heavy metal wastewater includes the following steps:
  • FIG. 6 shows the relationship between the amount of heavy metal adsorption of manganese dioxide@polym-phenylenediamine@ferric oxide composite material over time. It can be seen from Fig.
  • the application of a manganese dioxide@polymeta-phenylenediamine@ferric oxide composite material in the treatment of heavy metal wastewater includes the following steps:
  • the first group Take 14 parts of the manganese dioxide@polymetaphenylenediamine@triiron tetraoxide composite material (FM150) in Example 1, 5mg each, and add them to the Pb concentration of 100mg/L and the Cd concentration of 50mg. /L heavy metal waste water (the volume of the heavy metal waste water is 20 mL, and the pH value is both 5.3), placed in a constant temperature water bath at 25° C., 170 rpm, and vibrated for 24 hours to complete the treatment of heavy metal waste water.
  • FM150 manganese dioxide@polymetaphenylenediamine@triiron tetraoxide composite material
  • the second group Take 14 parts of the manganese dioxide@polymetaphenylenediamine@triiron tetraoxide composite material (FM150) in Example 1, 5mg each, and add them to the Pb concentration of 100mg/L and the Cd concentration of 50mg. /L heavy metal waste water (the volume of the heavy metal waste water is 20 mL, and the pH value is both 5.3), placed in a constant temperature water bath at 35° C., 170 rpm, and oscillated for 24 hours to complete the treatment of heavy metal waste water.
  • FM150 manganese dioxide@polymetaphenylenediamine@triiron tetraoxide composite material
  • the third group Take 14 parts of manganese dioxide@polym-phenylenediamine@triiron tetraoxide composite material (FM150) in Example 1, 5mg each, and add them to Pb concentration of 100mg/L and Cd concentration of 50mg /L heavy metal waste water (the volume of the heavy metal waste water is 20 mL, and the pH value is both 5.3), placed in a constant temperature water bath at 45° C., 170 rpm, and oscillated for 24 hours to complete the treatment of heavy metal waste water.
  • FM150 manganese dioxide@polym-phenylenediamine@triiron tetraoxide composite material
  • Fig. 7 is a graph showing the relationship between the adsorption amount of heavy metals and the initial concentration of the manganese dioxide@polym-phenylenediamine@triiron tetraoxide composite material FM150 in Example 4 of the present invention at different temperatures.
  • the application of a manganese dioxide@polym-phenylenediamine@ferric oxide composite material in the treatment of heavy metal wastewater includes the following steps:
  • the application of a manganese dioxide@polym-phenylenediamine@ferric oxide composite material in the treatment of heavy metal wastewater includes the following steps:
  • the manganese dioxide@polymetaphenylenediamine@triiron tetraoxide composite material of the present invention has the advantages of low cost, easy synthesis, easy separation, and good adsorption performance. It can effectively adsorb heavy metals in wastewater and has good The use value and application prospects of

Abstract

The present invention pertains to the field of environment-friendly adsorption materials. Disclosed are a manganese dioxide@polymetaphenylenediamine@ferroferric oxide shell core structure composite material, a preparation method therefor, and an application thereof. The manganese dioxide@polymetaphenylenediamine@ferroferric oxide composite material comprises ferroferric oxide, manganese dioxide, and polymetaphenylenediamine. The polymetaphenylenediamine is supported on the surface of the ferroferric oxide, and the manganese oxide is supported on the surface of the polymetaphenylenediamine, finally forming a ternary composite material with a double-layer core-shell structure. The proportion in mass of the ferroferric oxide in the manganese dioxide@polymetaphenylenediamine@ferroferric oxide composite material is not more than 40%. The composite material of the present invention can be applied to the treatment of heavy metal polluted wastewater, has the advantages of having a simple process, convenient operation, low costs, high treatment efficiency, good adsorption effects, etc., and has good application value and commercial value.

Description

二氧化锰@聚间苯二胺@四氧化三铁复合材料及其制备方法和应用Manganese dioxide@polym-phenylenediamine@ferric oxide composite material and preparation method and application thereof 技术领域Technical field
本发明属于环保吸附材料技术领域，涉及一种二氧化锰@聚间苯二胺@四氧化三铁壳核结构复合材料及其制备方法和应用。The invention belongs to the technical field of environmentally friendly adsorption materials, and relates to a manganese dioxide@polymetaphenylenediamine@tetraoxide three iron shell core structure composite material and a preparation method and application thereof.
背景技术Background technique
水是生物生存的关键因素，水污染问题是公众健康水平日益下降的一个重要原因。在几十年的时间里，重金属污染治理一直是水处理领域内具有挑战性的问题。重金属污染很普遍存在，重金属离子不能通过自然生物过程被降解，对水环境和生物健康具有威胁。它能通过多种途径进入水生环境，包括电镀厂，采矿工业，电子制造业，无机颜料制造业，木材加工业排放的废水等。重金属具有很强的化学稳定性和生物难降解性，可以长期存在水体中，对生物的神经***、组织器官造成损害，持续造成严重的环境和健康问题。目前，为了减少重金属污染物对环境的污染，光催化降解、膜过滤、絮凝与沉淀、电化学技术以及吸附等方法被应用于复合处理中，其中吸附法处理重金属污染水体因具有操作简单、投资少、处理后出水水质好等特点而受到重视，但大部分吸附剂因吸附能力低，成本高，有的吸附剂甚至在吸附过程中可能出现降解等问题不能广泛应用于重金属污染水体的处理过程中，因而需要开发更加高效、环保、低成本的吸附剂材料。Water is a key factor for the survival of organisms, and water pollution is an important reason for the decline in public health. For decades, the treatment of heavy metal pollution has been a challenging problem in the field of water treatment. Heavy metal pollution is very common. Heavy metal ions cannot be degraded through natural biological processes, posing a threat to the water environment and biological health. It can enter the aquatic environment through a variety of ways, including electroplating plants, mining industry, electronics manufacturing, inorganic pigment manufacturing, and waste water from the wood processing industry. Heavy metals have strong chemical stability and biodegradability, and can exist in water for a long time, causing damage to the nervous system, tissues and organs of organisms, and continuing to cause serious environmental and health problems. At present, in order to reduce the pollution of heavy metal pollutants to the environment, methods such as photocatalytic degradation, membrane filtration, flocculation and precipitation, electrochemical technology, and adsorption are used in composite treatment. Among them, the adsorption method to treat heavy metal polluted water has simple operation and investment. However, most of the adsorbents have low adsorption capacity and high cost. Some adsorbents may even degrade during the adsorption process and cannot be widely used in the treatment of heavy metal polluted water bodies. Therefore, it is necessary to develop more efficient, environmentally friendly and low-cost adsorbent materials.
聚间苯二胺常被运用于污染水体的处理过程中，其作为一种典型的氨基共轭聚合物具有密集的胺基和亚胺基团，对很多污染物展现出很强的吸附能力。然而，根据以往的研究，因为聚间苯二胺比表面积较小并且表面电荷为正，致使其对重金属的亲和能力较低，吸附效果不佳。而二氧化锰因为其具有大表面积，强重金属吸附能力，易合成，低成本，高环境稳定性等优点而受到关注，并且更重要的是，二氧化锰可以通过碳和高锰酸钾之间简单的氧化还原反应被负载到有机材料表面，形成多元壳核结构复合材料。另外，四氧化三铁自身具有固有的超顺磁特性，将其作为复合材料的内核使得复合材料可以从溶液中被轻易的磁性分离出来。专利申请201610065134.0合成的二氧化锰@聚间苯二胺@四氧化三铁壳核结构复合材料用于砷的吸附，但是该现有技术存在如下缺陷：1.合成过程中的高锰酸钾用量较高，存在资源浪费；2.聚间苯二胺合成温度太低会影响合成产量，导致吸附效果不佳。3.聚间苯二胺合成过程中的pH未进行调控，影响间苯二胺的氧化过程，导致吸附能力受到影响。Poly-m-phenylene diamine is often used in the treatment of polluted water bodies. As a typical amino conjugated polymer, it has dense amine groups and imine groups and exhibits strong adsorption capacity for many pollutants. However, according to previous studies, because poly-m-phenylene diamine has a small specific surface area and a positive surface charge, it has a low affinity for heavy metals and a poor adsorption effect. Manganese dioxide has attracted attention because of its large surface area, strong heavy metal adsorption capacity, easy synthesis, low cost, high environmental stability, etc., and more importantly, manganese dioxide can pass between carbon and potassium permanganate. A simple redox reaction is loaded on the surface of the organic material to form a multi-core shell-core composite material. In addition, ferroferric oxide has inherent superparamagnetic properties. Using it as the core of the composite material allows the composite material to be easily magnetically separated from the solution. Patent application 201610065134.0 synthesized manganese dioxide@polymetaphenyldiamine@tetraoxide three iron shell core structure composite material for arsenic adsorption, but the prior art has the following defects: 1. The amount of potassium permanganate in the synthesis process Higher, there is a waste of resources; 2. Too low synthesis temperature of poly-m-phenylene diamine will affect the synthesis yield, resulting in poor adsorption effect. 3. The pH in the synthesis process of poly-m-phenylenediamine is not adjusted, which affects the oxidation process of m-phenylenediamine, which affects the adsorption capacity.
发明内容Summary of the invention
本发明要解决的技术问题是克服现有技术的不足，优化了二氧化锰@聚间苯二胺@四氧化三铁壳核结构复合材料的合成方法，提供一种成本低、吸附性能好的二氧化锰@聚间苯二胺@四氧化三铁复合材料吸附剂，还提供了一种制备工艺简单、操作简便、反应条件温和、成本低、生产效率高、生产周期短、产品收益率高的二氧化锰@聚间苯二胺@四氧化三铁复合材料的制备方法，以及该二氧化锰@聚间苯二胺@四氧化三铁复合材料在处理重金属废水中的应用。The technical problem to be solved by the present invention is to overcome the shortcomings of the prior art, optimize the synthesis method of manganese dioxide@polymetaphenyldiamine@tetraoxide three iron shell core structure composite material, and provide a low cost and good adsorption performance Manganese dioxide@polymeta-phenylenediamine@iron tetroxide composite adsorbent also provides a simple preparation process, simple operation, mild reaction conditions, low cost, high production efficiency, short production cycle, and high product yield. A method for preparing manganese dioxide@polymeta-phenylenediamine@triiron tetraoxide composite material and the application of the manganese dioxide@polymetaphenylenediamine@triiron tetraoxide composite material in the treatment of heavy metal wastewater.
为解决上述技术问题，本发明采用以下技术方案：To solve the above technical problems, the present invention adopts the following technical solutions:
一种二氧化锰@聚间苯二胺@四氧化三铁复合材料，其特征在于，包括四氧化三铁、二氧化锰和聚间苯二胺，所述聚间苯二胺负载在四氧化三铁表面，二氧化锰负载在聚间苯二胺表面，最后形成双层的核壳结构的三元复合材料；所述四氧化三铁在所述二氧化锰@聚间苯二胺@四氧化三铁复合材料中的质量占比不高于40％。A manganese dioxide@polymetaphenylenediamine@triiron tetroxide composite material, which is characterized in that it comprises ferroferric oxide, manganese dioxide and poly-m-phenylene diamine. The poly-m-phenylene diamine is supported on On the surface of tri-iron, manganese dioxide is supported on the surface of poly-m-phenylene diamine, and finally a ternary composite material with a double-layer core-shell structure is formed; The mass ratio in the ferroferric oxide composite material is not higher than 40%.
所述二氧化锰@聚间苯二胺@四氧化三铁复合材料中的四氧化三铁、聚间苯二胺、二氧化锰的质量比例范围为1∶1.1∶0.9-1∶2∶0.1；所述二氧化锰@聚间苯二胺@四氧化三铁复合材料的比表面积为150m 2/g-220m 2/g。 The mass ratio of ferroferric oxide, polym-phenylene diamine, and manganese dioxide in the manganese dioxide@polym-phenylenediamine@ferric oxide composite material ranges from 1:1.1:0.9-1:2:0.1 The specific surface area of the manganese dioxide@polym-phenylenediamine@ferric oxide composite material is 150m 2 /g-220m 2 /g.
所述四氧化三铁为球状，表面粗糙，尺寸约50-100nm；所述聚间苯二胺为球状，表面光滑；所述二氧化锰@聚间苯二胺@四氧化三铁复合材料为海胆状，表面粗糙。相对间苯二胺而言，海胆状比表面积会增大，会提高材料的吸附性能。The ferroferric oxide has a spherical shape with a rough surface and a size of about 50-100 nm; the poly-m-phenylene diamine has a spherical shape and a smooth surface; the manganese dioxide@polym-phenylenediamine@tetrairon tetraoxide composite material is Sea urchin-like, rough surface. Compared with m-phenylenediamine, the sea urchin-like specific surface area will increase, which will improve the adsorption performance of the material.
所述的二氧化锰@聚间苯二胺@四氧化三铁复合材料的制备方法，其特征在于，包括以下步骤：The method for preparing the manganese dioxide@polymetaphenylenediamine@ferric oxide composite material is characterized in that it comprises the following steps:
S1、将四氧化三铁超声分散到水中，得到四氧化三铁分散液；S1, ultrasonically disperse ferroferric oxide into water to obtain a ferroferric oxide dispersion;
S2、将间苯二胺与四氧化三铁分散液混合，超声分散，得到四氧化三铁和间苯二胺的分散液；S2. Mix the m-phenylenediamine and the ferroferric oxide dispersion liquid, and ultrasonically disperse to obtain a dispersion liquid of ferroferric oxide and m-phenylenediamine;
S3、将步骤S2中得到的四氧化三铁和间苯二胺的分散液与氧化剂混合进行氧化聚合反应，得到聚间苯二胺@四氧化三铁复合材料；S3, mixing the dispersion of ferroferric oxide and m-phenylenediamine obtained in step S2 with an oxidizing agent for oxidative polymerization to obtain a polym-phenylene diamine@triiron tetraoxide composite material;
S4、将步骤S3中得到聚间苯二胺@四氧化三铁复合材料分散到水中得到胶体分散液，向其中加入高锰酸钾溶液以进行氧化还原反应，得到二氧化锰@聚间苯二胺@四氧化三铁壳核结构复合材料。S4. Disperse the poly-m-phenylenediamine@triiron tetraoxide composite material obtained in step S3 into water to obtain a colloidal dispersion, and add potassium permanganate solution to it to perform oxidation-reduction reaction to obtain manganese dioxide@polymetaphthalene Amine@Tri-iron tetraoxide shell core structure composite material.
所述四氧化三铁、间苯二胺、氧化剂和高锰酸钾的质量比为1∶1.1∶0.9-1∶2∶0.1；The mass ratio of the ferroferric oxide, m-phenylenediamine, oxidant and potassium permanganate is 1:1.1:0.9-1:2:0.1;
优选地，所述氧化剂为过硫酸铵和/或过硫酸钠。Preferably, the oxidant is ammonium persulfate and/or sodium persulfate.
四氧化三铁仅仅是提供磁性，吸附位点位于间苯二胺上，四氧化三铁的含量越高会导致 单位质量的吸附量下降，因此需要控制复合材料中四氧化三铁的含量，并在制备过程中控制原料四氧化三铁的加入量。Ferroferric oxide only provides magnetism, and the adsorption site is located on m-phenylenediamine. The higher the content of ferroferric oxide, the lower the adsorption capacity per unit mass. Therefore, it is necessary to control the content of ferroferric oxide in the composite material. During the preparation process, the amount of ferroferric oxide added is controlled.
所述步骤S2中，所述超声分散的温度为15℃～45℃；所述超声分散的时间为0.5h～1h。超声为了使间苯二胺和四氧化三铁在水中分散更均匀，有助于二者的均匀结合，防止成团结合不均匀，温度为了保持与后续反应一致。时间是能达到效果情况下的最少超声时间。In the step S2, the temperature of the ultrasonic dispersion is 15°C to 45°C; the time of the ultrasonic dispersion is 0.5h to 1h. Ultrasound is to make m-phenylenediamine and ferroferric oxide disperse more uniformly in water, help the uniform combination of the two, and prevent the uneven combination of agglomerates, and the temperature is to keep consistent with subsequent reactions. The time is the minimum ultrasound time that can achieve the effect.
所述步骤S3中，所述氧化聚合反应过程中加入碱液以维持反应体系的pH值，聚间苯二胺@四氧化三铁产率约提高了5％－10％。所述碱液的添加量为反应体系总体积的10％～30％；所述碱液为氢氧化钠溶液和/或氢氧化钾溶液；所述碱液中OH —的浓度为1M～3M；所述氧化聚合反应在搅拌条件下进行；所述氧化聚合反应的温度为25℃～45℃，聚间苯二胺@四氧化三铁产率约提高了5％－15％。所述氧化聚合反应的时间为5h～10h。 In the step S3, lye is added during the oxidative polymerization reaction to maintain the pH value of the reaction system, and the yield of poly(m-phenylene diamine@ferric oxide) is increased by about 5%-10%. 10% to 30% of the total volume of the reaction system is added in an amount of lye; the alkaline solution is sodium hydroxide and / or potassium hydroxide solution; the lye OH - concentration of 1M ~ 3M; The oxidative polymerization reaction is carried out under stirring conditions; the temperature of the oxidative polymerization reaction is 25° C. to 45° C., and the yield of poly-m-phenylene diamine@ferric oxide is increased by about 5%-15%. The oxidative polymerization reaction time is 5h-10h.
所述步骤S4中，所述氧化还原反应过程中加入酸以维持反应体系的pH值，所述酸为盐酸/硝酸/硫酸溶液；所述酸中H +的浓度为5M～15M；所述氧化还原反应在搅拌条件下进行；所述氧化还原反应的温度为0℃～5℃；所述氧化还原反应的时间为1h～12h。 In the step S4, an acid is added during the oxidation-reduction reaction process to maintain the pH value of the reaction system, the acid is a hydrochloric acid/nitric acid/sulfuric acid solution; the concentration of H + in the acid is 5M-15M; the oxidation The reduction reaction is carried out under stirring conditions; the temperature of the redox reaction is 0°C to 5°C; the time of the redox reaction is 1h-12h.
所述的二氧化锰@聚间苯二胺@四氧化三铁复合材料或所述的制备方法制得的二氧化锰@聚间苯二胺@四氧化三铁复合材料在处理重金属废水中的应用。The manganese dioxide@polymetaphenylenediamine@triiron tetraoxide composite material or the manganese dioxide@polymetaphenylenediamine@triiron tetraoxide composite material prepared by the preparation method is useful in the treatment of heavy metal wastewater application.
所述的应用包括以下步骤：将二氧化锰@聚间苯二胺@四氧化三铁复合材料与重金属废水混合进行振荡吸附，完成对重金属废水的处理；所述二氧化锰@聚间苯二胺@四氧化三铁复合材料的添加量为每升重金属废水中添加二氧化锰@聚间苯二胺@四氧化三铁复合材料0.1g～0.5g。The application includes the following steps: mixing manganese dioxide@polymeta-phenylenediamine@tetrairon tetraoxide composite material and heavy metal wastewater for vibration adsorption to complete the treatment of heavy metal wastewater; The addition amount of the amine@triiron tetraoxide composite material is 0.1g～0.5g per liter of heavy metal wastewater.
所述重金属废水的浓度为50mg/L～100mg/L Cd和/或50mg/L～200mg/L Pb；所述重金属废水的pH值为2～7；The concentration of the heavy metal wastewater is 50 mg/L to 100 mg/L Cd and/or 50 mg/L to 200 mg/L Pb; the pH value of the heavy metal wastewater is 2 to 7;
优选地，所述振荡吸附的转速为100rpm～200rpm；所述振荡吸附的温度为15℃～45℃；所述振荡吸附的时间为1min～1440min。Preferably, the rotational speed of the oscillating adsorption is 100 rpm to 200 rpm; the temperature of the oscillating adsorption is 15° C. to 45° C.; the time of the oscillating adsorption is 1 min to 1440 min.
一种二氧化锰@聚间苯二胺@四氧化三铁复合材料，所述二氧化锰@聚间苯二胺@四氧化三铁复合材料包括四氧化三铁、二氧化锰和聚间苯二胺，所述聚间苯二胺负载在四氧化三铁表面，二氧化锰负载在聚间苯二胺表面。A manganese dioxide@polymetaphenylenediamine@triiron tetraoxide composite material, the manganese dioxide@polymetaphenylenediamine@tetraoxide triiron composite material includes triiron tetroxide, manganese dioxide and polymetaphenylene Diamine, the poly-m-phenylene diamine is supported on the surface of ferroferric oxide, and the manganese dioxide is supported on the surface of the poly-m-phenylene diamine.
上述的二氧化锰@聚间苯二胺@四氧化三铁复合材料，进一步改进的，所述二氧化锰@聚间苯二胺@四氧化三铁复合材料中的四氧化三铁、聚间苯二胺、二氧化锰的质量比例范围为1∶1.1∶0.9-1∶2∶0.1；所述四氧化三铁为球状，表面粗糙，尺寸较小；所述聚间苯二胺为球状，表面光滑；所述二氧化锰@聚间苯二胺@四氧化三铁复合材料为海胆状，表面粗糙。The above-mentioned manganese dioxide@polymeta-phenylenediamine@triiron tetraoxide composite material is further improved. In the manganese dioxide@polymetaphenylenediamine@triiron tetraoxide composite material, the triiron tetroxide and polymeta The mass ratio of phenylenediamine and manganese dioxide is in the range of 1:1.1:0.9-1:2:0.1; the ferroferric oxide has a spherical shape with a rough surface and a small size; the poly-m-phenylenediamine is spherical, The surface is smooth; the manganese dioxide@polymetaphenylenediamine@triiron tetroxide composite material is sea urchin-like with a rough surface.
作为一个总的技术构思，本发明还提供了一种上述的二氧化锰@聚间苯二胺@四氧化三 铁复合材料的制备方法，包括以下步骤：As a general technical idea, the present invention also provides a method for preparing the above-mentioned manganese dioxide@polymetaphenylenediamine@three iron composite material, which includes the following steps:
S1、将四氧化三铁超声分散到水中，得到四氧化三铁分散液；S1, ultrasonically disperse ferroferric oxide into water to obtain a ferroferric oxide dispersion;
S2、将间苯二胺与四氧化三铁分散液混合，超声分散，得到四氧化三铁和间苯二胺的分散液；S2. Mix the m-phenylenediamine and the ferroferric oxide dispersion liquid, and ultrasonically disperse to obtain a dispersion liquid of ferroferric oxide and m-phenylenediamine;
S3、将步骤S2中得到的四氧化三铁和间苯二胺的分散液与氧化剂混合进行氧化聚合反应，得到聚间苯二胺@四氧化三铁复合材料。S3, mixing the dispersion of ferroferric oxide and m-phenylenediamine obtained in step S2 with an oxidizing agent to perform an oxidative polymerization reaction to obtain a polym-phenylene diamine@triiron tetraoxide composite material.
S4、将步骤S3中得到聚间苯二胺@四氧化三铁复合材料分散到水中得到胶体分散液，向其中加入高锰酸钾溶液以进行氧化还原反应，得到二氧化锰@聚间苯二胺@四氧化三铁壳核结构复合材料。S4. Disperse the poly-m-phenylenediamine@triiron tetraoxide composite material obtained in step S3 into water to obtain a colloidal dispersion, and add potassium permanganate solution to it to perform oxidation-reduction reaction to obtain manganese dioxide@polymetaphthalene Amine@Tri-iron tetraoxide shell core structure composite material.
上述的制备方法，进一步改进的，所述四氧化三铁、间苯二胺、氧化剂和高锰酸钾的质量比为1∶1.1∶0.9-1∶2∶0.1。The above preparation method is further improved, and the mass ratio of the ferroferric oxide, m-phenylenediamine, oxidant and potassium permanganate is 1:1.1:0.9-1:2:0.1.
上述的制备方法，进一步改进的，所述氧化剂为过硫酸铵和/或过硫酸钠。The above preparation method is further improved, and the oxidant is ammonium persulfate and/or sodium persulfate.
上述的制备方法，进一步改进的，所述步骤S2中，所述超声分散的温度为25℃～45℃；所述超声分散的时间为0.5h～1h；The above preparation method is further improved. In the step S2, the temperature of the ultrasonic dispersion is 25° C. to 45° C.; the time of the ultrasonic dispersion is 0.5 h to 1 h;
上述的制备方法，进一步改进的，所述氧化聚合反应过程中加入碱液以维持反应体系的pH值；所述碱液的添加量为反应体系总体积的10％～30％；所述碱液为氢氧化钠溶液和/或氢氧化钾溶液；所述碱液中OH @的浓度为1M～3M；所述氧化聚合反应在搅拌条件下进行；所述氧化聚合反应的温度为15℃～45℃；所述氧化聚合反应的时间为5h～10h。 The above preparation method is further improved. During the oxidative polymerization reaction, lye is added to maintain the pH value of the reaction system; the added amount of lye is 10% to 30% of the total volume of the reaction system; the lye It is sodium hydroxide solution and/or potassium hydroxide solution; the concentration of OH @ in the lye is 1M～3M; the oxidative polymerization reaction is carried out under stirring conditions; the temperature of the oxidative polymerization reaction is 15°C～45 °C; the time of the oxidative polymerization reaction is 5h-10h.
上述的制备方法，进一步改进的，所述步骤S4中，所述氧化还原反应过程中加入酸以维持反应体系的pH值，所述酸为盐酸溶液；所述酸中H +的浓度为5M～12M；所述氧化还原反应在搅拌条件下进行；所述氧化还原反应的温度为0℃～5℃；所述氧化还原反应的时间为4h～12h The above preparation method is further improved. In the step S4, an acid is added during the redox reaction to maintain the pH of the reaction system, the acid is a hydrochloric acid solution; the concentration of H + in the acid is 5M～ 12M; The redox reaction is carried out under stirring conditions; the temperature of the redox reaction is 0℃～5℃; the time of the redox reaction is 4h～12h
作为一个总的发明构思，本发明还提供了一种上述的二氧化锰@聚间苯二胺@四氧化三铁复合材料或上述的制备方法制得的二氧化锰@聚间苯二胺@四氧化三铁复合材料在处理重金属废水中的应用。As a general inventive concept, the present invention also provides a manganese dioxide@polymetaphenylenediamine@tetrairon tetraoxide composite material or manganese dioxide@polymetaphenylenediamine@ prepared by the above preparation method. The application of ferroferric oxide composite material in the treatment of heavy metal wastewater.
上述的应用，进一步改进的，包括以下步骤：将二氧化锰@聚间苯二胺@四氧化三铁复合材料与重金属废水混合进行振荡吸附，完成对重金属废水的处理；所述二氧化锰@聚间苯二胺@四氧化三铁复合材料的添加量为每升重金属废水中添加二氧化锰@聚间苯二胺@四氧化三铁复合材料0.25g～0.5g。The above application is further improved and includes the following steps: mixing the manganese dioxide@polymetaphenylenediamine@triiron tetraoxide composite material with heavy metal wastewater for vibration adsorption to complete the treatment of the heavy metal wastewater; the manganese dioxide@ The addition amount of poly-m-phenylene diamine@triiron tetraoxide composite material is 0.25g～0.5g per liter of heavy metal wastewater with manganese dioxide@polymeta-phenylene diamine@triiron tetraoxide composite material.
上述的应用，进一步改进的，所述重金属废水的浓度为50mg/L～100mg/L Cd和/或50mg/L～200mg/L Pb；所述重金属废水的pH值为2～7。The above application is further improved. The concentration of the heavy metal wastewater is 50 mg/L-100 mg/L Cd and/or 50 mg/L-200 mg/L Pb; the pH value of the heavy metal wastewater is 2-7.
上述的应用，进一步改进的，所述振荡吸附的转速为150rpm～200rpm；所述振荡吸附的温度为15℃～45℃；所述振荡吸附的时间为1min～1440min。The above application is further improved. The rotational speed of the oscillating adsorption is 150 rpm to 200 rpm; the temperature of the oscillating adsorption is 15° C. to 45° C.; and the time of the oscillating adsorption is 1 min to 1440 min.
与现有技术相比，本发明的优点在于：Compared with the prior art, the advantages of the present invention are:
(1)本发明提供了一种二氧化锰@聚间苯二胺@四氧化三铁复合材料，包括四氧化三铁、二氧化锰和聚间苯二胺，所述聚间苯二胺负载在四氧化三铁表面，二氧化锰负载在聚间苯二胺表面。本发明中，聚间苯二胺是一种典型的氨基共轭聚合物可为多种污染物，具有大量胺基和亚胺基团，可为污染物提供吸附位点。同时，丰富的官能团使得其表面上易于接枝其他功能性材料；二氧化锰表面积很大，对污染物具有较强亲和能力，对重金属离子具有良好的吸附效果，可以通过有机物和高锰酸钾间简单的氧化还原反应负载到有机物表面。同时，二氧化锰负载后改变了聚间苯二胺表面的电负性，复合材料由正电变为负电，有助于该材料通过静电引力吸附带正电的有机物(如重金属)。四氧化三铁磁性内核则使得复合材料可以从溶液中被轻易的磁性分离出来，有利于其实际应用。本发明的二氧化锰@聚间苯二胺@四氧化三铁复合材料中，通过静电引力、离子交换(Pb(II)/Cd(II)和-NH-基团上的H(I)的离子交换、Pb(II)/Cd(II)和MnO 2上的Mn的离子交换)、Pb(II)/Cd(II)和–N＝基团形成共轭键等作用吸附水体中的重金属。本发明二氧化锰@聚间苯二胺@四氧化三铁复合材料具有成本低、易合成、吸附性能好、易分离等优点，能够有效吸附废水中的重金属，具有较好的使用价值和应用前景。 (1) The present invention provides a manganese dioxide@polymetaphenylenediamine@triiron tetraoxide composite material, including triiron tetroxide, manganese dioxide and polymetaphenylene diamine, the polymetaphenylene diamine supporting On the surface of ferroferric oxide, manganese dioxide is supported on the surface of poly-m-phenylenediamine. In the present invention, poly-m-phenylenediamine is a typical amino conjugated polymer that can be a variety of pollutants, has a large number of amine groups and imine groups, and can provide adsorption sites for pollutants. At the same time, the abundant functional groups make it easy to graft other functional materials on the surface; manganese dioxide has a large surface area, has a strong affinity for pollutants, and has a good adsorption effect on heavy metal ions. It can pass through organic matter and permanganic acid. The simple oxidation-reduction reaction between potassium loads the surface of organic matter. At the same time, the loading of manganese dioxide changes the electronegativity of the surface of the poly-m-phenylene diamine, and the composite material changes from positive to negative, which helps the material to adsorb positively charged organics (such as heavy metals) through electrostatic attraction. The ferroferric oxide magnetic core allows the composite material to be easily magnetically separated from the solution, which is beneficial to its practical application. In the manganese dioxide@polymeta-phenylenediamine@ferric oxide composite material of the present invention, through electrostatic attraction, ion exchange (Pb(II)/Cd(II) and H(I) on the -NH- group) Ion exchange, ion exchange of Pb(II)/Cd(II) and Mn on MnO 2 ), Pb(II)/Cd(II) and -N= groups form conjugate bonds to adsorb heavy metals in water. The manganese dioxide@polymetaphenylenediamine@ferric oxide composite material of the present invention has the advantages of low cost, easy synthesis, good adsorption performance, easy separation, etc., can effectively adsorb heavy metals in wastewater, and has good use value and application prospect.
(2)本发明的二氧化锰@聚间苯二胺@四氧化三铁复合材料中，所述二氧化锰@聚间苯二胺@四氧化三铁复合材料中的四氧化三铁、聚间苯二胺、二氧化锰的质量比例范围为1∶1.1∶0.9-1∶2∶0.1，能够保证材料具有足够的吸附位点，从而能够提高材料对重金属污染物的吸附能力，进而具有较好的吸附效果。(2) In the manganese dioxide@polymetaphenylenediamine@triiron tetraoxide composite material of the present invention, the triiron tetroxide and poly The mass ratio of m-phenylenediamine and manganese dioxide is in the range of 1:1.1:0.9-1:2:0.1, which can ensure that the material has sufficient adsorption sites, thereby improving the material's adsorption capacity for heavy metal pollutants, and thus has a better Good adsorption effect.
(3)本发明的二氧化锰@聚间苯二胺@四氧化三铁复合材料中，四氧化三铁为球状，表面粗糙，尺寸较小，使得表面光滑的球状聚间苯二胺更易负载到四氧化三铁表面。而聚间苯二胺丰富的官能团使得其表面上易于接枝二氧化锰，由此形成的二氧化锰@聚间苯二胺@四氧化三铁复合材料性能更加稳定。二氧化锰@聚间苯二胺@四氧化三铁复合材料为海胆状，表面粗糙，具有很大的表面积与大量重金属吸附位点。(3) In the manganese dioxide@polymetaphenylenediamine@triiron tetraoxide composite material of the present invention, the ferroferric oxide is spherical, the surface is rough, and the size is small, making the spherical polymetaphenylene diamine with smooth surface easier to load To the surface of Fe3O4. The rich functional groups of poly-m-phenylenediamine make it easy to graft manganese dioxide on its surface, and the resulting manganese dioxide@polym-phenylenediamine@triiron tetraoxide composite has more stable properties. Manganese dioxide@polymetaphenylenediamine@ferric oxide composite material is sea urchin-like with rough surface, large surface area and a large number of heavy metal adsorption sites.
(4)本发明还提供了一种二氧化锰@聚间苯二胺@四氧化三铁复合材料的制备方法，先将四氧化三铁超声分散于水中使得四氧化三铁上的结合位点暴露在外面，此时加入间苯二胺，使得间苯二胺更容易与四氧化三铁上的结合位点结合，经超声分散形成四氧化三铁@间苯二胺，然后在氧化剂的作用下发生氧化聚合反应，将间苯二胺转化为聚间苯二胺负载在四氧化三铁表面。然后将聚间苯二胺@四氧化三铁分散于水中，加入高锰酸钾溶液，通过高锰酸钾 与聚间苯二胺上的碳的氧化还原反应将二氧化锰负载到聚间苯二胺表面，从而制得稳定性能更好的二氧化锰@聚间苯二胺@四氧化三铁复合材料。本发明制备方法具有工艺简单、操作方便、反应条件温和(常温即可制备)、成本低、生产效率高、生产周期短、产品收益率高等优点，适合于大规模制备，利于工业化应用。(4) The present invention also provides a preparation method of manganese dioxide@polym-phenylenediamine@triiron tetroxide composite material. First, ferric oxide is ultrasonically dispersed in water to make the binding sites on ferric oxide When exposed to the outside, m-phenylenediamine is added at this time, which makes it easier for the m-phenylenediamine to combine with the binding sites on ferroferric oxide, and it is dispersed by ultrasonic to form ferroferric oxide@meta-phenylenediamine, and then acts as an oxidizer An oxidative polymerization reaction takes place under the condition that meta-phenylenediamine is converted into poly-m-phenylenediamine and loaded on the surface of ferroferric oxide. Then disperse the poly-m-phenylene diamine@tetrairon tetraoxide in water, add potassium permanganate solution, and load the manganese dioxide onto the poly-m-phenylene through the redox reaction of potassium permanganate and the carbon on the poly-m-phenylene diamine Diamine surface, so as to prepare manganese dioxide@polymeta-phenylenediamine@tetraoxide composite material with better stability. The preparation method of the invention has the advantages of simple process, convenient operation, mild reaction conditions (preparation at room temperature), low cost, high production efficiency, short production cycle, high product yield, etc., is suitable for large-scale preparation and is beneficial to industrial application.
(5)本发明还提供了一种二氧化锰@聚间苯二胺@四氧化三铁复合材料在处理重金属废水中的应用，将二氧化锰@聚间苯二胺@四氧化三铁复合材料与重金属废水混合通过振荡吸附即可实现对废水中重金属的有效吸附，具有工艺简单、操作方便、易分离、成本低廉、处理效率高、吸附效果好等优点，能大规模应用于处理重金属废水，有着很高的应用价值和商业价值。(5) The present invention also provides an application of manganese dioxide@polymeta-phenylenediamine@triiron tetraoxide composite material in the treatment of heavy metal wastewater. The mixing of materials and heavy metal wastewater can achieve effective adsorption of heavy metals in wastewater through vibration adsorption. It has the advantages of simple process, convenient operation, easy separation, low cost, high treatment efficiency, and good adsorption effect. It can be applied to treat heavy metal wastewater on a large scale. , Has high application value and commercial value.
本发明公开了一种二氧化锰@聚间苯二胺@四氧化三铁壳核结构复合材料及其制备方法和应用，该二氧化锰@聚间苯二胺@四氧化三铁复合材料包括四氧化三铁、二氧化锰和聚间苯二胺，四氧化三铁作为磁性内核，将聚间苯二胺负载在四氧化三铁表面，再用二氧化锰包裹聚间苯二胺@四氧化三铁复合物，最后形成二氧化锰@聚间苯二胺@四氧化三铁三元复合材料。其制备方法包括制备四氧化三铁分散液；制备四氧化三铁和间苯二胺的分散液；将四氧化三铁和间苯二胺的分散液与氧化剂混合进行氧化聚合反应；将得到的聚间苯二胺@四氧化三铁制备成分散液；将聚间苯二胺@四氧化三铁分散液与高锰酸钾溶液混合发生氧化还原反应生成二氧化锰，使二氧化锰负载到材料表面。本发明二氧化锰@聚间苯二胺@四氧化三铁壳核结构复合材料具有成本低、易合成、吸附性能好、适应性强、易分离等优点，其制备方法具有工艺简单、操作方便、反应条件温和、成本低、生产效率高、生产周期短、产品收益率高等优点，适合于大规模制备，利于实际工业化应用。本发明复合材料能够应用于处理重金属污染废水，具有工艺简单、操作方便、成本低、处理效率高、吸附效果好等优点，有着很高的应用价值和商业价值。The invention discloses a manganese dioxide@polymetaphenylenediamine@tetrairon tetraoxide shell-core structure composite material, and a preparation method and application thereof. The manganese dioxide@polymetaphenylenediamine@tetrairon tetraoxide composite material includes Ferroferric oxide, manganese dioxide and poly-m-phenylenediamine, ferroferric oxide is used as the magnetic core, the poly-m-phenylene diamine is loaded on the surface of the ferro-ferric oxide, and the poly-m-phenylene diamine is wrapped with manganese dioxide@四The ferroferric oxide compound finally forms the manganese dioxide@polymeta-phenylenediamine@tetraoxide ternary composite material. The preparation method includes preparing a dispersion of ferroferric oxide; preparing a dispersion of ferroferric oxide and m-phenylenediamine; mixing the dispersion of ferroferric oxide and m-phenylenediamine with an oxidizing agent for oxidative polymerization; The poly(m-phenylenediamine@tetraoxide) is prepared as a dispersion; the poly(m-phenylene diamine@tetraoxide) dispersion is mixed with the potassium permanganate solution to undergo redox reaction to generate manganese dioxide, so that the manganese dioxide is loaded to Material surface. The manganese dioxide@polymetaphenylenediamine@triiron tetraoxide shell core structure composite material of the present invention has the advantages of low cost, easy synthesis, good adsorption performance, strong adaptability, easy separation, etc., and its preparation method has simple process and convenient operation , The advantages of mild reaction conditions, low cost, high production efficiency, short production cycle, high product yield, etc., are suitable for large-scale preparation and are conducive to practical industrial applications. The composite material of the invention can be applied to the treatment of heavy metal polluted wastewater, has the advantages of simple process, convenient operation, low cost, high treatment efficiency, good adsorption effect, etc., and has high application value and commercial value.
附图说明Description of the drawings
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整的描述。In order to make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be described clearly and completely in conjunction with the accompanying drawings in the embodiments of the present invention.
图1(a)为对比例2中制得的聚间苯二胺的TEM图；图1(b)为对比例1中制得的聚间苯二胺@四氧化三铁复合材料的TEM图；图1(c)为本发明实施例1中加入150mL含有0.02M高锰酸钾的溶液所制得的二氧化锰@聚间苯二胺@四氧化三铁复合材料(FM150)的TEM图。Figure 1(a) is the TEM image of the poly-m-phenylene diamine prepared in Comparative Example 2; Figure 1(b) is the TEM image of the poly-m-phenylene diamine@triiron tetraoxide composite material prepared in Comparative Example 1 Figure 1(c) is the TEM image of the manganese dioxide@polym-phenylenediamine@tetrairon tetraoxide composite material (FM150) prepared by adding 150mL of a solution containing 0.02M potassium permanganate in Example 1 of the present invention .
[根据细则91更正 17.07.2019]　
图2(a)为本发明实施例1中制得的FP和FM150的X射线光电子能谱(xps)分析图。(b)为N Is能谱分析图，（c）为0 Is能谱分析图，（d）为C Is能谱分析图。[Corrected according to Rule 91 17.07.2019]
Figure 2 (a) is an X-ray photoelectron spectroscopy (xps) analysis diagram of FP and FM150 prepared in Example 1 of the present invention. (b) is the N Is energy spectrum analysis diagram, (c) is the 0 Is energy spectrum analysis diagram, and (d) is the C Is energy spectrum analysis diagram.
[根据细则91更正 17.07.2019]　
图3(a)为本发明实施例1中制得的FP和FM150的热重分析图；图1(b)为FP和FM150的磁滞回线图；（b）为FP和FM150的磁滞回线图。
[Corrected according to Rule 91 17.07.2019]
Figure 3 (a) is the thermogravimetric analysis diagram of FP and FM150 prepared in Example 1 of the present invention; Figure 1 (b) is the hysteresis loop diagram of FP and FM150; (b) is the hysteresis of FP and FM150 Loop graph.
图4(a)为本发明实施例2中8种不同材料对重金属Pb和Cd吸附量的对比图；(b)为6种不同材料zeta电位图。Fig. 4 (a) is a comparison diagram of the adsorption amount of heavy metals Pb and Cd by 8 different materials in Example 2 of the present invention; (b) is a zeta potential diagram of 6 different materials.
图5(a)为本发明实施例1中合成的FP和FM，对比例4中合成的FP(对应图中的“FP未加NaOH”)，对比例3中合成的FP(对应图中的“对比例FP”)和FM(对应图中的“对比例FM”)对铅离子的吸附量对比；(b)为实施例1中制得FM分离后的溶液以及对比例3中对比例FM分离后的溶液中高锰酸钾含量对比图。Figure 5(a) shows the FP and FM synthesized in Example 1 of the present invention, the FP synthesized in Comparative Example 4 (corresponding to "FP without NaOH" in the figure), and the FP synthesized in Comparative Example 3 (corresponding to the figure in the figure). "Comparative Example FP") and FM (corresponding to the "Comparative Example FM" in the figure) to compare the adsorption amount of lead ions; (b) is the FM separated solution prepared in Example 1 and Comparative Example FM in Comparative Example 3. Comparison chart of potassium permanganate content in the separated solution.
图6为本发明实施例3中FM150对重金属吸附量随时间变化关系图。Fig. 6 is a diagram showing the relationship between the amount of heavy metal adsorption by FM150 in Example 3 of the present invention over time.
图7为本发明实施例4中FM150在不同温度下对重金属的吸附量与初始浓度的关系曲线图。Fig. 7 is a graph showing the relationship between the amount of heavy metals adsorbed by FM150 at different temperatures and the initial concentration in Example 4 of the present invention.
图8为本发明实施例5中FM150对重金属吸附量随pH变化关系图，以及相应的Zeta电位变化。Fig. 8 is a diagram showing the relationship between the amount of heavy metal adsorption by FM150 and the change in pH in Example 5 of the present invention, and the corresponding change in Zeta potential.
图9为本发明实施6中FM150对重金属吸附量随共存离子以及腐殖酸变化关系图，Figure 9 is a graph showing the relationship between the amount of heavy metal adsorption by FM150 and the coexisting ions and humic acid in the sixth embodiment of the present invention.
具体实施方式Detailed ways
以下结合说明书附图和具体优选的实施例对本发明作进一步描述，但并不因此而限制本发明的保护范围。以下实施例中所采用的原料和仪器均为市售。以下实施例中，若无特别说明，所得数据均是三次以上重复实验的平均值。The following further describes the present invention with reference to the accompanying drawings of the specification and specific preferred embodiments, but the protection scope of the present invention is not limited thereby. The raw materials and instruments used in the following examples are all commercially available. In the following examples, unless otherwise specified, the data obtained are the average of three or more repeated experiments.
第1组实施例、本发明的复合材料The first group of examples, the composite material of the present invention
本组实施例提供一种二氧化锰@聚间苯二胺@四氧化三铁复合材料，其特征在于，包括四氧化三铁、二氧化锰和聚间苯二胺，所述聚间苯二胺负载在四氧化三铁表面，二氧化锰负载在聚间苯二胺表面，最后形成双层的核壳结构的三元复合材料；所述四氧化三铁在所述二氧化锰@聚间苯二胺@四氧化三铁复合材料中的质量占比不高于40％。This group of embodiments provides a composite material of manganese dioxide@polymetaphenylenediamine@triiron tetraoxide, which is characterized in that it includes ferroferric oxide, manganese dioxide and polymetaphenylene diamine. The amine is supported on the surface of ferroferric oxide, and the manganese dioxide is supported on the surface of poly(metaphenylene diamine), and finally a ternary composite material with a double-layer core-shell structure is formed; the ferroferric oxide is on the manganese dioxide@聚间The mass proportion of phenylenediamine@ferric oxide composite material is not more than 40%.
在一些实施例中，所述二氧化锰@聚间苯二胺@四氧化三铁复合材料中的四氧化三铁、聚间苯二胺、二氧化锰的质量比例范围为1∶1.1∶0.9-1∶2∶0.1；所述二氧化锰@聚间苯二胺@四氧化三铁复合材料的比表面积为150m 2/g-220m 2/g。 In some embodiments, the mass ratio of ferroferric oxide, polym-phenylene diamine, and manganese dioxide in the manganese dioxide@polym-phenylenediamine@triiron tetraoxide composite material ranges from 1:1.1:0.9 -1:2:0.1; the specific surface area of the manganese dioxide@polym-phenylenediamine@ferric oxide composite material is 150m 2 /g-220m 2 /g.
第2组实施例、本发明的复合材料的制备方法The second group of embodiments, the preparation method of the composite material of the present invention
本组实施例提供第1组实施例任一项所述的二氧化锰@聚间苯二胺@四氧化三铁复合材 料的制备方法，其特征在于，包括以下步骤：This group of embodiments provides a method for preparing the manganese dioxide@polymetaphenylenediamine@triiron tetraoxide composite material described in any one of the first group of embodiments, which is characterized in that it comprises the following steps:
S1、将四氧化三铁超声分散到水中，得到四氧化三铁分散液；S1, ultrasonically disperse ferroferric oxide into water to obtain a ferroferric oxide dispersion;
S2、将间苯二胺与四氧化三铁分散液混合，超声分散，得到四氧化三铁和间苯二胺的分散液；S2. Mix the m-phenylenediamine and the ferroferric oxide dispersion liquid, and ultrasonically disperse to obtain a dispersion liquid of ferroferric oxide and m-phenylenediamine;
S3、将步骤S2中得到的四氧化三铁和间苯二胺的分散液与氧化剂混合进行氧化聚合反应，得到聚间苯二胺@四氧化三铁复合材料；S3, mixing the dispersion of ferroferric oxide and m-phenylenediamine obtained in step S2 with an oxidizing agent for oxidative polymerization to obtain a polym-phenylene diamine@triiron tetraoxide composite material;
S4、将步骤S3中得到聚间苯二胺@四氧化三铁复合材料分散到水中得到胶体分散液，向其中加入高锰酸钾溶液以进行氧化还原反应，得到二氧化锰@聚间苯二胺@四氧化三铁壳核结构复合材料。S4. Disperse the poly-m-phenylenediamine@triiron tetraoxide composite material obtained in step S3 into water to obtain a colloidal dispersion, and add potassium permanganate solution to it to perform oxidation-reduction reaction to obtain manganese dioxide@polymetaphthalene Amine@Tri-iron tetraoxide shell core structure composite material.
在优选的实施例中，所述四氧化三铁、间苯二胺、氧化剂和高锰酸钾的质量比为1∶1.1∶0.9-1∶2∶0.1；In a preferred embodiment, the mass ratio of the ferroferric oxide, m-phenylenediamine, oxidant and potassium permanganate is 1:1.1:0.9-1:2:0.1;
在另一些实施例中，所述步骤S2中，所述超声分散的温度为15℃～45℃；所述超声分散的时间为0.5h～1h。超声为了使间苯二胺和四氧化三铁在水中分散更均匀，有助于二者的均匀结合，防止成团结合不均匀，温度为了保持与后续反应一致。时间是能达到效果情况下的最少超声时间。In some other embodiments, in the step S2, the temperature of the ultrasonic dispersion is 15° C. to 45° C.; the time of the ultrasonic dispersion is 0.5 h to 1 h. Ultrasound is to make m-phenylenediamine and ferroferric oxide disperse more uniformly in water, help the uniform combination of the two, and prevent the uneven combination of agglomerates, and the temperature is to keep consistent with subsequent reactions. The time is the minimum ultrasound time that can achieve the effect.
在具体的实施例中，所述步骤S3中，所述氧化聚合反应过程中加入碱液以维持反应体系的pH值，聚间苯二胺@四氧化三铁产率约提高了5％－10％。所述碱液的添加量为反应体系总体积的10％～30％；所述碱液为氢氧化钠溶液和/或氢氧化钾溶液；所述碱液中OH —的浓度为1M～3M；所述氧化聚合反应在搅拌条件下进行；所述氧化聚合反应的温度为25℃～45℃，聚间苯二胺@四氧化三铁产率约提高了5％－15％。所述氧化聚合反应的时间为5h～10h。 In a specific embodiment, in the step S3, lye is added during the oxidative polymerization reaction to maintain the pH value of the reaction system, and the yield of poly(m-phenylene diamine@ferric oxide) is increased by about 5%-10 %. 10% to 30% of the total volume of the reaction system is added in an amount of lye; the alkaline solution is sodium hydroxide and / or potassium hydroxide solution; the lye OH - concentration of 1M ~ 3M; The oxidative polymerization reaction is carried out under stirring conditions; the temperature of the oxidative polymerization reaction is 25° C. to 45° C., and the yield of poly-m-phenylene diamine@ferric oxide is increased by about 5%-15%. The oxidative polymerization reaction time is 5h-10h.
在另一些实施例中，所述步骤S4中，所述氧化还原反应过程中加入酸以维持反应体系的pH值，所述酸为盐酸/硝酸/硫酸溶液；所述酸中H +的浓度为5M～15M；所述氧化还原反应在搅拌条件下进行；所述氧化还原反应的温度为0℃～5℃；所述氧化还原反应的时间为1h～12h。 In other embodiments, in the step S4, an acid is added during the redox reaction to maintain the pH of the reaction system, the acid is a hydrochloric acid/nitric acid/sulfuric acid solution; the concentration of H + in the acid is 5M～15M; the redox reaction is carried out under stirring conditions; the temperature of the redox reaction is 0°C to 5°C; the time of the redox reaction is 1h-12h.
第3组实施例、本发明的复合材料的应用The third group of examples, the application of the composite material of the present invention
本组实施例提供第1组实施例任一项所述的二氧化锰@聚间苯二胺@四氧化三铁复合材料或第2组实施例任一项所述的制备方法制得的二氧化锰@聚间苯二胺@四氧化三铁复合材料在处理重金属废水中的应用。This group of embodiments provides the manganese dioxide@polymetaphenylenediamine@tetrairon tetraoxide composite material described in any one of the first group of embodiments or the two prepared by the preparation method described in any one of the second group of embodiments The application of manganese oxide@polymetaphenylenediamine@ferric oxide composite material in the treatment of heavy metal wastewater.
在具体的实施例中，所述的应用包括以下步骤：将二氧化锰@聚间苯二胺@四氧化三铁 复合材料与重金属废水混合进行振荡吸附，完成对重金属废水的处理；所述二氧化锰@聚间苯二胺@四氧化三铁复合材料的添加量为每升重金属废水中添加二氧化锰@聚间苯二胺@四氧化三铁复合材料0.1g～0.5g。In a specific embodiment, the application includes the following steps: mixing manganese dioxide@polymeta-phenylenediamine@triiron tetraoxide composite material with heavy metal wastewater for vibration adsorption to complete the treatment of heavy metal wastewater; The addition amount of manganese oxide@polym-phenylenediamine@triiron tetraoxide composite material is 0.1g～0.5g per liter of heavy metal wastewater.
在优选的实施例中，所述重金属废水的浓度为50mg/L～100mg/L Cd和/或50mg/L～200mg/L Pb；所述重金属废水的pH值为2～7；In a preferred embodiment, the concentration of the heavy metal wastewater is 50mg/L-100mg/L Cd and/or 50mg/L-200mg/L Pb; the pH value of the heavy metal wastewater is 2-7;
在更优选的实施例中，所述振荡吸附的转速为100rpm～200rpm；所述振荡吸附的温度为15℃～45℃；所述振荡吸附的时间为1min～1440min。In a more preferred embodiment, the rotational speed of the oscillation adsorption is 100 rpm to 200 rpm; the temperature of the oscillation adsorption is 15° C. to 45° C.; and the time of the oscillation adsorption is 1 min to 1440 min.
实施例1Example 1
一种二氧化锰@聚间苯二胺@四氧化三铁复合材料，包括四氧化三铁、二氧化锰和聚间苯二胺，其中聚间苯二胺负载在四氧化三铁表面，二氧化锰负载在聚间苯二胺负载在表面，与聚间苯二胺化学结合。A manganese dioxide@polymetaphenylenediamine@triiron tetroxide composite material, including ferroferric oxide, manganese dioxide and polymetaphenylene diamine, wherein the polymetaphenylene diamine is supported on the surface of ferroferric oxide, two Manganese oxide is supported on the surface of poly-m-phenylene diamine and chemically combined with poly-m-phenylene diamine.
本实施例中，聚间苯二胺的负载量为二氧化锰@聚间苯二胺@四氧化三铁复合材料质量的44.6％，二氧化锰的负载量为二氧化锰@聚间苯二胺@四氧化三铁复合材料质量的24.4％。In this embodiment, the loading amount of poly-m-phenylene diamine is 44.6% of the mass of the composite material of manganese dioxide@polym-phenylenediamine@tetraoxide, and the loading amount of manganese dioxide is manganese dioxide@poly-p-phenylene two 24.4% of the mass of amine@ferroferric oxide composite material.
本实施例中，四氧化三铁为表面粗糙的球状；聚间苯二胺为表面光滑的球状；所述二氧化锰@聚间苯二胺@四氧化三铁复合材料为表面粗糙的海胆状。In this embodiment, ferroferric oxide is spherical with a rough surface; poly-m-phenylene diamine is spherical with a smooth surface; the manganese dioxide@polym-phenylenediamine@triiron tetraoxide composite material is a sea urchin with rough surface .
本实施例中，二氧化锰@聚间苯二胺@四氧化三铁复合材料为深褐色粉末。In this embodiment, the manganese dioxide@polym-phenylenediamine@ferric oxide composite material is a dark brown powder.
一种上述本实施例的二氧化锰@聚间苯二胺@四氧化三铁复合材料的制备方法，包括以下步骤：A method for preparing the manganese dioxide@polym-phenylenediamine@triiron tetraoxide composite material of the above embodiment includes the following steps:
1.聚间苯二胺@四氧化三铁复合材料(FP)的制备1. Preparation of poly(m-phenylenediamine@ferric oxide) composite material (FP)
将1g通过水热反应制备的四氧化三铁粉末溶于100mL水中，超声溶解，得到混合溶液；将2g间苯二胺加入溶液中，25℃超声分散15min，使四氧化三铁和间苯二胺分散均匀。向所得溶液中滴加入11mL等摩尔量的过硫酸钠溶液，随后滴加11mL含有2M氢氧化钠的溶液(维持反应体系的pH值)。在25℃下搅拌5h，反应完成后磁性分离过滤，所得黑色固体用水和甲醇各洗三遍，得到聚间苯二胺@四氧化三铁复合材料。Dissolve 1g of ferroferric oxide powder prepared by hydrothermal reaction in 100mL of water and dissolve it ultrasonically to obtain a mixed solution; add 2g of m-phenylenediamine to the solution and disperse ultrasonically at 25°C for 15 minutes to make ferroferric oxide and isophthalic acid The amine is uniformly dispersed. To the obtained solution, 11 mL of an equimolar sodium persulfate solution was added dropwise, and then 11 mL of a solution containing 2M sodium hydroxide was added dropwise (to maintain the pH value of the reaction system). Stir at 25°C for 5 hours, after the reaction is completed, magnetic separation and filtration, the resulting black solid is washed with water and methanol three times each to obtain poly-m-phenylenediamine@tetrairon tetraoxide composite material.
2.二氧化锰@聚间苯二胺@四氧化三铁复合材料(FM)的制备2. Preparation of manganese dioxide@polym-phenylenediamine@ferric oxide composite (FM)
称取0.3g步骤1中制得的聚间苯二胺@四氧化三铁复合材料分散到50mL去离子水中，得到聚间苯二胺@四氧化三铁胶体，向所得的聚间苯二胺@四氧化三铁胶体中滴加入0.5mL12M浓盐酸的溶液。随后向混合液中滴加入一定体积的含有0.02M高锰酸钾的溶液(分别加入50,100,150,200mL，分别记为FM50，FM100，FM150，FM200，以得到具有不同二氧化锰比重的复合材料)，混合液在冰水浴中搅拌四小时，磁性分离过滤，所得产物用水和甲醇 各洗三遍，在60℃下干燥过夜，得到了二氧化锰@聚间苯二胺@四氧化三铁复合材料。Weigh 0.3 g of the poly-m-phenylene diamine@tetrairon tetraoxide composite material prepared in step 1 and disperse it into 50 mL of deionized water to obtain poly-m-phenylene diamine@tetra-iron oxide colloid. @Triiron tetraoxide colloid was added dropwise 0.5mL12M concentrated hydrochloric acid solution. Then add a certain volume of solution containing 0.02M potassium permanganate (50, 100, 150, 200 mL, respectively, denoted as FM50, FM100, FM150, FM200, respectively, to obtain composite materials with different specific gravity of manganese dioxide) into the mixed solution, and mix The solution was stirred in an ice-water bath for four hours, magnetically separated and filtered. The resulting product was washed three times with water and methanol, and dried overnight at 60°C to obtain a manganese dioxide@polymet-phenylenediamine@triiron tetraoxide composite material.
对比例1：Comparative example 1:
按以上所述1中聚间苯二胺@四氧化三铁复合材料制备方法制备聚间苯二胺@四氧化三铁复合材料。According to the preparation method of poly-m-phenylenediamine@triiron tetraoxide composite material in 1 above, the poly-m-phenylene diamine@triiron tetraoxide composite material was prepared.
对比例2：Comparative example 2:
一种聚间苯二胺的制备方法，包括以下步骤：将2g间苯二胺与100mL水混合，于25℃超声分散15min，使间苯二胺充分混合均匀，得到间苯二胺分散液；往所得的间苯二胺分散液中滴加11mL等摩尔量的过硫酸铵的溶液，随后滴加11mL含有2M氢氧化钠的溶液(维持反应体系的pH值)，在搅拌、温度为25℃的条件下进行氧化聚合反应5h，过滤，洗涤干燥，得到聚间苯二胺。A preparation method of poly-m-phenylene diamine, comprising the following steps: mixing 2 g of m-phenylene diamine with 100 mL of water, and ultrasonically dispersing at 25° C. for 15 min, so that the m-phenylene diamine is fully mixed uniformly to obtain a m-phenylene diamine dispersion; Add 11 mL of an equimolar amount of ammonium persulfate solution to the resulting m-phenylenediamine dispersion, and then add 11 mL of a solution containing 2M sodium hydroxide (to maintain the pH of the reaction system), and stir at 25°C. The oxidative polymerization reaction was carried out for 5h under the conditions of, filtered, washed and dried to obtain poly-m-phenylenediamine.
对比例3：Comparative example 3:
公开的专利201610065134.0中Fe 3O 4聚间苯二胺MnO 2磁性核壳结构纳米复合材料的制备方法，包括以下步骤： The method for preparing Fe 3 O 4 poly-m-phenylenediamine MnO 2 magnetic core-shell structure nanocomposite material in the published patent 201610065134.0 includes the following steps:
1、Fe 3O 4聚间苯二胺复合材料(对比例FP)的制备 1. Preparation of Fe 3 O 4 poly-m-phenylenediamine composite material (comparative example FP)
等物质的量的间苯二胺单体和Na 2S 2O 8依次加入Fe 3O 4分散液中，Fe 3O 4分散液的浓度为0.5‐2g/L，Fe 3O 4和间苯二胺单体的质量比为1:2。冰水浴条件下震荡反应；反应结束后，经水、乙醇洗涤，烘干，即得Fe 3O 44聚间苯二胺纳米粒子。 The same amount of m-phenylenediamine monomer and Na 2 S 2 O 8 were added to the Fe 3 O 4 dispersion in turn, the concentration of the Fe 3 O 4 dispersion was 0.5-2g/L, Fe 3 O 4 and m-benzene The mass ratio of the diamine monomer is 1:2. The reaction under ice shock; After completion of the reaction, with water, washed with ethanol, and drying, to obtain poly-3 O 4 4-phenylenediamine nanoparticles Fe.
2、Fe 3O 4聚间苯二胺MnO 2磁性核壳结构纳米复合材料的制备(对比例FM) 2. Preparation of Fe 3 O 4 poly-m-phenylenediamine MnO 2 magnetic core-shell structure nanocomposite (comparative example FM)
称取0.1g步骤1中制得的Fe 3O 4聚间苯二胺复合材料超声分散于pH＝2的溶液中。然后称量为0.8g的高锰酸钾加入到上述Fe 3O 4聚间苯二胺复合材料分散液中，震荡反应5h，磁性分离，水洗3次，无水乙醇洗2次，洗涤后的样品60℃烘干，即得Fe 3O 4聚间苯二胺MnO 2磁性核壳结构纳米复合材料。 Weigh 0.1 g of the Fe 3 O 4 poly-m-phenylenediamine composite material prepared in step 1 and ultrasonically disperse it in a solution with pH=2. Then weighed 0.8g potassium permanganate was added to the above Fe 3 O 4 poly-m-phenylenediamine composite material dispersion liquid, oscillated for 5 hours, magnetic separation, washed with water 3 times, washed with absolute ethanol 2 times, the washed The sample is dried at 60°C to obtain Fe 3 O 4 poly-m-phenylenediamine MnO 2 magnetic core-shell structure nanocomposite.
对比例4：未添加氢氧化钠的聚间苯二胺@四氧化三铁复合材料(FP未加NaOH)的制备Comparative Example 4: Preparation of poly-m-phenylenediamine@triiron tetraoxide composite without sodium hydroxide (FP without NaOH)
将1g通过水热反应制备的四氧化三铁粉末溶于100mL水中，超声溶解，得到混合溶液；将2g间苯二胺加入溶液中，25℃超声分散15min，使四氧化三铁和间苯二胺分散均匀。向所得溶液中滴加入11mL等摩尔量的过硫酸钠溶液。在25℃下搅拌5h，反应完成后磁性分离过滤，所得黑色固体用水和甲醇各洗三遍，得到聚间苯二胺@四氧化三铁复合材料。Dissolve 1g of ferroferric oxide powder prepared by hydrothermal reaction in 100mL of water and dissolve it ultrasonically to obtain a mixed solution; add 2g of m-phenylenediamine to the solution and disperse ultrasonically at 25°C for 15 minutes to make ferroferric oxide and isophthalic acid The amine is uniformly dispersed. 11 mL of an equimolar sodium persulfate solution was added dropwise to the resulting solution. Stir at 25°C for 5 hours, after the reaction is completed, magnetic separation and filtration, the resulting black solid is washed with water and methanol three times each to obtain poly-m-phenylenediamine@tetrairon tetraoxide composite material.
图1(b)为对比例1中制得的聚间苯二胺@四氧化三铁复合材料的TEM图。Figure 1(b) is a TEM image of the poly(m-phenylenediamine@triiron tetraoxide) composite prepared in Comparative Example 1.
图1(a)为对比例2中制得的聚间苯二胺的TEM图。由图一(a)可见，聚间苯二胺的 微观结构为球状。Figure 1(a) is a TEM image of the polym-phenylene diamine prepared in Comparative Example 2. It can be seen from Figure 1(a) that the microstructure of poly-m-phenylenediamine is spherical.
图1(c)为本发明实施例1中加入150mL含有0.02M高锰酸钾的溶液所制得的二氧化锰@聚间苯二胺@四氧化三铁复合材料FM150的TEM图。由图3可见，本发明二氧化锰@聚间苯二胺@四氧化三铁复合材料中在负载二氧化锰后变成了海胆状。Figure 1(c) is a TEM image of manganese dioxide@polymetaphenylenediamine@triiron tetraoxide composite material FM150 prepared by adding 150 mL of a solution containing 0.02M potassium permanganate in Example 1 of the present invention. It can be seen from Figure 3 that the manganese dioxide@polymetaphenylenediamine@triiron tetraoxide composite material of the present invention becomes a sea urchin after being loaded with manganese dioxide.
图2为本发明实施例1中制得的二氧化锰@聚间苯二胺@四氧化三铁复合材料的XPS图谱，广谱x射线光电子能谱结果同样显示了复合物中锰、碳、氧、氮元素的存在。对比FP的C 1s(图2b)，FM的C 1s图谱可以归于到sp2碳原子(C＝C),C-N键，以及另一个由碳原子(O-C＝O)产生的峰(图3b)。其中，O-C＝O键来自羧酸基团(-COOH)，其是苯环被高锰酸钾氧化后的产物之一。O 1s显示的图谱也证明了复合物中羧基的存在。具有强氧化性的高锰酸钾同时也对FP中的含氮基团产生了一定的作用。在FM的N 1s图谱中可以看出苯环型胺的含量从19.4％降到了11.5％，苯环型胺是一类可以被氧化剂转化为醌型亚胺(-N＝)的还原性基团。Figure 2 is the XPS spectrum of the manganese dioxide@polymetaphenylenediamine@triiron tetraoxide composite prepared in Example 1 of the present invention. The results of the broad spectrum X-ray photoelectron spectroscopy also show that the manganese, carbon, The presence of oxygen and nitrogen elements. Compared with the C 1s of FP (Figure 2b), the C 1s spectrum of FM can be attributed to sp2 carbon atoms (C=C), C-N bonds, and another peak generated by carbon atoms (O-C=O) (Figure 3b). Among them, the O-C=O bond comes from the carboxylic acid group (-COOH), which is one of the products after the benzene ring is oxidized by potassium permanganate. The pattern shown by O 1s also proves the presence of carboxyl groups in the complex. Potassium permanganate, which has strong oxidizing properties, also has a certain effect on the nitrogen-containing groups in FP. In the N 1s spectrum of FM, it can be seen that the content of benzene cyclic amines has dropped from 19.4% to 11.5%. Benzene cyclic amines are a type of reducing group that can be converted into quinoid imines (-N=) by oxidizing agents. .
图3(a)为本发明实施例1中制得的二氧化锰@聚间苯二胺@四氧化三铁复合材料的热重分析图。聚间苯二胺@四氧化三铁在200-630℃失重约44.6％，其包括聚间苯二胺热分解所导致的重量损失，而聚间苯二胺@四氧化三铁复合材料中聚间苯二胺负载量为44.6％。根据TGA图像显示，在负载二氧化锰后，复合材料的热稳定性增加了，二氧化锰@聚间苯二胺@四氧化三铁复合材料FM150中二氧化锰的负载量经计算为24.4％。Figure 3(a) is a thermogravimetric analysis diagram of the manganese dioxide@polymetaphenylenediamine@triiron tetraoxide composite material prepared in Example 1 of the present invention. The weight loss of poly-m-phenylenediamine@tetrairon tetraoxide at 200-630℃ is about 44.6%, which includes the weight loss caused by the thermal decomposition of poly-m-phenylene diamine. The loading of m-phenylenediamine is 44.6%. According to the TGA image, after loading manganese dioxide, the thermal stability of the composite material increases. The loading amount of manganese dioxide in the composite material FM150 of manganese dioxide@polymetaphenyldiamine@tetraoxide is calculated to be 24.4% .
图3(b)为材料的磁滞回线，聚间苯二胺@四氧化三铁和二氧化锰@聚间苯二胺@四氧化三铁壳核复合材料的磁性曲线在室温下展现出没有剩磁和矫顽力，表明了材料的超顺磁特性。聚间苯二胺@四氧化三铁的磁性饱和值是70.88emu g -1，尽管二氧化锰@聚间苯二胺@四氧化三铁壳核复合材料磁性饱和值磁性下降至59.07emu g -1，但仍然可以保证在低磁域梯度下能将二氧化锰@聚间苯二胺@四氧化三铁核壳复合材料从水溶液中简单分离。 Figure 3(b) shows the hysteresis loop of the material. The magnetic curves of polym-phenylene diamine@tetra铁三铁 and manganese dioxide@polymeta-phenylenediamine@tetraoxide three iron shell core composites show at room temperature There is no remanence and coercivity, indicating the superparamagnetic properties of the material. The magnetic saturation value of the condenser-phenylenediamine @ triiron tetroxide is 70.88emu g -1, manganese dioxide, although poly-m-phenylenediamine @ @ tetroxide steel nuclear magnetic saturation value of the magnetic composite material down to 59.07emu g - 1 , but it can still ensure that the manganese dioxide@polymeta-phenylenediamine@tetraoxide core-shell composite can be easily separated from the aqueous solution under the low magnetic field gradient.
经过测量聚间苯二胺@四氧化三铁的BET比表面积为88.16m 2g -1，而负载二氧化锰后的二氧化锰@聚间苯二胺@四氧化三铁增加到214.72m 2g -1，表明了二氧化锰的加入可以增加材料表面积。 After measuring the BET specific surface area of poly-m-phenylene diamine@tetrairon tetraoxide to be 88.16m 2 g -1 , the manganese dioxide@polymeta-phenylene diamine@tetrogen oxide after loading manganese dioxide increased to 214.72m 2 g -1 , indicating that the addition of manganese dioxide can increase the surface area of the material.
实施例2：Example 2:
1、一种二氧化锰@聚间苯二胺@四氧化三铁复合材料在处理重金属废水中的应用，包括以下步骤：1. The application of a manganese dioxide@polymeta-phenylenediamine@ferric oxide composite material in the treatment of heavy metal wastewater, including the following steps:
取对比例1中用到的四氧化三铁、二氧化锰、对比例1中制得的聚间苯二胺@四氧化三铁复合材料、对比例2中制得的聚间苯二胺、实施例1中具有不同比重的二氧化锰负载量的 二氧化锰@聚间苯二胺@四氧化三铁复合材料(FM50，FM100，FM150，FM200)各两份各5mg，分别加入到20mL、Pb浓度为100mg/L、Cd浓度为50mg/L、pH为5.3的重金属废水中，置于25℃、170rpm的恒温水浴锅中振荡吸附24h，完成对重金属废水的处理。Take the ferroferric oxide and manganese dioxide used in Comparative Example 1, the poly-m-phenylene diamine@tetra-iron composite material prepared in Comparative Example 1, and the poly-m-phenylene diamine prepared in Comparative Example 2. In Example 1, the manganese dioxide@polymetaphenylenediamine@triiron tetraoxide composite material (FM50, FM100, FM150, FM200) with different specific gravity of manganese dioxide loading amount of each 5mg, respectively added to 20mL, The heavy metal wastewater with a Pb concentration of 100 mg/L, a Cd concentration of 50 mg/L and a pH of 5.3 is placed in a constant temperature water bath at 25° C. and 170 rpm for 24 hours to absorb and vibrate to complete the treatment of the heavy metal wastewater.
2、取对比例3中用到的制得的对比例FP、对比例FM，对比例4中制得的未加氢氧化钠的聚间苯二胺@四氧化三铁复合材料(FP未加NaOH)、实施例1中具有FM150各5mg，分别加入到20mL、Pb浓度为50mg/L、pH为5.3的重金属废水中，置于25℃、170rpm的恒温水浴锅中振荡吸附24h，完成对重金属废水的处理。2. Take the comparative example FP and comparative example FM used in comparative example 3, and the poly-m-phenylene diamine@tetrairon tetraoxide composite material without sodium hydroxide prepared in comparative example 4 (without FP NaOH), 5mg each of FM150 in Example 1, was added to 20mL, Pb concentration of 50mg/L, pH of 5.3 heavy metal wastewater, placed in a constant temperature water bath at 25℃, 170rpm for 24h to absorb the heavy metals. Wastewater treatment.
3、对比例3中用到的制得的对比例FM和实施例1中制的FM150各5mg，分别加入到20mL、As(III)浓度为12.5mg/L的重金属废水中，置于25℃、170rpm的恒温水浴锅中振荡吸附24h，完成对重金属废水的处理。3. 5mg each of the comparative FM prepared in comparative example 3 and the FM150 prepared in example 1 were added to 20 mL of heavy metal wastewater with an As(III) concentration of 12.5 mg/L, and placed at 25°C. , Vibration and adsorption in a 170rpm constant temperature water bath for 24 hours to complete the treatment of heavy metal wastewater.
振荡吸附完成后，取5mL处理后溶液过0.45μm的水系滤膜，每个滤液均采用电感耦合等离子体发射光谱仪(ICP-AES)测定重金属含量，并计算得出不同材料对重金属的吸附量。图4为四氧化三铁、聚间苯二胺、对比例1中得到的聚间苯二胺@四氧化三铁复合材料、二氧化锰和本发明实施例2中得到的四种二氧化锰@聚间苯二胺@四氧化三铁复合材料对重金属吸附量的对比图。由图4(a)可知，起初吸附量随着高锰酸钾的含量增加而增加，但是达到一定值后再增加高锰酸钾的浓度不会导致材料的吸附量的增加。本发明中材料FM150对Pb的吸附量均高于四氧化三铁、聚间苯二胺、二氧化锰三个单体和聚间苯二胺@四氧化三铁复合材料以及其他三种二氧化锰@聚间苯二胺@四氧化三铁复合材料。由图4(b)可知，聚间苯二胺在添加了四氧化三铁磁芯后表面负电荷增加，随后负载二氧化锰使得材料从带正点转为带负电荷。增强了材料与重金属之前的静电引力。After the vibration adsorption is completed, take 5mL of the treated solution and pass it through a 0.45μm water-based filter membrane. Each filtrate is measured with an inductively coupled plasma emission spectrometer (ICP-AES) for heavy metal content, and the amount of heavy metal adsorbed by different materials is calculated. Figure 4 shows the triiron tetroxide, polymetaphenylene diamine, polymetaphenylene diamine@tetrairon tetraoxide composite material obtained in Comparative Example 1, manganese dioxide and four manganese dioxides obtained in Example 2 of the present invention @Polym-phenylenediamine@Triiron tetroxide composite material to compare the amount of heavy metal adsorption. It can be seen from Figure 4(a) that the initial adsorption capacity increases with the increase of the potassium permanganate content, but increasing the potassium permanganate concentration after reaching a certain value will not lead to an increase in the adsorption capacity of the material. The adsorption capacity of the material FM150 to Pb in the present invention is higher than the three monomers of ferroferric oxide, poly-m-phenylene diamine, manganese dioxide, poly-m-phenylene diamine@tetra-iron tetraoxide composite material and other three kinds of dioxide Manganese@polymeta-phenylenediamine@ferric oxide composite material. It can be seen from Figure 4(b) that the negative charge on the surface of polymetaphenylene diamine is increased after the ferroferroic oxide core is added, and then the loading of manganese dioxide makes the material change from a positive point to a negative charge. Strengthen the electrostatic attraction between the material and heavy metals.
图5(a)中为本发明的FP对铅的吸附量明显高于对比例4中合成的FP未加NaOH，约是对比例4中合成的吸附效果1.2倍。说明NaOH的加入会明显促进FP对铅的吸附。原因是因为羟基可以促进聚合物的聚合过程，NaOH会提高聚间苯二胺的产率。FP产率约提高了5％－10％。因此本发明中添加的NaOH优化了FP的合成。通过对比例1中制得的FP和对比例3中合成的FP对重金属铅的吸附量对比，发现本发明合成的FP比对比例3中合成的吸附效果约高1.9倍。对比例2中不仅没有添加NaOH，而且对比例中FP是在0度合成的，而本发明是在25度恒温反应。温度对聚合物的产率也有促进作用，FP产率约提高了5％－15％。对比例3中合成的FM与本发明FM吸附铅的比较发现，本发明合成的吸附效果更优。同时，通过对比实施例1中制得FM150分离后的溶液以及对比例3中对比例FM分离后的溶液(图5b)，发现对比例中高锰酸钾有大量剩余，对比例3中剩余高锰酸钾约为300mg，是总添加量 的37％。造成严重的资源浪费，实施例1基本上没有高锰酸钾剩余。根据本图4(a)结果显示，高锰酸钾的含量达到一定程度不会对材料的吸附产生促进作用，因此高锰酸钾含量不宜过多，会造成资源浪费。高锰酸钾含量与FP的质量比约为1:0.1-0.9。Figure 5(a) shows that the FP of the present invention has a significantly higher adsorption capacity for lead than the FP synthesized in Comparative Example 4 without NaOH, which is about 1.2 times the adsorption effect synthesized in Comparative Example 4. It shows that the addition of NaOH will obviously promote the adsorption of FP to lead. The reason is because the hydroxyl group can promote the polymerization process of the polymer, and NaOH can increase the yield of poly-m-phenylenediamine. The yield of FP is increased by about 5%-10%. Therefore, the NaOH added in the present invention optimizes the synthesis of FP. By comparing the adsorption capacity of the FP prepared in Comparative Example 1 and the FP synthesized in Comparative Example 3 on heavy metal lead, it is found that the adsorption effect of the FP synthesized in the present invention is about 1.9 times higher than that synthesized in Comparative Example 3. In Comparative Example 2, not only was NaOH not added, but in Comparative Example FP was synthesized at 0°C, while the present invention reacted at a constant temperature of 25°C. Temperature also promotes the yield of the polymer, and the yield of FP is increased by approximately 5%-15%. Comparing the FM synthesized in Comparative Example 3 with the FM of the present invention adsorbing lead, it is found that the adsorption effect of the synthesis of the present invention is better. At the same time, by comparing the separated solution of FM150 prepared in Example 1 and the separated solution of FM in Comparative Example 3 (Figure 5b), it is found that a large amount of potassium permanganate remains in Comparative Example, and high manganese remains in Comparative Example 3. Potassium acid is about 300mg, which is 37% of the total added amount. This caused serious waste of resources, and Example 1 basically had no potassium permanganate remaining. According to the results of Fig. 4(a), reaching a certain level of potassium permanganate will not promote the adsorption of materials. Therefore, the content of potassium permanganate should not be too much, which will cause waste of resources. The mass ratio of potassium permanganate content to FP is about 1:0.1-0.9.
本实验还研究了对比例FM和实施例1中具有FM150对三价砷的吸附效果。处理初始浓度为12.5ppm的砷，其中本发明的FM150对砷的去除率为39％，吸附量为20mg/g。而对比例FM对砷的去除率为16％，吸附量为8mg/g。从结果可以看出本发明的FM150吸附量约对比利FM的2.5倍。虽然吸附能力优于对比例材料，但是本发明材料对砷的去除效率很低，不到40％，原因在于材料表面带负电荷，而砷在水体中也是以负电荷的砷酸盐形式存在，二者之间会存在静电斥力，会影响砷的吸附导致吸附效果不佳。因而不太适合对含砷废水的处理，而该材料应用带正电的重金属如本发明的铅由于静电引力作用，可以有很高的吸附量约438.6mg/g。This experiment also studied the adsorption effect of FM150 in Comparative Example FM and Example 1 on trivalent arsenic. Treating arsenic with an initial concentration of 12.5 ppm, the removal rate of arsenic by the FM150 of the present invention is 39%, and the adsorption capacity is 20 mg/g. The arsenic removal rate of the comparative example FM is 16%, and the adsorption capacity is 8mg/g. It can be seen from the results that the adsorption capacity of the FM150 of the present invention is about 2.5 times that of the FM. Although the adsorption capacity is better than that of the comparative material, the removal efficiency of the material of the present invention for arsenic is very low, less than 40%, because the surface of the material is negatively charged, and arsenic is also present in the form of negatively charged arsenate in water. There will be electrostatic repulsion between the two, which will affect the adsorption of arsenic and cause poor adsorption. Therefore, it is not suitable for the treatment of arsenic-containing wastewater, and the material using positively charged heavy metals such as lead of the present invention can have a high adsorption capacity of about 438.6 mg/g due to electrostatic attraction.
实施例3：Example 3:
一种二氧化锰@聚间苯二胺@四氧化三铁复合材料在处理重金属废水中的应用，包括以下步骤：The application of a manganese dioxide@polym-phenylenediamine@ferric oxide composite material in the treatment of heavy metal wastewater includes the following steps:
取18份实施例1中的二氧化锰@聚间苯二胺@四氧化三铁复合材料(FM150)，每份5mg，分别加入到20mL、Pb浓度为100mg/L，Cd浓度为50mg/L、pH为5.3的重金属废水中，置于25℃、170rpm的恒温水浴锅中振荡吸附，其中振荡吸附的时间分别为1min、5min、10min、30min、60min、120min、240min、360min、720min、1440min和完成对重金属废水的处理。Take 18 parts of the manganese dioxide@polymetaphenylenediamine@triiron tetraoxide composite material (FM150) in Example 1, 5mg each, add to 20mL, Pb concentration is 100mg/L, Cd concentration is 50mg/L , Heavy metal wastewater with a pH of 5.3, placed in a constant temperature water bath at 25°C and 170rpm for oscillating adsorption. The oscillation adsorption time is 1min, 5min, 10min, 30min, 60min, 120min, 240min, 360min, 720min, 1440min and Complete the treatment of heavy metal wastewater.
振荡吸附完成后，取5mL处理后溶液过0.45μm的水系滤膜，每个滤液均采用电感耦合等离子体发射光谱仪(ICP-AES)测定重金属含量，并计算得出FM150对两种重金属离子的吸附量随时间变化的趋势，结果如图6所示。图6为二氧化锰@聚间苯二胺@四氧化三铁复合材料对重金属吸附量随时间变化关系图。由图6可知，本发明二氧化锰@聚间苯二胺@四氧化三铁复合材料对重金属的吸附随时间的增加而增大，在5min内，FM150对Pb的吸附达到了吸附量的73％，对Cd的吸附达到了了87％，说明FM150对重金属的吸附不仅吸附量高而且过程速度快，在6h已基本达到平衡，24h达到平衡，吸附量分别为Pb 281mg/g，Cd 70mg/g。本发明二氧化锰@聚间苯二胺@四氧化三铁复合材料对重金属的吸附过程符合二级吸附动力学模型。After the oscillating adsorption is completed, take 5mL of the treated solution and pass it through a 0.45μm water-based filter membrane, and each filtrate is measured with an inductively coupled plasma emission spectrometer (ICP-AES) for heavy metal content, and the adsorption of two heavy metal ions by FM150 is calculated The trend of the quantity over time, the result is shown in Figure 6. Figure 6 shows the relationship between the amount of heavy metal adsorption of manganese dioxide@polym-phenylenediamine@ferric oxide composite material over time. It can be seen from Fig. 6 that the adsorption of heavy metals on the manganese dioxide@polymetaphenylenediamine@triiron tetraoxide composite material of the present invention increases with the increase of time. Within 5 minutes, the adsorption of FM150 on Pb reached 73% %, the adsorption of Cd reached 87%, indicating that the adsorption of heavy metals by FM150 is not only high but also fast. It has basically reached equilibrium at 6h and reached equilibrium at 24h. The adsorbed amounts are Pb 281mg/g and Cd 70mg/ g. The adsorption process of the manganese dioxide@polym-phenylenediamine@ferric oxide composite material of the present invention for heavy metals conforms to the two-stage adsorption kinetic model.
实施例4：Example 4:
一种二氧化锰@聚间苯二胺@四氧化三铁复合材料在处理重金属废水中的应用，包括以下 步骤：The application of a manganese dioxide@polymeta-phenylenediamine@ferric oxide composite material in the treatment of heavy metal wastewater includes the following steps:
第一组：取14份实施例1中的二氧化锰@聚间苯二胺@四氧化三铁复合材料(FM150)，每份5mg，分别加入到Pb浓度为100mg/L，Cd浓度为50mg/L的重金属废水(该重金属废水的体积均为20mL、pH值均为5.3)中，置于25℃、170rpm的恒温水浴锅中振荡吸附24h，完成对重金属废水的处理。The first group: Take 14 parts of the manganese dioxide@polymetaphenylenediamine@triiron tetraoxide composite material (FM150) in Example 1, 5mg each, and add them to the Pb concentration of 100mg/L and the Cd concentration of 50mg. /L heavy metal waste water (the volume of the heavy metal waste water is 20 mL, and the pH value is both 5.3), placed in a constant temperature water bath at 25° C., 170 rpm, and vibrated for 24 hours to complete the treatment of heavy metal waste water.
第二组：取14份实施例1中的二氧化锰@聚间苯二胺@四氧化三铁复合材料(FM150)，每份5mg，分别加入到Pb浓度为100mg/L，Cd浓度为50mg/L的重金属废水(该重金属废水的体积均为20mL、pH值均为5.3)中，置于35℃、170rpm的恒温水浴锅中振荡吸附24h，完成对重金属废水的处理。The second group: Take 14 parts of the manganese dioxide@polymetaphenylenediamine@triiron tetraoxide composite material (FM150) in Example 1, 5mg each, and add them to the Pb concentration of 100mg/L and the Cd concentration of 50mg. /L heavy metal waste water (the volume of the heavy metal waste water is 20 mL, and the pH value is both 5.3), placed in a constant temperature water bath at 35° C., 170 rpm, and oscillated for 24 hours to complete the treatment of heavy metal waste water.
第三组：取14份实施例1中的二氧化锰@聚间苯二胺@四氧化三铁复合材料(FM150)，每份5mg，分别加入到Pb浓度为100mg/L，Cd浓度为50mg/L的重金属废水(该重金属废水的体积均为20mL、pH值均为5.3)中，置于45℃、170rpm的恒温水浴锅中振荡吸附24h，完成对重金属废水的处理。The third group: Take 14 parts of manganese dioxide@polym-phenylenediamine@triiron tetraoxide composite material (FM150) in Example 1, 5mg each, and add them to Pb concentration of 100mg/L and Cd concentration of 50mg /L heavy metal waste water (the volume of the heavy metal waste water is 20 mL, and the pH value is both 5.3), placed in a constant temperature water bath at 45° C., 170 rpm, and oscillated for 24 hours to complete the treatment of heavy metal waste water.
振荡吸附完成后，取5mL处理后溶液过0.45μm的水系滤膜，每个滤液均采用电感耦合等离子体发射光谱仪(ICP-AES)测定重金属含量，结果如图7所示。图7为本发明实施例4中二氧化锰@聚间苯二胺@四氧化三铁复合材料FM150在不同温度下对重金属的吸附量与初始浓度的关系曲线图。由图7可知，本发明二氧化锰@聚间苯二胺@四氧化三铁复合材料对重金属吸附随温度的增高而增加，同时随初始浓度的增加而增大，通过Langmuir等温线拟合计算得出最大吸附量分别为Pb 438.6mg/g，Cd 121.5mg/g。After the oscillating adsorption was completed, 5 mL of the treated solution was passed through a 0.45 μm water-based filter membrane, and the heavy metal content of each filtrate was measured by inductively coupled plasma emission spectrometer (ICP-AES). The results are shown in Figure 7. Fig. 7 is a graph showing the relationship between the adsorption amount of heavy metals and the initial concentration of the manganese dioxide@polym-phenylenediamine@triiron tetraoxide composite material FM150 in Example 4 of the present invention at different temperatures. It can be seen from Figure 7 that the adsorption of heavy metals on the manganese dioxide@polymetaphenylenediamine@triiron tetroxide composite material of the present invention increases with the increase of temperature and at the same time increases with the increase of the initial concentration, which is calculated by Langmuir isotherm The maximum adsorption capacity is Pb 438.6mg/g and Cd 121.5mg/g.
实施例5：Example 5:
一种二氧化锰@聚间苯二胺@四氧化三铁复合材料在处理重金属废水中的应用，包括以下步骤：The application of a manganese dioxide@polym-phenylenediamine@ferric oxide composite material in the treatment of heavy metal wastewater includes the following steps:
取12份实施例1中的二氧化锰@聚间苯二胺@四氧化三铁复合材料(FM150)，每份5mg，分别加入到20mL、pH分别为2、3、4、5、6、7的重金属废水中(使用盐酸和氢氧化钠溶液调节溶液的pH，并使用玻璃电极pH计测定溶液pH)、Pb浓度为100mg/L、Cd浓度为50mg/L、置于25℃、170rpm的恒温水浴锅中振荡吸附24h，完成对重金属废水的处理。Take 12 parts of the manganese dioxide@polym-phenylenediamine@triiron tetraoxide composite material (FM150) in Example 1, 5mg each, add to 20mL, pH 2, 3, 4, 5, 6, 7 heavy metal wastewater (use hydrochloric acid and sodium hydroxide solution to adjust the pH of the solution, and use a glass electrode pH meter to measure the pH of the solution), the Pb concentration is 100mg/L, the Cd concentration is 50mg/L, placed at 25℃, 170rpm Vibration and adsorption in a constant temperature water bath for 24 hours to complete the treatment of heavy metal wastewater.
振荡吸附完成后，取5mL处理后溶液过0.45μm的水系滤膜，每个滤液均采用电感耦合等离子体发射光谱仪(ICP-AES)测定重金属含量。结果如图8所示，FM150对重金属离子铅和镉的吸附能力在pH为2-7的范围内随pH增加显著上升。这与zeta电位的降低趋势大体一致，说明FM150与重金属之前存在静电引力。After the oscillating adsorption was completed, 5 mL of the treated solution was passed through a 0.45 μm water-based filter membrane, and the heavy metal content of each filtrate was measured by inductively coupled plasma emission spectrometer (ICP-AES). The results are shown in Figure 8. The adsorption capacity of FM150 for heavy metal ions lead and cadmium increases significantly with the increase of pH in the range of pH 2-7. This is generally consistent with the decreasing trend of zeta potential, indicating that there is electrostatic attraction between FM150 and heavy metals.
实施例6：Example 6:
一种二氧化锰@聚间苯二胺@四氧化三铁复合材料在处理重金属废水中的应用，包括以下步骤：The application of a manganese dioxide@polym-phenylenediamine@ferric oxide composite material in the treatment of heavy metal wastewater includes the following steps:
取20份实施例1中的二氧化锰@聚间苯二胺@四氧化三铁复合材料(FM150)，每份5mg，分别加入到20mL、Pb浓度为100mg/L，Cd浓度为50mg/L、pH为5.3、分别含有0.01M硝酸钠、0.01M氯化钠、0.01M氯化钾、0.01M氯化镁、0.01M氯化钙和含有腐殖酸(HA)且其浓度分别为2mg/L、4mg/L、6mg/L、8mg/L、10mg/L的重金属废水中，置于25℃、170rpm的恒温水浴锅中振荡吸附24h，完成对重金属废水的处理。Take 20 parts of manganese dioxide@polym-phenylenediamine@triiron tetraoxide composite material (FM150) in Example 1, 5mg each, add to 20mL, Pb concentration is 100mg/L, Cd concentration is 50mg/L , PH is 5.3, respectively containing 0.01M sodium nitrate, 0.01M sodium chloride, 0.01M potassium chloride, 0.01M magnesium chloride, 0.01M calcium chloride and containing humic acid (HA) and its concentration is 2mg/L, 4mg/L, 6mg/L, 8mg/L, and 10mg/L heavy metal wastewater are placed in a constant temperature water bath at 25°C and 170rpm for 24 hours to oscillate and absorb to complete the treatment of heavy metal wastewater.
振荡吸附完成后，取5mL处理后溶液过0.45μm的水系滤膜，每个滤液均采用电感耦合等离子体发射光谱仪(ICP-AES)测定重金属含量，结果如图7所示。图9可见多种共存阳离子(包括一价和二价的)的存在和低浓度的HA的存在均不会对FM150对Pb和Cd的吸附产生明显影响，因此材料可应用与实际的污水处理中。After the oscillating adsorption was completed, 5 mL of the treated solution was passed through a 0.45 μm water-based filter membrane, and the heavy metal content of each filtrate was measured by inductively coupled plasma emission spectrometer (ICP-AES). The results are shown in Figure 7. Figure 9 shows that the presence of a variety of coexisting cations (including monovalent and divalent) and the presence of low concentrations of HA will not significantly affect the adsorption of FM150 on Pb and Cd, so the material can be used in actual sewage treatment .
综上所述，本发明二氧化锰@聚间苯二胺@四氧化三铁复合材料具有成本低、易合成、易分离、吸附性能好等优点，能够有效吸附废水中的重金属，具有较好的使用价值和应用前景。In summary, the manganese dioxide@polymetaphenylenediamine@triiron tetraoxide composite material of the present invention has the advantages of low cost, easy synthesis, easy separation, and good adsorption performance. It can effectively adsorb heavy metals in wastewater and has good The use value and application prospects of
以上实施例仅是本发明的优选实施方式，本发明的保护范围并不仅局限于上述实施例。凡属于本发明思路下的技术方案均属于本发明的保护范围。应该指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下的改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited to the above embodiments. All technical solutions under the idea of the present invention belong to the protection scope of the present invention. It should be pointed out that for those of ordinary skill in the art, improvements and modifications made without departing from the principle of the present invention should also be regarded as the protection scope of the present invention.

Claims (10)

  1. 一种二氧化锰@聚间苯二胺@四氧化三铁复合材料，其特征在于，包括四氧化三铁、二氧化锰和聚间苯二胺，所述聚间苯二胺负载在四氧化三铁表面，二氧化锰负载在聚间苯二胺表面，最后形成双层的核壳结构的三元复合材料；所述四氧化三铁在所述二氧化锰@聚间苯二胺@四氧化三铁复合材料中的质量占比不高于40％。A manganese dioxide@polymetaphenylenediamine@triiron tetroxide composite material, which is characterized in that it comprises ferroferric oxide, manganese dioxide and poly-m-phenylene diamine. The poly-m-phenylene diamine is supported on On the surface of tri-iron, manganese dioxide is supported on the surface of poly-m-phenylene diamine, and finally a ternary composite material with a double-layer core-shell structure is formed; The mass ratio in the ferroferric oxide composite material is not higher than 40%.
  2. 根据权利要求1所述的二氧化锰@聚间苯二胺@四氧化三铁复合材料，其特征在于，The manganese dioxide@polym-phenylenediamine@triiron tetraoxide composite material according to claim 1, characterized in that:
    所述二氧化锰@聚间苯二胺@四氧化三铁复合材料中的四氧化三铁、聚间苯二胺、二氧化锰的质量比例范围为1∶1.1∶0.9-1∶2∶0.1；所述二氧化锰@聚间苯二胺@四氧化三铁复合材料的比表面积为150m 2/g-220m 2/g。 The mass ratio of ferroferric oxide, polym-phenylene diamine, and manganese dioxide in the manganese dioxide@polym-phenylenediamine@ferric oxide composite material ranges from 1:1.1:0.9-1:2:0.1 The specific surface area of the manganese dioxide@polym-phenylenediamine@ferric oxide composite material is 150m 2 /g-220m 2 /g.
  3. 根据权利要求1或2所述的二氧化锰@聚间苯二胺@四氧化三铁复合材料，其特征在于，所述四氧化三铁为球状，表面粗糙，尺寸约50-100nm；所述聚间苯二胺为球状，表面光滑；所述二氧化锰@聚间苯二胺@四氧化三铁复合材料为海胆状，表面粗糙。The manganese dioxide@polym-phenylenediamine@ferroferric oxide composite material according to claim 1 or 2, wherein the ferroferric oxide is spherical in shape with rough surface and a size of about 50-100 nm; The poly-m-phenylene diamine is spherical and the surface is smooth; the manganese dioxide@polym-phenylene diamine@triiron tetraoxide composite material is sea urchin-shaped with a rough surface.
  4. 权利要求1-3任一所述的二氧化锰@聚间苯二胺@四氧化三铁复合材料的制备方法，其特征在于，包括以下步骤：The preparation method of manganese dioxide@polym-phenylenediamine@triiron tetraoxide composite material according to any one of claims 1 to 3, characterized in that it comprises the following steps:
    S1、将四氧化三铁超声分散到水中，得到四氧化三铁分散液；S1, ultrasonically disperse ferroferric oxide into water to obtain a ferroferric oxide dispersion;
    S2、将间苯二胺与四氧化三铁分散液混合，超声分散，得到四氧化三铁和间苯二胺的分散液；S2. Mix the m-phenylenediamine and the ferroferric oxide dispersion liquid, and ultrasonically disperse to obtain a dispersion liquid of ferroferric oxide and m-phenylenediamine;
    S3、将步骤S2中得到的四氧化三铁和间苯二胺的分散液与氧化剂混合进行氧化聚合反应，得到聚间苯二胺@四氧化三铁复合材料；S3, mixing the dispersion of ferroferric oxide and m-phenylenediamine obtained in step S2 with an oxidizing agent for oxidative polymerization to obtain a polym-phenylene diamine@triiron tetraoxide composite material;
    S4、将步骤S3中得到聚间苯二胺@四氧化三铁复合材料分散到水中得到胶体分散液，向其中加入高锰酸钾溶液以进行氧化还原反应，得到二氧化锰@聚间苯二胺@四氧化三铁壳核结构复合材料。S4. Disperse the poly-m-phenylenediamine@triiron tetraoxide composite material obtained in step S3 into water to obtain a colloidal dispersion, and add potassium permanganate solution to it to perform oxidation-reduction reaction to obtain manganese dioxide@polymetaphthalene Amine@Tri-iron tetraoxide shell core structure composite material.
  5. 根据权利要求4所述的制备方法，其特征在于，所述四氧化三铁、间苯二胺、氧化剂和高锰酸钾的质量比为1∶1～4∶3～6∶0.1～0.9；The preparation method according to claim 4, wherein the mass ratio of the ferroferric oxide, m-phenylenediamine, oxidant and potassium permanganate is 1:1～4:3～6:0.1～0.9;
    优选地，所述氧化剂为过硫酸铵和/或过硫酸钠。Preferably, the oxidant is ammonium persulfate and/or sodium persulfate.
  6. 根据权利要求4或5所述的制备方法，其特征在于，所述步骤S2中，所述超声分散的温度为15℃～45℃；所述超声分散的时间为0.5h～1h。The preparation method according to claim 4 or 5, wherein in the step S2, the temperature of the ultrasonic dispersion is 15° C. to 45° C.; the time of the ultrasonic dispersion is 0.5 h to 1 h.
  7. 根据权利要求3～5中任一项所述的制备方法，其特征在于，所述步骤S4中，所述氧化还原反应过程中加入酸以维持反应体系的pH值，所述酸为盐酸/硝酸/硫酸溶液；所述酸中H +的浓度为5M～15M；所述氧化还原反应在搅拌条件下进行；所述氧化还原反应的温度为0℃～5℃；所述氧化还原反应的时间为1h～12h。 The preparation method according to any one of claims 3 to 5, wherein in the step S4, an acid is added during the redox reaction to maintain the pH of the reaction system, and the acid is hydrochloric acid/nitric acid /Sulfuric acid solution; the concentration of H + in the acid is 5M-15M; the redox reaction is carried out under stirring conditions; the temperature of the redox reaction is 0°C to 5°C; the time of the redox reaction is 1h～12h.
  8. 权利要求1-3任一所述的二氧化锰@聚间苯二胺@四氧化三铁复合材料或权利要求 4～7任一项所述的制备方法制得的二氧化锰@聚间苯二胺@四氧化三铁复合材料在处理重金属废水中的应用。The manganese dioxide@polymetaphenylenediamine@triiron tetraoxide composite material according to any one of claims 1-3 or the manganese dioxide@polyisobenzene prepared by the preparation method according to any one of claims 4-7 The application of diamine@ferric oxide composite material in the treatment of heavy metal wastewater.
  9. 根据权利要求8所述的应用，其特征在于，包括以下步骤：将二氧化锰@聚间苯二胺@四氧化三铁复合材料与重金属废水混合进行振荡吸附，完成对重金属废水的处理；所述二氧化锰@聚间苯二胺@四氧化三铁复合材料的添加量为每升重金属废水中添加二氧化锰@聚间苯二胺@四氧化三铁复合材料0.1g～0.5g。The application according to claim 8, characterized in that it comprises the following steps: mixing manganese dioxide@polymeta-phenylenediamine@triiron tetraoxide composite material with heavy metal wastewater for oscillating adsorption to complete the treatment of heavy metal wastewater; The addition amount of manganese dioxide@polymetaphenylenediamine@triiron tetraoxide composite material is 0.1g～0.5g per liter of heavy metal wastewater.
  10. 根据权利要求8所述的应用，其特征在于，所述重金属废水的浓度为50mg/L～100mg/L Cd和/或50mg/L～200mg/L Pb；所述重金属废水的pH值为2～7；The application according to claim 8, wherein the concentration of the heavy metal wastewater is 50mg/L-100mg/L Cd and/or 50mg/L-200mg/L Pb; the pH value of the heavy metal wastewater is 2～ 7;
    优选地，所述振荡吸附的转速为100rpm～200rpm；所述振荡吸附的温度为15℃～45℃；所述振荡吸附的时间为1min～1440min。Preferably, the rotational speed of the oscillating adsorption is 100 rpm to 200 rpm; the temperature of the oscillating adsorption is 15° C. to 45° C.; the time of the oscillating adsorption is 1 min to 1440 min.
PCT/CN2019/091977 2019-06-05 2019-06-20 Manganese dioxide@polymetaphenylenediamine@ferroferric oxide composite material, preparation method therefor, and application thereof WO2020243996A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201910485155.1A CN112044410A (en) 2019-06-05 2019-06-05 Manganese dioxide @ poly (m-phenylenediamine) @ ferroferric oxide composite material and preparation method and application thereof
CN201910485155.1 2019-06-05

Publications (1)

Publication Number Publication Date
WO2020243996A1 true WO2020243996A1 (en) 2020-12-10

Family

ID=73609423

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/091977 WO2020243996A1 (en) 2019-06-05 2019-06-20 Manganese dioxide@polymetaphenylenediamine@ferroferric oxide composite material, preparation method therefor, and application thereof

Country Status (2)

Country Link
CN (1) CN112044410A (en)
WO (1) WO2020243996A1 (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130161570A1 (en) * 2011-12-22 2013-06-27 Ewha University - Industry Collaboration Foundation Manganese oxide/graphene nanocomposite and producing method of the same
CN104353437A (en) * 2014-11-05 2015-02-18 中南大学 Core-shell magnetic poly(m-phenylene diamine) nano-particle, preparation method and application thereof
CN105642255A (en) * 2016-01-29 2016-06-08 中南大学 Fe3O4@poly(m-phenylenediamine)@MnO2 magnetic core-shell structure nanocomposite material and preparation and application methods thereof
CN105771934A (en) * 2016-05-06 2016-07-20 扬州大学 Preparation method of nanometer magnetic adsorbent with core-shell structure

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130161570A1 (en) * 2011-12-22 2013-06-27 Ewha University - Industry Collaboration Foundation Manganese oxide/graphene nanocomposite and producing method of the same
CN104353437A (en) * 2014-11-05 2015-02-18 中南大学 Core-shell magnetic poly(m-phenylene diamine) nano-particle, preparation method and application thereof
CN105642255A (en) * 2016-01-29 2016-06-08 中南大学 Fe3O4@poly(m-phenylenediamine)@MnO2 magnetic core-shell structure nanocomposite material and preparation and application methods thereof
CN105771934A (en) * 2016-05-06 2016-07-20 扬州大学 Preparation method of nanometer magnetic adsorbent with core-shell structure

Also Published As

Publication number Publication date
CN112044410A (en) 2020-12-08

Similar Documents

Publication Publication Date Title
Bao et al. One-pot synthesis of magnetic graphene oxide composites as an efficient and recoverable adsorbent for Cd (II) and Pb (II) removal from aqueous solution
Zheng et al. Novel anionic polyacrylamide-modify-chitosan magnetic composite nanoparticles with excellent adsorption capacity for cationic dyes and pH-independent adsorption capability for metal ions
Wang et al. Sustainable advanced Fenton-like catalysts based on mussel-inspired magnetic cellulose nanocomposites to effectively remove organic dyes and antibiotics
Wang et al. Facile synthesis of polypyrrole decorated reduced graphene oxide–Fe3O4 magnetic composites and its application for the Cr (VI) removal
Ji et al. Sorption enhancement of nickel (II) from wastewater by ZIF-8 modified with poly (sodium 4-styrenesulfonate): Mechanism and kinetic study
Chen et al. Synergetic effect in a self-doping polyaniline/TiO2 composite for selective adsorption of heavy metal ions
He et al. Design and fabrication of highly ordered ion imprinted SBA-15 and MCM-41 mesoporous organosilicas for efficient removal of Ni2+ from different properties of wastewaters
Zhou et al. Enhanced removal of toxic hexavalent chromium from aqueous solution by magnetic Zr-MOF@ polypyrrole: performance and mechanism
Karthikeyan et al. Magnesium ferrite-reinforced polypyrrole hybrids as an effective adsorbent for the removal of toxic ions from aqueous solutions: Preparation, characterization, and adsorption experiments
Huang et al. Hydroxyl-functionalized TiO2@ SiO2@ Ni/nZVI nanocomposites fabrication, characterization and enhanced simultaneous visible light photocatalytic oxidation and adsorption of arsenite
CN112316906B (en) Preparation method of ferromagnetic amino-modified lanthanide metal organic framework material and application of ferromagnetic amino-modified lanthanide metal organic framework material in adsorption dephosphorization
Liu et al. Synthesis and characterization of magnetic Fe 3 O 4@ CaSiO 3 composites and evaluation of their adsorption characteristics for heavy metal ions
CN108704610B (en) Magnetic carbon modified magnesium-iron hydrotalcite composite material and preparation method and application thereof
CN107088398A (en) The preparation method of galapectite load aciculiform ferriferrous oxide nano composite
Zeng et al. Adsorption of heavy metal ions in water by surface functionalized magnetic composites: a review
CN112978983B (en) Iron-based biochar-based heavy metal complexing wastewater treatment and recycling process thereof
Zhang et al. A biomass resource strategy for alginate-polyvinyl alcohol double network hydrogels and their adsorption to heavy metals
Zhu et al. Nano-manganese oxides-modified biochar for efficient chelated copper citrate removal from water by oxidation-assisted adsorption process
Wang et al. Selective removal of Cr (VI) by tannic acid and polyethyleneimine modified zero-valent iron particles with air stability
Zhu et al. Ternary Fe 3 O 4@ PANI@ Au nanocomposites as a magnetic catalyst for degradation of organic dyes
Meng et al. Improving the adsorption of poly (o-phenylenediamine) to heavy metal ions in aqueous solution through its composite with carbon dots
Peng et al. Immobilization of nano-zero-valent irons by carboxylated cellulose nanocrystals for wastewater remediation
Liu et al. Octopus tentacle-like molecular chains in magnetic flocculant enhances the removal of Cu (II) and malachite green in water
Zhou et al. Nitrilotriacetic acid modified magnetic Prussian blue for efficient removal of cadmium from wastewater
Donga et al. (3-Aminopropyl) Triethoxysilane (APTES) functionalized magnetic nanosilica graphene oxide (MGO) nanocomposite for the comparative adsorption of the heavy metal [Pb (II), Cd (II) and Ni (II)] ions from aqueous solution

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19931722

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19931722

Country of ref document: EP

Kind code of ref document: A1