CN106345437A - Preparation method for conductive polymer sulfur fixation material and application thereof in water treatment - Google Patents

Preparation method for conductive polymer sulfur fixation material and application thereof in water treatment Download PDF

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Publication number
CN106345437A
CN106345437A CN201610979990.7A CN201610979990A CN106345437A CN 106345437 A CN106345437 A CN 106345437A CN 201610979990 A CN201610979990 A CN 201610979990A CN 106345437 A CN106345437 A CN 106345437A
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conducting polymer
solid sulfur
water
preparation
sulfur materials
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CN106345437B (en
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王忠德
刘晔
杨庆锁
林乃明
田思航
于学佳
田伟
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Shanxi Lvyuan Carbon Suo Technology Co.,Ltd.
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Taiyuan University of Technology
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    • 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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—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
    • 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
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C02F2001/46138—Electrodes comprising a substrate and a coating
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/203—Iron or iron compound
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/206—Manganese or manganese compounds

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

Abstract

The invention relates to the technical field of water treatment and specifically relates to a preparation method for a conductive polymer sulfur fixation material and an application thereof in removing heavy metal ions from water. A conductive polymer sulfur fixation material electrode is prepared, and the heavy metal ions are absorbed by applying voltage under two electrode systems. The method provided by the invention has the advantages of simplicity and low cost; the conductive polymer is taken as a sulfur fixation material, so that the conductivity is promoted; the reduction voltage is reduced, the reaction rate is increased, the energy consumption is reduced, the sulfide can be effectively fixed, and the secondary pollution caused by the sulfide entering water can be prevented; no complex instrument is required, and the subsequent treatment is not required; the adsorption capacity is high, and the speed is high; and one or more heavy metals, including iron, manganese, cobalt, cadmium, mercury, lead, silver, copper, zinc, arsenic, nickel, and the like, can be simultaneously removed from water.

Description

The preparation of the solid sulfur materials of conducting polymer and its application in water process
Technical field
The present invention relates to the invention belongs to water-treatment technology field field, particularly relating to the solid sulfur material of conducting polymer Application in the preparation method of material and its removal of heavy metal ions in water.
Background technology
With the development of modern industry, the smelting of the metal of heavy metal, the course of processing produce plurality of heavy metal ion Enter water body, the heavy metal ion such as cadmium, lead, chromium, copper, nickel it is difficult to biodegradation, after absorption of human body or absorption it will usually People's cylinder accumulation, then can cause disease and disorder when reaching a certain amount of, for example, damage central nervous system, affect intelligence Level and memory, destroy blood composition, also will produce very big harm to vital organs such as lung, kidney, livers.Process and go Except the heavy metal ion in waste water becomes the urgent needss of human society sound development.
The removal main method of heavy metal ion has chemical precipitation method, microbial method, electrolytic reduction, ion exchange Method, absorption method etc..Chemical precipitation method and absorption method are the methods of separation of heavy metal ions the most frequently used at present.
Chemical precipitation method is mainly introducing sulphur source in water body and forms sulfide precipitation, or forms chelating by chelating effect Thing, this method Precipitation Potential is strong, precipitate stable, easy and simple to handle, low cost.But there is also certain problem, sulfide sinks Shallow lake granularity is thin, bad filtration, reacts remaining s2-Need to process again.Chelate thing is all dynamic equilibrium in the solution , once being broken, chelate will continue to release metal ions and causes new pollution balance.
Absorption method absorption is considered as most efficient method, and easy to operate, adsorbent has conducting polymer, porous material Deng mainly using its more duct, larger specific surface area carrys out Adsorption of Heavy Metal Ions, conducting polymer is that one kind has The macromolecular material of conjugated system, electric conductivity and electrochemical stability that the high molecular polymer through overdoping has had, it is received Rice structure has larger surface area and abundant functional group, makes conducting polymer become good adsorbing material.These materials Heavy metal has stronger adsorption, but adsorption rate is slow, and adsorption capacity is limited, and the removal efficiency of heavy metal is not high enough.
For solving the above problems, the present invention adopts conducting polymer as solid sulfur materials with processing with heavy metal in water, with Prior art is compared and is had the advantage that (1) conducting polymer improves electric conductivity as solid sulfur materials, reduces recovery voltage, plus Fast response speed, reduces energy consumption；(2) conducting polymer effectively can fix sulfide as solid sulfur materials, prevents sulfide from expanding Dissipate to enter in water and cause secondary pollution；(3) conducting polymer is with low cost, convieniently synthesized, environmental friendliness；(4) the method operation Simplicity, the rate of adsorption is fast, and adsorption capacity is high.
Content of the invention
It is an object of the invention to overcoming some shortcomings of heavy metal processing method in existing water, there is provided conducting polymer Gu the application in the preparation method of sulfur materials and its removal of heavy metal ions in water.
The present invention is achieved by the following technical solutions: the preparation method of the solid sulfur materials of conducting polymer, including as follows Step:
Iron chloride and ferrous chloride react generation nano ferriferrous oxide granule under ammonia environment, are then aoxidized using nanometer four Three iron particles make template, add polymer monomer, be polymerized, form conducting polymer under oxidant effect, and being subsequently adding acid will Template removes, and obtains the conducting polymer materials of spherical shell shape；Adopt ball-milling method or heat treatment method by conducting polymer afterwards and Sulfur is combined, you can obtain the solid sulfur materials of conducting polymer.
When being embodied as, described polymer monomer is selected from pyrroles, aniline, acrylonitrile, one of thiophene.
Further, oxidant is selected from one of ferric chloride, Ammonium persulfate., potassium peroxydisulfate, sodium peroxydisulfate.
Further, described acid is selected from one of hydrochloric acid, sulphuric acid.
Preferably, the mass ratio of described conducting polymer and sulfur is 3:7 ~ 7:3.
For further description technical scheme, the invention provides the solid sulfur material of described conducting polymer Application in material removal of heavy metal ions in water.
In addition, the step of the using method of the solid sulfur materials of conducting polymer is: the solid sulfur materials of conducting polymer make electrode React with the heavy metal ion in water under electrochemical action, form the metal sulfide being coated in conducting polymer, realize The removal of heavy metal ion in water.
Wherein, the principle of application of the present invention and using method is: the solid sulfur materials of conducting polymer polymer are in electrification Effect is lower to reduce sulfur rapidly, quickly anti-with the heavy metal ion (fe, mn, co, cd, hg, pb, ag, cu, zn, as) in water Should, form stable metal sulfide, conducting polymer can effectively prevent the diffusion of sulfide simultaneously, it is to avoid causes secondary dirt Dye.
During concrete application, described electrochemical action applied voltage is 0v, and 2.5v.Namely process of the present invention Method can be carried out at lower voltages, and power consumption is low.
In addition, the invention provides a kind of preparation method of electrode, comprise the steps: the solid sulfur materials of conducting polymer and Binding agent mix homogeneously, solubilizer stirring forms uniform pasty state, is evenly applied on stainless steel substrates with blade applicator, is dried, shape Become electrode.
Further, described binding agent is Kynoar (pvdf), polyvinyl alcohol (pva), politef (ptfe), carboxylic At least one in sodium carboxymethylcellulose pyce (cmc), polyolefin (po), polyurethane (pu).
The solid sulfur materials of conducting polymer of the present invention are used for processing heavy metal ion in water, at lower voltages with water in Fe, mn, co, cd, hg, pb, ag, cu, zn, as, ni ion fast reaction, forms and is coated on stable metal in conducting polymer Sulfide effectively prevents the diffusion of sulfide, it is to avoid cause secondary pollution, and the rate of adsorption is fast, and adsorption capacity is high, makes in waste water Heavy metal ion reaches discharging standards, partly can reach drinking water standard.
Compared with prior art, the invention has the beneficial effects as follows: (1) conducting polymer improves conductive as solid sulfur materials Property, reduce recovery voltage, accelerate reaction rate, reduce energy consumption；(2) conducting polymer can effectively fix sulfur as solid sulfur materials Compound, prevents sulfide from diffusing in water and causes secondary pollution；(3) conducting polymer is with low cost, convieniently synthesized, environment friend Good；(4) the method is easy and simple to handle, and the rate of adsorption is fast, and adsorption capacity is high.
Brief description
Fig. 1 is the polypyrrole solid sulfur materials xrd figure of embodiment 1 preparation.
Fig. 2 is the polypyrrole solid sulfur materials absorption cu of embodiment 1 preparation2+Concentration is with adsorption time change curve.In 2.2 v After 10 min electrochemical treatments under voltage, copper ion concentration is reduced to 3.8 ppm, and absorption after 40 min reaches balance, to copper in water Ion concentration is 0.027 ppm, reaches drinking water standard.
Fig. 3 is the polyaniline solid sulfur materials absorption cd of embodiment 2 preparation2+Concentration is with adsorption time change curve.In 2.5 v After 10 min electrochemical treatments under voltage, absorption reach balance, in water to concentration of cadmium ions be 0.01 ppm, reach and drink water gauge Accurate.
Specific embodiment
The enforcement it is clear that described will be clearly and completely described to the technical scheme in the embodiment of the present invention below Example is only a part of embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, this area is common The every other embodiment that technical staff is obtained under not making creative work precursor, broadly falls into the model of present invention protection Enclose.
The present invention is intended to provide a kind of solid sulfur materials of conducting polymer are improving adsorption capacity, and by adjusting voltage The heavy metal ions in wastewater electrochemical process for treating controlling the rate of adsorption comprises the following steps:
(1) the solid sulfur materials of conducting polymer are prepared.Iron chloride and ferrous chloride react generation nanometer four under ammonia environment and aoxidize Three iron particles make template, add monomer, be polymerized, form conducting polymer under oxidant effect, are subsequently adding acid and go template Remove, obtain the conducting polymer materials of spherical shell shape.With ball-milling method or heat treatment method, conducting polymer and sulfur are combined, you can Obtain the solid sulfur materials of conducting polymer.
(2) prepare the solid sulfur materials electrode of conducting polymer.Upper step is reacted the solid sulfur materials of the conducting polymer obtaining and glues Knot agent mix homogeneously, solubilizer stirring forms uniform pasty state, is evenly applied on stainless steel substrates with blade applicator, is dried, and is formed The solid sulfur materials electrode of conducting polymer.
(3) electrochemical method removes heavy metal ions in wastewater.In certain density heavy metal ion solution, conductive poly- The solid sulfur materials electrode of compound is working electrode, with graphite paper as to electrode, is adsorbed under certain voltage.
Preferably, the treatment temperature of described heat treatment method is 130 ~ 200 DEG C, and the time is 5 ~ 30 hours.
According to the present invention, it is as follows that the solid sulfur materials of conducting polymer prepare concrete grammar:
30 min are stirred, Deca strong aqua ammonia adjusts ph to 9 ~ 12, in ammonia environment under iron chloride and ferrous chloride aqueous solution room temperature Lower reaction 20 ~ 120min, generates black nano ferriferrous oxide particles, is re-dispersed in water and makees template, press after being cleaned with water Ferroso-ferric oxide: the amount of polymer monomer material adds polymer monomer than for 1:1 to 1:10, is polymerized under oxidant effect, Form conducting polymer, be subsequently adding acid and template is removed, obtain the conducting polymer materials of spherical shell shape.With ball-milling method or heat Conducting polymer and sulfur are combined by processing method (130 ~ 200 DEG C), you can obtain the solid sulfur materials of conducting polymer.Reaction is obtained The solid sulfur materials of conducting polymer and binding agent (by polymer and sulfur gross mass 0.5 ~ 30%) mix homogeneously, solubilizer stirs shape Uniformly pasty state, is evenly applied on stainless steel substrates with blade applicator (30 ~ 500 μm), is dried, and forms the solid sulfur material of conducting polymer Material electrode.Configure certain density heavy metal ion solution, the solid sulfur materials electrode of conducting polymer is working electrode, uses graphite paper As to electrode, adsorbed at lower voltages.
Further, described heavy metal is one or more of ferrum, manganese, cobalt, cadmium, hydrargyrum, lead, silver, copper, zinc, arsenic, nickel.
The present invention is explained further below in conjunction with example, but embodiment does not limit in any form to the present invention.
Embodiment 1:
0.08 mol iron chloride and 0.04 mol ferrous chloride stir 30 min, Deca strong aqua ammonia under aqueous solution 400 ml room temperature Adjust ph to 10, react 30 min under ammonia environment, generate black nano ferriferrous oxide particles, again divide after being cleaned with water It is scattered in water make template, adds 2 mol pyrrole monomers, be polymerized under 4 mol iron chloride effects, form electric polypyrrole, then Add excessive hydrochloric acid to remove template, obtain the conducting polymer materials of spherical shell shape.Polypyrrole hollow ball shell and sulfur are pressed 1:1's Ratio mix homogeneously, ball milling 30 min, adds binding agent pvdf by polypyrrole and sulfur gross mass 10%, and adds solvent nmp to stir Form slurry, be evenly applied to stainless steel substrates surface with blade applicator (120 μm), after 12 h are dried, the solid sulfur materials of electric polypyrrole Electrode is working electrode, with graphite paper as to electrode, forms closed-loop path in 100 ppm copper-containing wastewaters.In 2.2 v voltages After lower 10 min electrochemical treatments, copper ion concentration is reduced to 3.8 ppm, and absorption after 40 min reaches balance, to copper ion in water Concentration is 0.027 ppm, reaches national drinking water conventional criteria.
Embodiment 2:
0.06 mol iron chloride and 0.3 mol ferrous chloride stir 30 min, Deca strong aqua ammonia under aqueous solution 200 ml room temperature Adjust ph to 11, react 30 min under ammonia environment, generate black nano ferriferrous oxide particles, again divide after being cleaned with water It is scattered in water make template, adds 2.5 mol aniline monomers, be polymerized under 2.5 mol Ammonium persulfate. effects, form conducting polyaniline Amine, is subsequently adding excess sulfuric acid and removes template, obtains the conducting polymer materials of spherical shell shape.By polyaniline hollow ball shell and sulfur In the ratio mix homogeneously of 3:7, at 150 DEG C, react 12 h, add binding agent pva by polyaniline and sulfur gross mass 25%, and plus Enter solvent dmf stirring and form slurry, be evenly applied to stainless steel substrates surface with blade applicator (70 μm), after 16 h are dried, conductive poly- The solid sulfur materials electrode of pyrroles is working electrode, with graphite paper as to electrode, forms closed-loop path in 50 ppm cadmium wastewater. After 10 min electrochemical treatments under 2.5 v voltages, absorption reach balance, in water to concentration of cadmium ions be 0.01 ppm, reach National drinking water conventional criteria.
Embodiment 3:
0.12 mol iron chloride and 0.6 mol ferrous chloride stir 30 min, Deca strong aqua ammonia under aqueous solution 200 ml room temperature Adjust ph to 11, react 30 min under ammonia environment, generate black nano ferriferrous oxide particles, again divide after being cleaned with water It is scattered in water make template, adds 2.5 mol acrylonitrile monemers, be polymerized under 3 mol potassium peroxydisulfate effects, form conducting polypropylene Nitrile, is subsequently adding excess sulfuric acid and removes template, obtains the conducting polypropylene nitrile material of spherical shell shape.By polyacrylonitrile hollow ball shell With sulfur in the ratio mix homogeneously of 7:3, at 160 DEG C, react 12 h, add binding agent ptfe by polyaniline and sulfur gross mass 25%, And add solvent nmp stirring to form slurry, it is evenly applied to stainless steel substrates surface with blade applicator (150 μm), after 14 h are dried, lead The solid sulfur materials electrode of voltolisation acrylonitrile is working electrode, with graphite paper as to electrode, leaded 1000 ppm, manganese 200 ppm, Form closed-loop path in nickel 100 ppm waste water.After 20 min electrochemical treatments under 2.5 v voltages, absorption reaches balance, in water The concentration of lead is 0.01 ppm, the concentration of manganese is 0.05 ppm, and the concentration of nickel reaches the conventional mark of national drinking water for 0.01 ppm Accurate.
Embodiment 4:
0.06 mol iron chloride and 0.03 mol ferrous chloride stir 30 min under aqueous solution 400 ml room temperature, the dense ammonia of Deca Water adjusts ph to 12, reacts 20 min under ammonia environment, generates black nano ferriferrous oxide particles, after being cleaned with water again It is distributed in water and makees template, add 2.5 mol pyrrole monomers, be polymerized under 2.5 mol sodium peroxydisulfate effects, form conductive poly- pyrrole Cough up, be subsequently adding excessive hydrochloric acid and template is removed, obtain the electric polypyrrole material of spherical shell shape.By polypyrrole hollow ball shell and sulfur In the ratio mix homogeneously of 6:4, at 200 DEG C, react 5 h, add binding agent cmc by polypyrrole and sulfur gross mass 0.5%, and plus Enter aqueous solvent stirring and form slurry, be evenly applied to stainless steel substrates surface with blade applicator (500 μm), after 12 h are dried, conductive poly- The solid sulfur materials electrode of pyrroles is working electrode, with graphite paper as to electrode, is formed in iron content, cobalt, each 100 ppm waste water of hydrargyrum Closed-loop path.After 30 min electrochemical treatments under 1.8 v voltages, in water the concentration of ferrum be 0.25 ppm, the concentration of cobalt be 0.05 ppm, the concentration of hydrargyrum is 0.0008 ppm, reaches national drinking water conventional criteria.
Embodiment 5:
0.1 mol iron chloride and 0.5 mol ferrous chloride stir 30 min under aqueous solution 200 ml room temperature, and Deca strong aqua ammonia is adjusted Section ph to 9, reacts 120 min under ammonia environment, generates black nano ferriferrous oxide particles, again disperses after being cleaned with water Make template in water, add 1.5 mol thiophene monomers, be polymerized under 1.5 mol potassium peroxydisulfate effects, form conductive polythiophene, It is subsequently adding excess sulfuric acid to remove template, obtain the conductive polythiophene material of spherical shell shape.Polythiophene hollow ball shell and sulfur are pressed The ratio mix homogeneously of 3:7, reacts 30 h at 130 DEG C, add binding agent pvdf by polythiophene and sulfur gross mass 30%, and add Solvent nmp stirring forms slurry, is evenly applied to stainless steel substrates surface with blade applicator (30 μm), after 10 h are dried, conductive poly- thiophene The solid sulfur materials electrode of fen is working electrode, with graphite paper as to electrode, shape in argentiferous, zinc, each 100 ppm waste water waste water of arsenic Become closed-loop path.After 20 min electrochemical treatments under 2.5 v voltages, absorption reaches balance, and in water, the concentration of silver is 0.03 Ppm, zinc concentration are 0.5 ppm, and the concentration of arsenic is 0.04 ppm, reaches national drinking water conventional criteria.

Claims (10)

1. the preparation method of the solid sulfur materials of conducting polymer is it is characterised in that comprise the steps:
Iron chloride and ferrous chloride react generation nano ferriferrous oxide granule under ammonia environment, are then aoxidized using nanometer four Three iron particles make template, add polymer monomer, be polymerized, form conducting polymer under oxidant effect, and being subsequently adding acid will Template removes, and obtains the conducting polymer materials of spherical shell shape；Adopt ball-milling method or heat treatment method by conducting polymer afterwards and Sulfur is combined, you can obtain the solid sulfur materials of conducting polymer.
2. the preparation method of the solid sulfur materials of conducting polymer according to claim 1 is it is characterised in that described polymer list Body is selected from pyrroles, aniline, acrylonitrile, one of thiophene.
3. the preparation method of the solid sulfur materials of conducting polymer according to claim 1 is it is characterised in that oxidant is selected from three One of iron chloride, Ammonium persulfate., potassium peroxydisulfate, sodium peroxydisulfate.
4. the preparation method of the solid sulfur materials of conducting polymer according to claim 1 is it is characterised in that described acid is selected from One of hydrochloric acid, sulphuric acid.
5. the preparation method of the solid sulfur materials of conducting polymer according to claim 1 is it is characterised in that described conducting polymer The mass ratio of thing and sulfur is 3:7 ~ 7:3.
6. in the solid sulfur materials removal of heavy metal ions in water of the conducting polymer described in claim 1 to 5 any claim Application.
7. the using method of the solid sulfur materials of conducting polymer is it is characterised in that the steps include: that the solid sulfur materials of conducting polymer are made Electrode is reacted with the heavy metal ion in water under electrochemical action, forms the metal sulfide being coated in conducting polymer, Realize the removal of heavy metal ion in water.
8. the using method of the solid sulfur materials of conducting polymer according to claim 7 is it is characterised in that described electrochemistry is made It is 0v with applied voltage, and 2.5v.
9. a kind of preparation method of electrode is it is characterised in that comprise the steps: that the solid sulfur materials of conducting polymer and binding agent mix Close uniformly, solubilizer stirring forms uniform pasty state, is evenly applied on stainless steel substrates with blade applicator, is dried, and forms electrode.
10. a kind of preparation method of electrode according to claim 9 is it is characterised in that described binding agent is polyvinylidene fluoride At least one in alkene, polyvinyl alcohol, politef, sodium carboxymethyl cellulose, polyolefin, polyurethane.
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Cited By (5)

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CN109502706A (en) * 2018-12-30 2019-03-22 太原理工大学 A kind of method that automatically controlled ion exchange material recycles metal ion in waste water
CN110624517A (en) * 2019-09-23 2019-12-31 成都先进金属材料产业技术研究院有限公司 Nano hollow polyaniline and preparation method and application thereof
CN111607085A (en) * 2020-05-27 2020-09-01 南方科技大学 Organic material, BDI system and removal method for water metal ions
CN113003701A (en) * 2021-02-08 2021-06-22 哈尔滨工业大学 Lead-zinc mine tailing pond wastewater deep purification device with electric coupling biological filter
CN114939441A (en) * 2022-04-20 2022-08-26 中联西北工程设计研究院有限公司 Light-operated ion exchange functional material and preparation method and application thereof

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