阅读说明：本技术 一种有机材料、bdi系统及用于水体金属离子的去除 (Organic material, BDI system and removal method for water metal ions ) 是由 陈洪 卫文飞 于 2020-05-27 设计创作，主要内容包括：本发明提供了一种有机材料、BDI系统及用于水体金属离子的去除,所述金属离子去除有机材料的制备方法包括：将醌类单体和硫化物置于溶剂中反应,得到所述有机材料；该有机材料为具有氧化还原官能团的有机聚合物材料,由于其非刚性的结构,不受非离子选择的限制,在不同的金属离子体系中均可发生可逆的电化学氧化还原反应,并能够与溶液中的金属离子配位形成配合物从而达到去除金属离子的目的；将该有机材料用于电化学电池离子去除(BDI)系统中,能够有效除去水体中的金属离子,且具有较高的去除容量,并能够循环使用；该BDI系统可广泛应用于海水淡化、污废水金属离子去除等领域,从而具有广阔的应用前景。(The invention provides an organic material, a BDI system and a method for removing metal ions in a water body, wherein the preparation method of the metal ion removal organic material comprises the following steps: placing the quinone monomer and the sulfide into a solvent for reaction to obtain the organic material; the organic material is an organic polymer material with redox functional groups, is not limited by non-ionic selection due to a non-rigid structure, can generate reversible electrochemical redox reaction in different metal ion systems, and can be coordinated with metal ions in a solution to form a complex so as to achieve the purpose of removing the metal ions; the organic material is used in an electrochemical cell ion removal (BDI) system, can effectively remove metal ions in a water body, has high removal capacity and can be recycled; the BDI system can be widely applied to the fields of seawater desalination, sewage and wastewater metal ion removal and the like, thereby having wide application prospect.)

1. A method for preparing an organic material, comprising: and (3) placing the quinone monomer and the sulfide into a solvent for reaction to obtain the organic material.

2. The method according to claim 1, wherein the quinone monomer comprises any one or a combination of at least two of naphthoquinone, phenanthrenequinone, anthraquinone, or benzoquinone substituted with amino group and/or halogen;

preferably, the quinone monomer comprises any one or a combination of at least two of 2, 6-diaminoquinone, 2, 4-dichloroanthraquinone, 1, 5-dichloroanthraquinone, tetrachlorobenzoquinone or dichlorohydroquinone;

preferably, the sulfide comprises lithium sulfide and/or sodium sulfide;

preferably, the solvent comprises any one of tetrahydrofuran, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide or dimethylacetamide, or a combination of at least two thereof;

preferably, the mass ratio of the quinone monomer to the sulfide is (0.5-1) to (1-3);

preferably, the reaction temperature is 160-250 ℃, and the reaction time is 3-10 h;

preferably, the preparation method further comprises sequentially separating, cleaning and drying reactants obtained after the reaction;

preferably, the separation comprises filtering the reactant obtained after the reaction, and removing the filtrate to obtain a solid precipitate;

preferably, the washing comprises washing with a mixture of water and ethanol.

3. The organic material prepared by the preparation method according to claim 1 or 2;

preferably, the organic material is a porous structure, the size of the pore channel of the porous structure is 2-40nm, and the pore volume of the porous structure is 0.1-0.15cm³/g；

Preferably, the organic material has a number average molecular weight of 5 to 10 ten thousand;

preferably, the content of sulphur in the organic material is between 10 and 16 wt%.

4. An electrode paste, characterized in that the electrode paste comprises the organic material according to claim 3;

preferably, the organic paste further includes a conductive agent, a binder, and a solvent;

preferably, the preparation method of the electrode slurry comprises: dissolving an organic material, a conductive agent and a binder in a solvent, and mixing to obtain the electrode slurry;

preferably, the conductive agent includes acetylene black and/or carbon nanotubes;

preferably, the binder is polyvinylidene fluoride and/or polytetrafluoroethylene;

preferably, the solvent is ethanol and/or N-methylpyrrolidone;

preferably, the mixing is carried out under stirring conditions;

preferably, the mixing rate is 300-.

5. An electrode sheet, characterized in that the electrode sheet comprises a current collector and an electrode slurry layer arranged on the surface of the current collector, wherein the electrode slurry used for the electrode slurry layer is the electrode slurry of claim 4;

preferably, the current collector comprises any one of stainless steel, carbon cloth or carbon paper;

preferably, the thickness of the electrode paste layer is 0.5-1.5 μm;

preferably, the preparation method of the electrode plate comprises the steps of coating electrode slurry on the surface of a current collector, and curing to obtain the electrode plate;

preferably, the coating is knife coating.

6. A BDI system, characterized in that the BDI system comprises a working electrode and a counter electrode, wherein the working electrode is the electrode slice of claim 5;

preferably, the counter electrode is selected from any one or a combination of at least two of a carbon-based material, a bismuth-based material, a silver-based material or an aluminum-based material;

preferably, the counter electrode is selected from any one or a combination of at least two of activated carbon, mesoporous carbon, carbon nanotubes, bismuth oxychloride, elemental bismuth, bismuth oxide or silver chloride.

7. Use of a BDI system according to claim 6 for removing metal ions from a body of water;

preferably, the metal ions include any one or a combination of at least two of sodium ions, magnesium ions, potassium ions, calcium ions, chromium ions, cobalt ions, nickel ions, copper ions, zinc ions, lead ions, cadmium ions, or mercury ions.

8. An electrochemical metal ion removal system comprising a cycling test device and the BDI system of claim 6.

9. Use of an electrochemical metal ion removal system according to claim 8 for removing metal ions from a body of water;

preferably, the metal ions include any one or a combination of at least two of sodium ions, magnesium ions, potassium ions, calcium ions, chromium ions, cobalt ions, nickel ions, copper ions, zinc ions, lead ions, cadmium ions, or mercury ions;

preferably, the water body includes any one of river water, sea water, drinking water or industrial wastewater.

10. The application according to claim 9, wherein the application comprises: under the action of a test voltage of a circulating test device, firstly removing target ions in a water body by using a BDI system, secondly calculating the removal capacity of the metal ions according to the concentration of the metal ions in the water body and charge transfer in an electrochemical reaction process, and then adjusting the arrangement of a working electrode and a counter electrode in the BDI system according to the removal capacity, so that the metal ions in the water body are removed to the maximum extent;

preferably, the concentration of metal ions in the water body is 50-50000 ppm;

preferably, the working voltage of the BDI system is-3V, and the working current density is 20-2000 mA/g;

preferably, the mass ratio of the working electrode to the counter electrode in the BDI system is (1-0.5): (1-2).

Technical Field

The invention belongs to the field of electrochemistry, relates to an organic material, a BDI system and a method for removing water body metal ions, in particular to the organic material, a preparation method thereof, the BDI system comprising the organic material and application thereof in removing the water body metal ions; further relates to an organic polymer material, electrode slurry, an electrode plate and an application of the electrochemical metal ion removal system in a seawater and sewage metal ion removal system.

Background

Water is a basic substance on which human beings rely to live, and with the rapid development of economy in China, the problems of shortage of fresh water resources and heavy metal water pollution are gradually highlighted. The method can effectively solve the problems of shortage of fresh water resources and heavy metal water pollution by removing ions from seawater and heavy metal sewage through a proper technical method, and accelerate ecological civilization construction in China and improvement of quality of life of people. The seawater desalination needs to remove metal ions such as sodium ions, magnesium ions, potassium ions, calcium ions and the like in the seawater. The heavy metal pollution of the water body mainly comes from electroplating industry, machining, mining, nonferrous metal smelting and the like, and mainly comprises chromium ions, cobalt ions, nickel ions, copper ions, zinc ions, arsenic ions, lead ions, cadmium ions, mercury ions and the like. The existing seawater desalination technologies (electrodialysis, reverse osmosis, distillation and the like) and heavy metal sewage treatment technologies (adsorption, coprecipitation, biological absorption and the like) have defects in the aspects of cost, energy consumption, secondary pollution, metal ion removal diversity and the like.

The electrochemical metal ion removal technology has the advantages of low energy consumption, high capacity, no secondary pollution of electrons, recyclability and the like, and has good application prospect in the aspect of removing capacitive and bulk phase Faraday electrochemical metal ions. However, the electrochemical method for removing ions by electric double layer capacitance type reported in 1966 has a problem of low metal ion removal capacity due to the limitation of the specific surface area of the electrode material and the pore structure. The battery-type ion removal technology (BDI) proposed in 2012 is based on the bulk phase reaction of faraday electrochemical reaction, and has the advantage of high metal ion removal capacity. However, the inorganic materials currently used in such technologies have the problem of ion removal unity, and are only suitable for removing sodium ions.

Therefore, the electrochemical metal ion removal system which can simultaneously remove a plurality of metal ions and has high removal capacity is provided, and has important application value for removing metal ions in sewage, seawater desalination, drinking water and the like.

Disclosure of Invention

Aiming at the defects of low metal ion removal capacity and ion removal unicity in the prior art, the invention aims to provide an organic material, a BDI system and a method for removing metal ions in a water body, wherein the organic material is an organic polymer material with redox functional groups, can generate reversible electrochemical redox reaction in different metal ion systems due to a non-rigid structure without being limited by non-ion selection, and can be coordinated with metal ions in a solution to form a complex so as to achieve the purpose of removing the metal ions; the BDI system mainly comprises a polymer working electrode for removing metal ions and a counter electrode for removing anions, can be widely applied to the fields of seawater desalination, metal ion removal of sewage and wastewater and the like, and has wide application prospect.

One of the purposes of the invention is to provide a preparation method of a polymer active material for removing metal ions in a water body, and the preparation method of the organic material comprises the following steps: and (3) placing the quinone monomer and the sulfide into a solvent for reaction to obtain the organic material.

The preparation method of the organic material is simple, the raw materials are easy to obtain, the price is low, the realization is easy, and the industrial large-scale production and application are facilitated.

In the present invention, the quinone monomer includes any one or a combination of at least two of naphthoquinone, phenanthrenequinone, anthraquinone, or benzoquinone substituted with amino group and/or halogen.

In the present invention, the quinone monomer includes any one or a combination of at least two of 2, 6-diaminoquinone, 2, 4-dichloroanthraquinone, 1, 5-dichloroanthraquinone, tetrachlorobenzoquinone and dichlorohydroquinone.

In the present invention, the sulfide includes lithium sulfide and/or sodium sulfide.

In the present invention, the solvent includes any one of tetrahydrofuran, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, or dimethylacetamide, or a combination of at least two thereof.

In the present invention, the mass ratio of the quinone monomer to the sulfide is (0.5-1): 1-3, for example, 0.5:3, 0.6:2.5, 0.7:2, 0.8:1.5, 0.9:1, 1:1, etc.

In the present invention, the reaction temperature is 160-.

In the invention, the preparation method further comprises the steps of separating, cleaning and drying reactants obtained after the reaction in sequence.

In the invention, the separation comprises filtering the reactant obtained after the reaction, and removing the filtrate to obtain solid precipitate.

In the present invention, the washing includes washing with a mixture of water and ethanol.

The second object of the present invention is to provide an organic material prepared by the preparation method according to the first object.

The organic material obtained by the invention is an organic polymer material with redox functional groups, and due to the non-rigid structure, the organic material is not limited by non-ionic selection, reversible electrochemical redox reaction can be generated in different metal ion systems, and the organic material can be coordinated with metal ions in a solution to form a complex, so that the aim of removing the metal ions is fulfilled.

In the present invention, the active material is a porous structure having a pore size of 2 to 40nm (e.g., 2nm, 5nm, 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, etc.), and having a pore volume of 0.1 to 0.15cm³/g。

The active material is of a porous structure, can realize rapid hydrated ion transmission, has a large specific surface area, and is beneficial to solution infiltration.

In the present invention, the number average molecular weight of the organic material is 5 to 10 ten thousand, for example, 5 ten thousand, 6 ten thousand, 7 ten thousand, 8 ten thousand, 9 ten thousand, 10 ten thousand, or the like.

In the present invention, the content of sulfur in the organic material is 10 to 16 wt%, for example, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, etc.

It is a third object of the present invention to provide an electrode paste comprising the organic material of the second object.

In the present invention, the active paste further includes a conductive agent, a binder, and a solvent.

In the present invention, the conductive agent includes acetylene black and/or carbon nanotubes.

In the invention, the binder is polyvinylidene fluoride and/or polytetrafluoroethylene.

In the present invention, the solvent is ethanol and/or N-methylpyrrolidone.

In the present invention, the preparation method of the electrode slurry comprises: and dissolving the organic material, the conductive agent and the binder in a solvent, and mixing to obtain the electrode slurry.

In the present invention, the mixing is performed under stirring conditions.

In the present invention, the mixing rate is 300-800rpm (e.g., 300rpm, 350rpm, 400rpm, 450rpm, 500rpm, 550rpm, 600rpm, 650rpm, 700rpm, 750rpm, 800rpm, etc.), and the mixing time is 1-5h (e.g., 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, etc.).

The fourth object of the present invention is to provide an electrode sheet comprising a current collector and an electrode slurry layer provided on the surface of the current collector, wherein the electrode slurry layer is the electrode slurry of the third object.

In the present invention, the current collector includes any one of stainless steel, carbon cloth, or carbon paper.

In the present invention, the thickness of the electrode paste layer is 0.5 to 1.5. mu.m, for example, 0.5. mu.m, 0.6. mu.m, 0.7. mu.m, 0.8. mu.m, 0.9. mu.m, 1. mu.m, 1.1. mu.m, 1.2. mu.m, 1.3. mu.m, 1.4. mu.m, 1.5. mu.m, etc.

In the preparation method of the electrode plate, the electrode slurry is coated on the surface of a current collector and solidified to obtain the electrode plate.

In the invention, the coating mode is knife coating.

In the present invention, the curing temperature is 60 to 100 ℃ (e.g., 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃ and the like), and the curing time is 8 to 12 hours (e.g., 8 hours, 8.5 hours, 9 hours, 9.5 hours, 10 hours, 10.5 hours, 11 hours, 11.5 hours, 12 hours and the like).

The fifth purpose of the present invention is to provide a BDI system, which comprises a working electrode and a counter electrode, wherein the working electrode is the electrode sheet described in the fourth purpose, and the counter electrode is selected from any one or a combination of at least two of a carbon-based material, a bismuth-based material, a silver-based material, and an aluminum-based material.

Preferably, the counter electrode and the reference electrode are respectively and independently selected from any one or a combination of at least two of activated carbon, mesoporous carbon, carbon nanotubes, bismuth oxychloride, elemental bismuth, bismuth oxide or silver chloride.

In the invention, the working electrode of the BDI system is used for removing metal ions in the aqueous solution, and the counter electrode is used for removing anions in the aqueous solution.

The BDI system comprises organic materials, the organic materials can generate reversible electrochemical redox reaction in different metal ion systems, and can be coordinated with metal ions in a solution to form a complex, so that the aim of removing the metal ions is fulfilled, the BDI system has high removal capacity, and the BDI system can be recycled.

In the present invention, the metal ions include any one or a combination of at least two of sodium ions, magnesium ions, potassium ions, calcium ions, chromium ions, cobalt ions, nickel ions, copper ions, zinc ions, arsenic ions, lead ions, cadmium ions, or mercury ions.

The sixth purpose of the present invention is to provide an electrochemical metal ion removal system, which comprises the BDI system described in the fifth purpose.

The seventh purpose of the present invention is to provide an application of the electrochemical metal ion removal system described in the sixth purpose in removing metal ions in a water body.

In the present invention, the metal ions include any one or a combination of at least two of sodium ions, magnesium ions, potassium ions, calcium ions, chromium ions, cobalt ions, nickel ions, copper ions, zinc ions, arsenic ions, lead ions, cadmium ions, or mercury ions.

In the present invention, the water body includes any one of river water, sea water, drinking water or industrial wastewater.

In the present invention, the application includes: the method comprises the steps of removing target ions in a water body through a BDI system, calculating the removal capacity of metal ions according to the concentration of the metal ions in the water body or charge transfer in an electrochemical reaction process, and adjusting the arrangement of a working electrode and a counter electrode in the BDI system through the removal capacity of the metal ions, so that the metal ions in the water body are removed.

Preferably, the concentration of metal ions in the body of water is 50-50000ppm, such as 50ppm, 1000ppm, 3000ppm, 5000ppm, 8000ppm, 10000ppm, 20000ppm, 30000ppm, 40000ppm, 50000ppm and the like.

The concentration of the metal ions in the present invention refers to the total concentration of the metal ions in the water body.

Preferably, the BDI system has an operating voltage of-3 to 3V (such as-3V, -2V, -1V, 0V, 1V, 2V, 3V and the like) and an operating current density of 20 to 2000mA/g (such as 20mA/g, 50mA/g, 100mA/g, 300mA/g, 500mA/g, 800mA/g, 1000mA/g, 1200mA/g, 1500mA/g, 1800mA/g, 2000mA/g and the like).

In the present invention, the mass ratio of the working electrode to the counter electrode in the BDI system is (1-0.5): 1-2, such as 1:1, 0.9:1.2, 0.8:1.4, 0.7:1.6, 0.6:1.8, 0.5:2, etc.

Compared with the prior art, the invention has the following beneficial effects:

the organic material is an organic polymer material with redox functional groups, is not limited by non-ionic selection due to a non-rigid structure, can generate reversible electrochemical redox reaction in different metal ion systems, and can be coordinated with metal ions in a solution to form a complex so as to achieve the purpose of removing the metal ions; the organic material is used in an electrochemical metal ion removal system, can effectively remove metal ions in a water source, has high removal capacity (the removal capacity of the metal ions can reach 120mg/g for the total concentration of the metal ions in a water body of 50-50000 ppm), and can be recycled; the BDI system mainly comprises a polymer working electrode for removing metal ions and a counter electrode for removing anions, and can be widely applied to the fields of seawater desalination, metal ion removal of sewage and wastewater and the like, so that the BDI system has a wide application prospect.

Drawings

FIG. 1 is a scanning electron microscope photograph of the polymeric quinone-based active material obtained in example 1, with a scale of 1 μm;

FIG. 2 shows the polymeric quinone active material N obtained in example 1₂Adsorption-desorption curve chart;

fig. 3 is an electrochemical cycling test chart of the electrochemical metal ion removal system for removing metal ions in an aqueous solution in example 1.

Detailed Description

The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.