Low-dimensional carbon / nitride adsorption material for enriching silver resource in silver electrolysis waste liquid as well as preparation method and application of low-dimensional carbon / nitride adsorption material

Abstract

The embodiment of the invention discloses a low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid as well as a preparation method and an application of the low-dimensional carbon / nitride adsorption material. The method comprises the following steps: arranging a titanium mesh as a substrate in a reactor, and regulating a reaction atmosphere into an inert atmosphere; argon is used as carrier gas to carry TiCl4 gas as a titanium source; methane, nitrogen or mixed gas of methane and nitrogen is used as a carbon source, a nitrogen source or a carbon-nitrogen source; under the coupling action of titanium halide gaseous salt and methane / nitrogen, a low-dimensional carbon / nitride adsorption material is obtained on the surface of a titanium mesh substrate through combined promotion of chemical vapor deposition and a self-consumption reaction, surface functional group functionalization is further achieved in an aqueous medium through ligand exchange of a nano-structure micro-interface, and the low-dimensional carbon / nitride adsorption material is obtained. The hydrophilic low-dimensional carbon / nitride adsorption material is obtained; the hydrophilic low-dimensional carbon / nitride adsorption material generated on the titanium mesh can simultaneously adsorb silver ions and silver microparticles in the solution, is good in selectivity and high in adsorption efficiency, and has a good application prospect in the aspects of resource treatment and subsequent sewage treatment of the silver-containing solution.

Description

Technical Field

[0001] The invention belongs to the technical field of new materials, and in particular relates to a low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid, a preparation method and an application thereof. Background Art

[0002] High-purity nonferrous metals are an important type of material with a wide range of application value, and silver is one of the typical representatives. The purity of silver determines the level of application performance. The higher the purity, the lower the impurities, and the higher the performance of the material. With the advancement of metal purification technology, the purity of high-purity silver metal used in various high-end fields has gradually transitioned from 4N to 5N and 6N, and even reached 7N in some application fields such as electronic semiconductors.

[0003] At present, the production of high-purity silver mainly adopts the electrolytic refining process. Silver ions are precipitated at the cathode after passing through the electrolyte, and the resulting silver electrolysis production waste liquid contains a large amount of metallic silver. Copper replacement method and sodium hydroxide neutralization method are currently the silver recovery processes commonly used by enterprises, but the recovered silver particles are seriously affected by the environment. When the concentration of reactants in the solution is as low as a certain value, its reaction rate approaches zero, and the generated metallic silver particles are also extremely small, making it difficult to recover silver resources in the terminal silver electrolysis wastewater.

[0004] Michaelis includes transition metal carbides, nitrides, carbonitrides, etc. It is a typical two-dimensional quasi-layered structure compound with huge surface area, electrical and thermal conductivity, stability, etc. It can form a uniform dispersion in the solvent. It has broad application potential as an adsorption material. It can effectively recycle silver particles and anions, and also has great application potential in the adsorption of heavy metals in environmental governance.

[0005] However, the current preparation process of michalcone usually uses etching to remove intercalated atoms in the MAX phase, and immerses the MAX material in hydrofluoric acid or other highly active solutions for dozens of hours. This chemical process is time-consuming and produces a large amount of hazardous waste, which increases costs and environmental pollution. Summary of the invention

[0006] In view of this, some embodiments disclose a method for preparing a low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid, comprising:

[0007] A titanium mesh is arranged in the reactor as a substrate, and the reaction atmosphere in the reactor is adjusted to an inert atmosphere;

[0008] Argon is used as a carrier gas to carry TiCl4 gas as a titanium source into the reactor;

[0009] Using methane or a mixture of methane and nitrogen as a carbon source or a carbon-nitrogen source to enter the reactor;

[0010] On the substrate surface, a carbon source or a carbon-nitrogen source reacts with a titanium source under set conditions to generate low-dimensional carbon / nitride; wherein the reaction temperature is set to 600-1000° C., and the reaction time is set to 5-60 min;

[0011] The obtained low-dimensional carbon / nitride adsorption material is subjected to surface hydrophilic modification to obtain a low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid.

[0012] Furthermore, some embodiments disclose a method for preparing a low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid, using methane as a carbon source to react with a titanium source to generate low-dimensional carbides; wherein the flow rate of methane is 10 to 1000 sccm.

[0013] Some embodiments disclose a method for preparing a low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid, which utilizes a mixed gas of methane and nitrogen as a carbon and nitrogen source to react with a titanium source to generate a low-dimensional carbon / nitride, wherein the low-dimensional carbon / nitride is composed of carbides, carbonitrides and nitrides; wherein the flow rate of the mixed gas is 10 to 1000 sccm, and the volume ratio of CH4 to N2 is greater than 5:1.

[0014] Some embodiments disclose a method for preparing a low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid, using nitrogen as a nitrogen source to react with a titanium source to generate a low-dimensional nitride; wherein the flow rate of the nitrogen is 10 to 1000 sccm.

[0015] Some embodiments disclose a method for preparing a low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid, wherein the method uses argon as a carrier gas to carry TiCl4 gas as a titanium source, including:

[0016] The TiCl4 salt is placed in a sealed container, wherein the air inlet of the sealed container is connected to an argon gas source, and the air outlet of the sealed container is connected to a reactor;

[0017] Place the sealed container in a water bath and heat to the set temperature;

[0018] The argon source is adjusted to provide a set flow rate of argon. The TiCl4 salt is heated and vaporized into gaseous TiCl4 at a set temperature, and forms a mixed gas with the argon gas to enter the reactor as a titanium source.

[0019] Some embodiments disclose a method for preparing a low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid, including a pretreatment method of a titanium mesh, specifically comprising:

[0020] A titanium mesh with a pore size of 500 to 2000 meshes is cleaned with dilute acid, alcohol and deionized water in sequence to obtain a pretreated titanium mesh; wherein the dilute acid includes dilute hydrochloric acid, dilute hydrofluoric acid, dilute sulfuric acid and dilute nitric acid.

[0021] Some embodiments disclose a method for preparing a low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid, wherein the obtained low-dimensional carbon / nitride adsorption material is subjected to surface hydrophilic modification using hydrofluoric acid, hydrochloric acid or lithium hydroxide aqueous solution to form hydroxyl and carboxyl hydrophilic functional groups on the surface of the low-dimensional carbon / nitride adsorption material.

[0022] Some embodiments disclose a method for preparing a low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid, wherein the flow rate of argon gas carrying TiCl4 gas is set to 10-200 sccm, and the temperature of heating a closed container to form TiCl4 gas is set to 70°C.

[0023] On the other hand, some embodiments disclose a low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid, which is obtained by a preparation method of a low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid. The low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid is a hydrophilic low-dimensional carbon / nitride adsorption material generated on the surface of a titanium mesh.

[0024] On the other hand, some embodiments disclose the use of a low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid, wherein the low-dimensional carbon / nitride adsorption material is used to enrich silver in the solution, specifically comprising:

[0025] The hydrophilic low-dimensional carbon / nitride adsorption material generated on the surface of the titanium mesh is arranged in a solution treatment device;

[0026] The silver-containing solution is input into the solution treatment device, and the low-dimensional carbon / nitride adsorption material enriches the silver in the solution; the silver is enriched on the low-dimensional carbon / nitride adsorption material. Usually, the silver-containing solution contains silver ions and silver microparticles. Usually, the silver ions or silver microparticles are positively charged and will spontaneously undergo electrostatic adsorption and chemical adsorption with the hydrophilic functional groups on the surface of the low-dimensional carbon / nitride adsorption material to achieve the enrichment of silver ions and silver microparticles and the recovery of silver resources.

[0027] The method for preparing a low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid disclosed in an embodiment of the present invention uses a titanium mesh as a substrate, and under the coupling action of titanium halide gaseous salt and methane, nitrogen or methane / nitrogen, a low-dimensional carbon / nitride adsorption material is obtained on the surface of the titanium mesh substrate through chemical vapor deposition and self-consumption reaction. The surface functional group is further functionalized by ligand exchange at a nanostructured microinterface in an aqueous medium to obtain a hydrophilic low-dimensional carbon / nitride adsorption material. The hydrophilic low-dimensional carbon / nitride adsorption material generated on the titanium mesh can simultaneously adsorb silver ions and silver microparticles in the solution, and has good selectivity and high adsorption efficiency, and has good application prospects in the resource disposal of solutions containing silver resources and subsequent sewage treatment. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 This is a flow chart of the method for preparing a low-dimensional carbon / nitride adsorption material for enriching silver disclosed in Example 1;

[0029] Figure 2 Schematic diagram of the growth mechanism of the low-dimensional carbon / nitride adsorption material for silver enrichment disclosed in Example 1;

[0030] Figure 3 This is a schematic diagram of the device composition disclosed in Example 2;

[0031] Figure 4 This is a TEM image of the low-dimensional carbide adsorption material for enriching silver disclosed in Example 5. DETAILED DESCRIPTION

[0032] The word "embodiment" used herein as an "exemplary" does not necessarily mean that any embodiment described is superior or better than other embodiments. Performance index tests in the embodiments of the present invention are performed using conventional test methods in the art unless otherwise specified. It should be understood that the terms described in the embodiments of the present invention are only used to describe specific implementation methods and are not intended to limit the contents disclosed in the embodiments of the present invention.

[0033] Unless otherwise specified, the technical and scientific terms used herein have the same meanings as commonly understood by ordinary technicians in the technical field to which the embodiments of the present invention belong; other experimental methods and technical means not specifically specified in the embodiments of the present invention refer to experimental methods and technical means commonly used by ordinary technicians in the field.

[0034] The terms "substantially" and "approximately" used herein are used to describe small fluctuations. For example, they can refer to less than or equal to ±5%, such as less than or equal to ±2%, such as less than or equal to ±1%, such as less than or equal to ±0.5%, such as less than or equal to ±0.2%, such as less than or equal to ±0.1%, such as less than or equal to ±0.05%. The numerical data represented or presented in the range format herein are used only for convenience and brevity, and should therefore be flexibly interpreted as including not only the values ​​clearly listed as the limits of the range, but also all independent values ​​or sub-ranges contained in the range. For example, the numerical range of "1-5%" should be interpreted as including not only the clearly listed values ​​of 1% to 5%, but also the independent values ​​and sub-ranges within the range shown. Therefore, independent values ​​such as 2%, 3.5% and 4% and sub-ranges such as 1%-3%, 2%-4% and 3%-5% are included in this numerical range. This principle also applies to the range of only one numerical value. In addition, such an interpretation applies regardless of the width of the range or the characteristics described.

[0035] In this document, including in the claims, transitional words such as "comprises," "includes," "with," "having," "containing," "involving," "accommodating," etc. are understood to be open-ended, i.e., meaning "including but not limited to." Only the transitional words "consisting of" and "composed of" are closed transitional words.

[0036] In order to better illustrate the present invention, numerous specific details are provided in the specific examples below. It should be understood by those skilled in the art that the present invention can be implemented without certain specific details. In the embodiments, some methods, means, instruments, equipment, etc. well known to those skilled in the art are not described in detail in order to highlight the gist of the present invention.

[0037] Under the premise of no conflict, the technical features disclosed in the embodiments of the present invention may be arbitrarily combined, and the resulting technical solutions belong to the contents disclosed in the embodiments of the present invention.

[0038] In some embodiments, a method for preparing a low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid comprises:

[0039] A titanium mesh is arranged in the reactor as a substrate, and the reaction atmosphere in the reactor is adjusted to an inert atmosphere;

[0040] Argon is used as a carrier gas to carry TiCl4 gas as a titanium source into the reactor;

[0041] Methane or a mixture of methane and nitrogen is used as a carbon source or a carbon-nitrogen source to enter the reactor; generally, a carbon source refers to a raw material containing carbon, such as methane, a nitrogen source refers to a raw material containing nitrogen, such as nitrogen, and a carbon-nitrogen source refers to a raw material containing carbon and nitrogen, such as a mixture of methane and nitrogen; generally, different reaction raw materials result in different compositions of the obtained low-dimensional carbon / nitride;

[0042] The carbon source or carbon-nitrogen source reacts with the titanium source on the substrate surface under set conditions to generate low-dimensional carbon / nitride; usually low-dimensional carbon / nitride refers to michelene generated on the surface of the titanium substrate. Michelene usually includes three types: carbides, nitrogen carbides and nitrides, and the surface functional groups of the three types of michelene are all -Cl. Usually the type of compound that makes up michelene is related to the reaction raw materials; for example, methane is used as a carbon source to react on a titanium substrate to generate two-dimensional carbon / nitride, and nitrogen and methane gas are mixed as carbon and nitrogen sources to react on a titanium substrate to generate two-dimensional carbides, two-dimensional carbonitrides and two-dimensional nitrides;

[0043] Generally, during the reaction of the reaction raw materials on the surface of the titanium substrate, TiCl4 gas and the carbon source, nitrogen source or carbon-nitrogen source converge on the surface of the titanium substrate, undergo cracking and phase reconstruction, and react to generate low-dimensional carbon / nitride adsorption materials that are deposited on the substrate surface, forming a two-dimensional array of low-dimensional carbon / nitride adsorption materials on the substrate surface; at the same time, the cracking products of the low-dimensional carbon / nitride also react with the surface of the titanium substrate, and the titanium substrate also participates in the generation reaction of the low-dimensional carbon / nitride as a carbon source;

[0044] The obtained low-dimensional carbon / nitride adsorption material is subjected to surface hydrophilic modification to obtain a low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid.

[0045] Some embodiments disclose a method for preparing a low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid, wherein the obtained low-dimensional carbon / nitride adsorption material is subjected to surface hydrophilic modification using hydrofluoric acid, hydrochloric acid or lithium hydroxide aqueous solution to form hydroxyl and carboxyl hydrophilic functional groups on the surface of the low-dimensional carbon / nitride adsorption material.

[0046] Some embodiments disclose a method for preparing a low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid, using methane as a carbon source to react with a titanium source to generate low-dimensional carbides, wherein the flow rate of methane is 10 to 1000 sccm.

[0047] Some embodiments disclose a method for preparing a low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid, using nitrogen as a nitrogen source to react with a titanium source to generate a low-dimensional nitride, wherein the flow rate of methane is 10 to 1000 sccm.

[0048] Some embodiments disclose a method for preparing a low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid, which utilizes a mixed gas of methane and nitrogen as a carbon and nitrogen source to react with a titanium source to generate a low-dimensional carbon / nitride, wherein the low-dimensional carbon / nitride is composed of carbides, carbonitrides and nitrides; wherein the flow rate of the mixed gas is 10 to 1000 sccm, and the volume ratio of CH4 to N2 is greater than 5:1.

[0049] Some embodiments disclose a method for preparing a low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid, wherein the method uses argon as a carrier gas to carry TiCl4 gas as a titanium source, including:

[0050] The TiCl4 salt is placed in a sealed container, wherein the air inlet of the sealed container is connected to an argon gas source, and the air outlet of the sealed container is connected to a reactor;

[0051] Place the sealed container in a water bath and heat to the set temperature;

[0052] The argon source is adjusted to provide a set flow rate of argon gas, and the TiCl4 salt is heated and vaporized into gaseous TiCl4 at a set temperature, and forms a mixed gas with the argon gas to enter the reactor as a titanium source. In some embodiments, the flow rate of the argon gas carrying the TiCl4 gas is set to 10-200 sccm, and the temperature of the closed container to form the TiCl4 gas is set to 70°C;

[0053] Some embodiments disclose a method for preparing a low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid, including a pretreatment method of a titanium mesh, specifically comprising:

[0054] A titanium mesh with a pore size of 500 to 2000 meshes is cleaned with dilute acid, alcohol and deionized water in sequence to obtain a pretreated titanium mesh; wherein the dilute acid includes dilute hydrochloric acid, dilute hydrofluoric acid, dilute sulfuric acid and dilute nitric acid.

[0055] Some embodiments disclose a method for preparing a low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid, wherein the set conditions for the reaction of a carbon source or a carbon-nitrogen source with a titanium source include: a reaction temperature of 600 to 1000° C. and a reaction time of 5 to 60 min.

[0056] On the other hand, some embodiments disclose a low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid, which is obtained by a preparation method of a low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid. The low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid is a hydrophilic low-dimensional carbon / nitride adsorption material generated on the surface of a titanium mesh.

[0057] On the other hand, some embodiments disclose the use of a low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid, wherein the low-dimensional carbon / nitride adsorption material is used to enrich silver in the solution, specifically comprising:

[0058] The hydrophilic low-dimensional carbon / nitride adsorption material generated on the surface of the titanium mesh is arranged in a solution treatment device;

[0059] The solution containing silver is input into the solution treatment device, and the low-dimensional carbon / nitride adsorption material enriches the silver in the solution; the silver is enriched on the low-dimensional carbon / nitride adsorption material.

[0060] The technical details are further illustrated below in conjunction with embodiments.

[0061] Example 1

[0062] Figure 1 The present invention is a flow chart of the preparation method of the low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid disclosed in Example 1.

[0063] In Example 1, the preparation method of the low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid includes:

[0064] pre-treating the titanium mesh to obtain a reaction substrate;

[0065] The pretreated titanium mesh is placed in a reactor as a reaction substrate, and the reaction atmosphere in the reactor is replaced and adjusted to an inert atmosphere using argon gas;

[0066] Argon is used as a carrier gas to carry TiCl4 gas as a titanium source into the reactor;

[0067] Using methane or a mixture of methane and nitrogen as a carbon source or a carbon-nitrogen source to enter the reactor;

[0068] adjusting and raising the temperature of the reactor to the reaction temperature;

[0069] A carbon source, a nitrogen source or a carbon-nitrogen source reacts with a titanium source on a reaction substrate in a reactor to generate low-dimensional carbon / nitride;

[0070] The obtained low-dimensional carbon / nitride adsorption material is subjected to surface hydrophilic modification to obtain a low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid.

[0071] like Figure 2The figure shows the growth mechanism of low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid; in the method disclosed in Example 1, TiCl4 gas and carbon source or carbon-nitrogen source converge on the surface of titanium substrate, undergo cracking and phase reconstruction process, react to generate low-dimensional carbon / nitride adsorption material and deposit it on the substrate surface, and reaction zone and two-dimensional array area are distributed on the substrate surface from bottom to top; the titanium substrate also participates in the generation reaction of low-dimensional carbon / nitride as a carbon source, and the cracking products of low-dimensional carbon / nitride are in-situ etched on the surface of titanium substrate to form dense grains, and solid-phase diffusion is carried out with titanium mesh matrix as the reaction proceeds, and the titanium resources diffused or decomposed in gas phase will start to grow in a directional manner with the grains on the surface of titanium mesh as the initial site to form a sheet-like or flower-ball-like array; after the reaction is completed, a two-dimensional array of low-dimensional carbon / nitride adsorption material is formed on the substrate surface.

[0072] The low-dimensional carbon / nitride adsorption material formed on the surface of the titanium mesh substrate is further used as an adsorption medium of a solution treatment device. The silver solution or silver electrolysis waste liquid is treated by the solution treatment device, and the silver ions and silver particles in the silver solution or silver electrolysis waste liquid can be enriched on the adsorption material by chemical adsorption or electrostatic adsorption, thereby realizing the recovery of silver resources in the silver solution or silver electrolysis waste liquid.

[0073] Example 2

[0074] Example 2 discloses a device for preparing low-dimensional carbon / nitride; Figure 3 As shown, the device comprises:

[0075] Reactor 4, which is a cylindrical container with one end open and the other end closed, and a heater 5 is sleeved on the closed end of reactor 4; a port plug is provided at the open end of reactor 4, and two inlet pipes and an exhaust pipe are provided in the port plug, and the ends of the inlet pipe and the exhaust pipe extend to the vicinity of the bottom of the closed end of reactor 4; reactor 4 is placed horizontally, which is conducive to the reaction gas entering from the inlet pipe entering the bottom of reactor 4, forming a stable and uniform reaction atmosphere at the bottom, and reacting on the titanium mesh substrate provided at the bottom of reactor 4;

[0076] A TiCl4 source is arranged in a heating container, and the heating container is provided with an air inlet pipe and an air outlet pipe; one end of the air inlet pipe is arranged to be connected with a first three-way valve 1, and the other end of the air inlet pipe is arranged inside the TiCl4 source in the heating container, one end of the air outlet pipe is located above the liquid level of the TiCl4 source inside the heating container, and the other end of the air outlet pipe is arranged to be connected with a second three-way valve 2; the first three-way valve 1 and the second three-way valve 2 are connected with each other; the heating container is a container capable of water bath heating, and is used to place TiCl4;

[0077] An argon gas source is arranged to be connected to the first three-way valve 1; a second three-way valve 2 is arranged to be connected to an air inlet pipe of the reactor 4;

[0078] Nitrogen source;

[0079] a methane gas source; a nitrogen source and a methane gas source are connected to a third three-way valve 3, and the third three-way valve 3 is connected to another air inlet pipe of the reactor 4;

[0080] The tail gas pipe of the reactor 4 is connected to the cooling physical precipitation washing bottle 6 and the chemical absorption washing bottle 7 in sequence;

[0081] Among them, argon gas enters the reactor 4 from the argon source through the first three-way valve 1 and the second three-way valve 2 as gas path I; argon gas enters the TiCl4 source from the argon source through the first three-way valve 1, and then enters the reactor 4 through the second three-way valve 2 as gas path II; nitrogen gas enters the reactor 4 from the nitrogen source through the third three-way valve 3 as gas path III; methane gas enters the reactor 4 from the methane source through the third three-way valve 3 as gas path IV;

[0082] The argon gas source, the nitrogen gas source and the methane gas source are respectively connected to a gas flow meter, and the gas flow meter is further configured to be controlled by a gas circuit controller;

[0083] The device disclosed in Example 2 can be used in Example 1. According to the method disclosed in Example 1, the titanium mesh substrate is placed at the bottom of the reactor, and the carbon source, nitrogen source or carbon-nitrogen source is controlled to react with the titanium source on the reaction substrate in the reactor to generate a low-dimensional carbon / nitride adsorption material.

[0084] Example 3

[0085] In Example 3, the preparation method of the low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid includes:

[0086] Pretreating the titanium mesh to obtain a reaction substrate; specifically comprising: ultrasonically cleaning a 600-mesh titanium mesh with a thickness of 1 cm using a 5 wt.% dilute hydrochloric acid solution and deionized water in sequence to obtain a titanium mesh substrate with a clean surface and a size of 5 cm×5 cm;

[0087] The pretreated titanium mesh is placed in a reactor as a reaction substrate, and the reaction atmosphere in the reactor is replaced and adjusted to an inert atmosphere by argon gas; argon gas is used as a carrier gas to carry TiCl4 gas as a titanium source into the reactor; methane or a mixed gas of methane and nitrogen is used as a carbon source or a carbon-nitrogen source to enter the reactor; the temperature of the reactor is adjusted and raised to the reaction temperature; specifically comprising: placing the pretreated titanium mesh in the constant temperature heating area at the bottom of the reactor of the device disclosed in Example 2, and opening gas path I to keep gas paths II, III, and IV closed, and introducing argon gas to replace the gas in the reactor, after repeating three times, an inert gas environment is formed in the reactor, and then the reactor is heated to 1000°C at a heating rate of 5°C / min under argon protection, and then the temperature is kept constant for 20 minutes;

[0088] A carbon source, a nitrogen source or a carbon-nitrogen source reacts with a titanium source on a reaction substrate in a reactor to generate low-dimensional carbon / nitride; specifically, the process includes: subsequently switching the gas path to open gas paths II and IV and keeping gas paths I and III closed, and the gas carrying TiCl4 and CH4 meets on the surface of the titanium mesh, and is induced to achieve cracking and deposition under high temperature conditions to promote structural and component reconstruction on the surface of the titanium mesh, and in-situ growth of a low-dimensional Michaelis array, i.e., a low-dimensional carbide adsorption material;

[0089] After the reaction lasts for 10 minutes, close gas lines II and IV and open gas line I to cool down under the protection of argon;

[0090] The obtained low-dimensional carbide adsorption material is subjected to surface hydrophilic modification to obtain a low-dimensional carbide adsorption material for enriching silver resources in silver electrolysis waste liquid. Specifically, the process includes: after the temperature drops to room temperature, all gas paths are closed and the sample is taken out, and it is placed in a 5M LiOH solution and soaked for 24 hours to achieve the induced transformation of the interface functional groups in the aqueous reaction medium to form oxygen-containing hydrophilic functional groups, and after the transformation is completed, it is washed with deionized water to obtain the target adsorption material;

[0091] Finally, the silver-enriched low-dimensional carbide adsorption material obtained in Example 3 was applied to the silver electrolysis waste liquid as an adsorbent. After 60 minutes of stirring and adsorption, the recovery rate of silver resources was 98%.

[0092] Example 4

[0093] In Example 4, the preparation method of the low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid includes:

[0094] Pre-treating the titanium mesh to obtain a reaction substrate; specifically comprising: ultrasonically cleaning a 1000 mesh titanium mesh with a thickness of 0.5 cm using a 5 wt.% dilute hydrochloric acid solution and deionized water in sequence to obtain a titanium mesh substrate with a clean surface and a size of 5 cm×5 cm;

[0095] The pretreated titanium mesh is placed in a reactor as a reaction substrate, and the reaction atmosphere in the reactor is replaced and adjusted to an inert atmosphere by argon gas; argon gas is used as a carrier gas to carry TiCl4 gas as a titanium source into the reactor; methane or a mixed gas of methane and nitrogen is used as a carbon source or a carbon-nitrogen source to enter the reactor; the temperature of the reactor is adjusted and raised to the reaction temperature; specifically comprising: placing the pretreated titanium mesh in the constant temperature heating area at the bottom of the reactor of the device disclosed in Example 2, and opening gas path I to keep gas paths II, III, and IV closed, and introducing argon gas to replace the gas in the reactor, after repeating three times, an inert gas environment is formed in the reactor, and then the reactor is heated to 650°C at a heating rate of 3°C / min under argon protection, and then the temperature is kept constant for 30 minutes;

[0096] A carbon source, a nitrogen source or a carbon-nitrogen source reacts with a titanium source on a reaction substrate in a reactor to generate low-dimensional carbon / nitride; specifically, the process includes: subsequently switching the gas path to open gas paths II and III and keeping gas paths I and IV closed, and the gas carrying TiCl4 and N2 meets on the surface of the titanium mesh, and is induced to achieve cracking and deposition under high temperature conditions to promote structural and component reconstruction on the surface of the titanium mesh, and in-situ growth of a low-dimensional Michaelis array, i.e., a low-dimensional nitride adsorption material;

[0097] After 20 minutes of reaction, close gas lines II and IV and open gas line I to cool down under the protection of argon;

[0098] The obtained low-dimensional nitride adsorbent material is subjected to surface hydrophilic modification to obtain a low-dimensional nitride adsorbent material for enriching silver. Specifically, the process includes: after the temperature drops to room temperature, all gas paths are closed and the sample is taken out, and it is placed in a 5M HF solution and soaked for 24 hours to achieve the interface functional group induction transformation in the water-based reaction medium to form oxygen-containing hydrophilic functional groups, and after the transformation is completed, it is washed with deionized water to obtain the target adsorbent material;

[0099] Finally, the silver-enriched low-dimensional nitride adsorption material obtained in Example 4 was applied to the silver electrolysis waste liquid as an adsorbent. After 120 minutes of stirring and adsorption, the recovery rate of silver resources was 99%.

[0100] Example 5

[0101] In Example 5, the preparation method of the low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid includes:

[0102] Pre-treating the titanium mesh to obtain a reaction substrate; specifically comprising: ultrasonically cleaning a 0.8 cm thick 800 mesh titanium mesh using a 5 wt.% dilute hydrochloric acid solution and deionized water in sequence to obtain a titanium mesh substrate with a clean surface and a size of 5 cm×5 cm;

[0103] The pretreated titanium mesh is placed in a reactor as a reaction substrate, and the reaction atmosphere in the reactor is replaced and adjusted to an inert atmosphere by argon gas; argon gas is used as a carrier gas to carry TiCl4 gas as a titanium source into the reactor; methane or a mixed gas of methane and nitrogen is used as a carbon source or a carbon-nitrogen source to enter the reactor; the temperature of the reactor is adjusted and raised to the reaction temperature; specifically comprising: placing the pretreated titanium mesh in the constant temperature heating area at the bottom of the reactor of the device disclosed in Example 2, and opening gas path I to keep gas paths II, III, and IV closed, and introducing argon gas to replace the gas in the reactor, after repeating three times, an inert gas environment is formed in the reactor, and then the reactor is heated to 950°C at a heating rate of 5°C / min under argon protection, and then the temperature is kept constant for 15 minutes;

[0104] A carbon source, a nitrogen source or a carbon-nitrogen source reacts with a titanium source on a reaction substrate in a reactor to generate low-dimensional carbon / nitride; specifically, the process includes: subsequently switching the gas path to open gas paths II and IV and keeping gas paths I and III closed, and the gas carrying TiCl4 and CH4 meets on the surface of the titanium mesh, and is induced to achieve cracking and deposition under high temperature conditions to promote structural and component reconstruction on the surface of the titanium mesh, and in-situ growth of a low-dimensional Michaelis array, i.e., a low-dimensional carbide adsorption material;

[0105] After the reaction lasts for 300 min, close gas lines II and IV and open gas line I to cool down under the protection of argon;

[0106] The obtained low-dimensional carbide adsorption material is subjected to surface hydrophilic modification to obtain a low-dimensional carbide adsorption material for enriching silver. Specifically, the process includes: after the temperature drops to room temperature, all gas paths are closed and the sample is taken out, and it is placed in a 5M KOH solution and soaked for 24 hours to achieve the interface functional group induction transformation in the water-based reaction medium to form oxygen-containing hydrophilic functional groups, and after the transformation is completed, it is washed with deionized water to obtain the target adsorption material; Figure 4 TEM image of the low-dimensional carbide adsorption material obtained in Example 5;

[0107] Finally, the silver-enriched low-dimensional carbide adsorption material obtained in Example 5 was applied to the silver electrolysis waste liquid as an adsorbent. After 60 minutes of stirring and adsorption, the recovery rate of silver resources was 99.5%.

[0108] The method for preparing a low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid disclosed in an embodiment of the present invention uses a titanium mesh as a substrate, and under the coupling action of titanium halide gaseous salt and methane / nitrogen, a low-dimensional carbon / nitride adsorption material is obtained on the surface of the titanium mesh substrate through the joint promotion of chemical vapor deposition and self-consumption reaction, and further the surface functional group functionalization is realized through ligand exchange of nanostructured microinterface in an aqueous medium to obtain a hydrophilic low-dimensional carbon / nitride adsorption material; the hydrophilic low-dimensional carbon / nitride adsorption material generated on the titanium mesh can simultaneously adsorb silver ions and silver microparticles in the solution, and has good selectivity and high adsorption efficiency, and has good application prospects in the resource disposal of silver-containing solutions and subsequent sewage treatment.

[0109] The technical solutions disclosed in the embodiments of the present invention and the technical details disclosed in the embodiments are merely illustrative of the inventive concept of the present invention and do not constitute a limitation on the technical solutions of the embodiments of the present invention. Any conventional changes, replacements or combinations of the technical details disclosed in the embodiments of the present invention have the same inventive concept as the present invention and are within the protection scope of the claims of the present invention.

Claims

1. A method for preparing a low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid, It is characterized in that include: A titanium mesh is arranged in the reactor as a substrate, and the reaction atmosphere in the reactor is adjusted to an inert atmosphere; Argon is used as carrier gas to carry TiCl 4 The gas, as a titanium source, enters the reactor; Using methane or a mixture of methane and nitrogen as a carbon source or a carbon-nitrogen source to enter the reactor; On the substrate surface, a carbon source or a carbon-nitrogen source reacts with a titanium source under set conditions to generate low-dimensional carbon / nitride; wherein the reaction temperature is set to 600-1000° C., and the reaction time is set to 5-60 min; The obtained low-dimensional carbon / nitride adsorption material is subjected to surface hydrophilic modification to obtain a low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid.

2. The method for preparing a low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid according to claim 1, It is characterized in that Methane is used as a carbon source to react with a titanium source to generate low-dimensional carbides; wherein the flow rate of methane is 10 to 1000 sccm.

3. The method for preparing a low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid according to claim 1, It is characterized in that A mixed gas of methane and nitrogen is used as a carbon and nitrogen source to react with a titanium source to generate a low-dimensional carbon / nitride, wherein the low-dimensional carbon / nitride is composed of carbides, carbonitrides and nitrides; wherein the flow rate of the mixed gas is 10 to 1000 sccm, CH 4 With N 2 The volume ratio is greater than 5:

1.

4. The method for preparing a low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid according to claim 1, It is characterized in that Nitrogen is used as a nitrogen source to react with a titanium source to generate low-dimensional nitrides; wherein the flow rate of the nitrogen is 10 to 1000 sccm.

5. The method for preparing a low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid according to claim 1, It is characterized in that Using argon as carrier gas to carry TiCl 4 Methods of using gas as a titanium source include: TiCl 4 The salt is placed in a sealed container, the air inlet of the sealed container is connected to an argon gas source, and the air outlet of the sealed container is connected to a reactor; Place the sealed container in a water bath and heat to the set temperature; Adjust the argon source to provide a set flow of argon, TiCl 4 The salt is heated at a set temperature and vaporized into gaseous TiCl 4 , forms a mixed gas with argon and enters the reactor as a titanium source.

6. The method for preparing a low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid according to claim 1, It is characterized in that The pretreatment method of the titanium mesh includes: A titanium mesh with a pore size of 500 to 2000 meshes is cleaned with dilute acid, alcohol and deionized water in sequence to obtain a pretreated titanium mesh; wherein the dilute acid includes dilute hydrochloric acid, dilute hydrofluoric acid, dilute sulfuric acid and dilute nitric acid.

7. The method for preparing a low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid according to claim 1, It is characterized in that The obtained low-dimensional carbon / nitride adsorption material is subjected to surface hydrophilic modification using hydrofluoric acid, hydrochloric acid or lithium hydroxide aqueous solution to form hydroxyl and carboxyl hydrophilic functional groups on the surface of the low-dimensional carbon / nitride adsorption material.

8. The method for preparing a low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid according to claim 4, It is characterized in that Carrying TiCl 4 The argon gas flow rate is set to 10-200 sccm, and the sealed container is heated to form TiCl 4 The temperature of the gas was set to 70°C.

9. Low-dimensional carbon / nitride adsorption materials for enriching silver resources in silver electrolysis wastewater, It is characterized in that Obtained by the preparation method described in any one of claims 1 to 8, the low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid is a hydrophilic low-dimensional carbon / nitride adsorption material generated on the surface of a titanium mesh.

10. The use of the low-dimensional carbon / nitride adsorption material for enriching silver resources in silver electrolysis waste liquid as claimed in claim 9, It is characterized in that The low-dimensional carbon / nitride adsorption material is used to enrich silver in a solution, and specifically comprises: The hydrophilic low-dimensional carbon / nitride adsorption material generated on the surface of the titanium mesh is arranged in a solution treatment device; The solution containing silver is input into the solution treatment device, and the low-dimensional carbon / nitride adsorption material enriches the silver in the solution; the silver is enriched on the low-dimensional carbon / nitride adsorption material.

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