A nickel-manganese-sulfur loaded nickel foam composite material and application thereof in heterogeneous activation of periodate treatment of organic pollutants

Abstract

The application belongs to the technical field of environmental engineering, and discloses a nickel-manganese-sulfur loaded foam nickel composite material and application thereof in heterogeneous activation of periodate treatment of organic pollutants, comprising: foam nickel material is sequentially subjected to calcination passivation, high-temperature hydrothermal treatment and ion exchange reaction to obtain a nickel-manganese-sulfur loaded foam nickel composite material, the morphology and composition of which are controllable; the composite material is self-assembled into a catalyst module, mixed waste liquid containing organic pollutants and periodate is allowed to flow through the catalyst, periodate is activated to produce active free radicals, and degradation of the organic pollutants is realized. The material obtained by the application has the advantages of no pollution, high catalytic activity, stable catalytic effect, uniform and firm distribution of active components, high mechanical strength, low self-weight and the like, and the self-supporting catalyst module constructed based on the material effectively avoids the problem of difficult separation and recovery of powder catalyst, is convenient for modular management and large-scale amplification, and has a broad application prospect in the technical field of environmental engineering.

Description

Technical Field

[0001] This invention relates to a nickel-manganese-sulfur supported foam nickel composite material and its application in heterogeneous activated periodate treatment of organic pollutants, belonging to the field of environmental engineering technology. Background Technology

[0002] Treating organic pollutants is crucial for promoting sustainable development in modern society and ensuring the safety of the human environment. Among numerous pollution remediation technologies, periodate has attracted widespread attention due to its unique environmentally friendly properties. Compared with traditional oxidants such as persulfate, periodate does not cause color problems or significant pH changes during application, and its ease of storage and transportation significantly enhances its appeal in the field of environmental engineering. However, the chemical stability of periodate itself limits its ability to directly oxidize organic pollutants. Furthermore, the catalysts currently receiving widespread attention suffer from agglomeration and difficulty in recycling during use, further hindering their widespread application and economic viability.

[0003] To address this challenge, one strategy is to load active metal nanoparticles onto well-organized supports with high specific surface area and abundant pore structure. This not only achieves effective immobilization of the metal nanoparticles but also fully utilizes the structural advantages of the support. Specifically, nickel foam materials are considered ideal for treating organic pollutants due to their excellent mechanical properties, uniform pore distribution, chemical stability, good corrosion resistance, and excellent anti-clogging properties. Transition metal-based catalysts, especially 3D transition metal compounds obtained by modifying composition and structure, have proven to be a promising approach for activating periodate. Compared with monometallic catalysts, binary metal oxides and sulfides with different oxidation states exhibit superior performance, attributed to their high chemical activity and synergistic effects between metal cations. Nevertheless, the preparation of current transition metal compounds typically involves complex processes. For example:

[0004] Patent CN109055972B describes a Mn-doped Ni3S2 nanoarray as a hydrogen evolution catalyst. Its preparation process includes ultrasonic pretreatment of nickel foam with dilute hydrochloric acid solution, which may leave acid residues that adversely affect the experiment. Furthermore, this method requires the addition of an extra nickel source and the use of non-productive chemical reagents such as urea, which not only increases costs but also wastes resources.

[0005] The trace iron ion doped nickel disulfide catalyst disclosed in patent CN109112566A requires electrochemical deposition and uses boric acid as the electrodeposition solution. This method also has environmental pollution problems, and the process is complex, requires many types of reagents, and is costly.

[0006] In summary, although various catalysts have been developed for activating periodate to treat organic pollutants, these methods often suffer from drawbacks such as subsequent pollution, cumbersome operation, high raw material costs, and high energy consumption, limiting their efficiency and economic viability in practical applications. Therefore, there is an urgent need to develop a catalyst that is structurally stable, environmentally friendly, cost-effective, easy to operate, and possesses superior performance to advance the development of organic pollutant treatment technologies. Summary of the Invention

[0007] The purpose of this invention is to address the shortcomings of existing technologies by providing a method for preparing nickel-manganese-sulfur supported foam nickel composite materials and their application in the treatment of organic pollutants using heterogeneous activated periodate. The technical problems to be solved are: subsequent pollution, waste of non-product chemical reagents, difficulty in separating and recovering powdered catalysts, poor overall catalyst catalytic effect, weak self-supporting ability, uneven distribution of active components, high energy consumption in preparation, and how to treat organic pollutants simply, efficiently and quickly.

[0008] To solve the above problems, the present invention adopts the following technical solution:

[0009] The preparation method of the nickel-manganese-sulfur supported nickel foam composite material of the present invention includes the following steps:

[0010] Step 1: Passivate the nickel foam material by calcining it in a muffle furnace at 300-400℃ for 6-12 hours to form a nickel oxide coating;

[0011] Step 2: Add the calcined nickel foam to the potassium permanganate solution, transfer it to a high-pressure reactor, and hydrothermally react at 120-180℃ for 1-6 hours. The resulting product is washed with water and dried to obtain the precursor.

[0012] Step 3: The precursor is transferred into a high-pressure reactor containing sodium sulfide solution and subjected to ion exchange reaction at 100-190℃ for 1-6 hours. The resulting product is washed with water and dried to obtain nickel-manganese-sulfur supported foam nickel composite material.

[0013] Preferably, in step 2, the concentration of the potassium permanganate solution is 10-50 mmol / L.

[0014] Preferably, in step 3, the concentration of the sodium sulfide solution is 10-100 mmol / L.

[0015] Preferably, in steps 2 and 3, the drying conditions are 60–80°C for 6–10 hours.

[0016] The nickel-manganese-sulfur supported foamed nickel composite material prepared in this invention can be used as a catalyst for heterogeneous activation of periodate to degrade organic pollutants and achieve the treatment of organic pollutants. The specific application method is as follows: construct an organic pollutant treatment device; assemble multiple pieces of the nickel-manganese-sulfur supported foamed nickel composite material into a catalyst module; use the catalyst module as a reaction unit in the organic pollutant treatment device; allow the mixed waste liquid containing organic pollutants and periodate to flow through the catalyst module, activate periodate to generate active free radicals, and achieve complete degradation of organic pollutants.

[0017] The catalyst module requires no adhesive for assembly and is self-supporting. The dimensions of the catalyst module can be flexibly altered by increasing or decreasing the amount of nickel-manganese-sulfur-loaded nickel foam composite material without damaging the module.

[0018] Preferably, the periodate contains at least one of potassium periodate and sodium periodate.

[0019] Preferably, the organic pollutant is at least one of Golden Orange II, Methylene Blue, Neutral Red, Tetracycline Hydrochloride, and Oxytetracycline Hydrochloride.

[0020] Preferably, the concentration of organic pollutants in the mixed waste liquid is 1-100 mg / L, and the ratio of organic pollutants to oxidant periodate is 1-100 mg: 1 mmol.

[0021] Preferably, the organic pollutant treatment device can consist of four parts: an oxidant storage tank, an organic pollutant tank, a mixing vessel, and a degradation reaction tank.

[0022] The core component of the degradation reaction tank is a series of catalyst modules arranged along the flow direction, which are the site of the organic oxidation reaction. During operation, the solution in the organic pollutant tank and the periodate solution in the oxidant storage tank are pumped into a mixing vessel by a centrifugal pump. After being stirred evenly in the mixing vessel, the mixture is then pumped into the degradation reaction tank. The periodate-containing organic pollutant solution flows through the catalyst modules. The nickel-manganese-sulfur-supported nickel foam composite material activates the periodate, decomposing it to generate highly reactive free radicals that mineralize the organic matter in the solution into CO2 and H2O. After the solution is treated to meet the standards through the oxidation reaction, it is discharged.

[0023] Compared with the prior art, the beneficial effects of the present invention are reflected in:

[0024] 1. By avoiding the use of acidic solutions to pretreat nickel foam, this invention avoids the subsequent contamination problems that may be caused by acid residue. Using a one-step passivation process, this invention forms a nickel oxide protective layer on the surface of the nickel foam, which not only enhances the stability of the material but also avoids damage to the nickel foam support material that may be caused by the hydrothermal process.

[0025] 2. This invention directly grows nickel-manganese-sulfur nanosheet arrays on a nickel foam block support via calcination passivation, high-temperature hydrothermal treatment, and ion exchange. This method utilizes the nickel foam itself as the nickel source, avoiding the addition of exogenous nickel sources, simplifying the operation process, reducing the use of non-productive chemical reagents, thereby significantly reducing costs and improving environmental friendliness.

[0026] 3. The nickel-manganese-sulfur supported nickel foam composite material prepared in this invention exhibits excellent catalytic efficiency and stability, as well as high mechanical strength and low weight. Through the optimized nickel-manganese-sulfur nanosheet array structure, the specific surface area and surface active sites of the catalyst are significantly increased. Utilizing the synergistic effect between Mn, Ni, and sulfur within the nickel foam matrix, redox active sites are enriched, effectively improving catalytic efficiency. Experimental results demonstrate that the composite material of this invention exhibits 100% degradation efficiency during periodate activation, and the operation is simple, requires no additional energy input, and the catalyst is easy to recover and recycle, fully complying with green environmental protection principles.

[0027] 4. The self-supporting catalyst module of this invention can efficiently activate periodate to generate active free radicals, thereby degrading organic pollutants. This design effectively overcomes the difficulties of separation and recovery of traditional powdered catalysts, and supports the modular management and large-scale expansion of oxidative degradation tanks, demonstrating excellent performance and broad application potential in the field of environmental engineering technology. Attached Figure Description

[0028] Figure 1 This is a SEM image of the nickel-manganese-sulfur supported nickel foam composite material prepared in Example 1 of the present invention;

[0029] Figure 2 This is a TEM image of the nickel-manganese-sulfur supported nickel foam composite material prepared in Example 1 of the present invention;

[0030] Figure 3 This is an EDS elemental scan of the nickel-manganese-sulfur supported nickel foam composite material prepared in Example 1 of the present invention;

[0031] Figure 4 This is a diagram of the organic pollutant treatment device constructed according to the present invention;

[0032] Figure 5 This is a repeatability test diagram of the degradation of Golden Orange II by the nickel-manganese-sulfur supported foam nickel composite material prepared in Example 1 of the present invention;

[0033] Figure 6 This is a comparison diagram showing the degradation effect of Golden Orange II on the nickel-manganese-sulfur-loaded nickel foam composite material prepared in Example 1 of the present invention and the nickel foam composite material with different elements as a comparison. Detailed Implementation

[0034] The embodiments of the present invention will be described in detail below with reference to the accompanying drawings. The following embodiments are implemented based on the technical solution of the present invention, and detailed implementation methods and specific operation processes are given. However, the protection scope of the present invention is not limited to the following embodiments.

[0035] Example 1

[0036] (I) Preparation of nickel-manganese-sulfur supported nickel foam composite material

[0037] The preparation method of the nickel-manganese-sulfur supported nickel foam composite material in this embodiment is as follows:

[0038] 1. Pretreatment: First, cut the nickel foam into small pieces with a length and width of 2cm×2cm. Then, repeatedly ultrasonically clean the nickel foam with anhydrous ethanol and deionized water to remove the adhering substances on the surface of the nickel foam. Then, dry it at 60℃ for later use.

[0039] 2. Passivate the pretreated nickel foam material by calcining it in a muffle furnace at 350°C for 6 hours to form a nickel oxide coating.

[0040] 3. Add the calcined nickel foam to a 25 mmol / L potassium permanganate solution, transfer to a high-pressure reactor, hydrothermally heat at 180°C for 1 h, wash repeatedly with deionized water, and dry at 60°C to obtain the precursor.

[0041] 4. The precursor was transferred into a high-pressure reactor containing 100 mmol / L sodium sulfide solution and subjected to ion exchange reaction at 160 °C for 2 h. After repeated washing with deionized water, it was dried at 60 °C to obtain nickel-manganese-sulfur supported nickel foam composite material (NiMnS@NF).

[0042] Figure 1 and Figure 2 The images show SEM and TEM images of the nickel-manganese-sulfur supported nickel foam composite material prepared in this embodiment. The nickel-manganese-sulfur nanosheet array structure can be clearly observed in both SEM and TEM images, and this structure is tightly and firmly bonded to the nickel foam matrix. Figure 3 This is an EDS elemental scan of the nickel-manganese-sulfur supported nickel foam composite material prepared in this embodiment. As can be seen from the figure, manganese, nickel, and sulfur elements are uniformly doped into the nickel foam.

[0043] (II) Constructing an organic pollutant treatment facility

[0044] like Figure 4As shown, the organic pollutant treatment device consists of four parts: an oxidant storage tank, an organic pollutant tank, a mixing vessel, and a degradation reaction tank. The core component in the degradation reaction tank is a series of catalyst modules arranged along the flow direction, which is the site of the organic oxidation reaction. During operation, the solution in the organic pollutant tank and the periodate solution in the oxidant storage tank are pumped into the mixing vessel by a centrifugal pump. After being thoroughly mixed in the mixing vessel, the solution is then pumped into the degradation reaction tank by another centrifugal pump.

[0045] First, multiple pieces of nickel-manganese-sulfur-supported nickel foam composite material are fixedly assembled using a stainless steel mold to produce an integral catalyst module of nickel-manganese-sulfur-supported nickel foam composite material. Then, the catalyst module is arranged in the degradation reaction tank along the flow direction.

[0046] A solution of organic pollutants containing Golden Orange II (20 mg / L) and a periodate solution (1 mmol / L) were separately placed into an organic pollutant tank and an oxidant storage tank, respectively. These were then pumped into a mixing vessel at a 1:1 volume ratio using a centrifugal pump. After thorough mixing in the mixing vessel, the mixture was pumped into the degradation reaction tank. The periodate-containing organic pollutant solution flowed through a catalyst module. The nickel-manganese-sulfur-supported nickel foam composite material activated the periodate, generating highly reactive free radicals that mineralized the organic matter in the solution into CO2 and H2O. The solution was then treated through the oxidation reaction to meet emission standards before being discharged. Testing showed that the final degradation rate of Golden Orange II was 100%.

[0047] Figure 5 The figure shows the repeatability of the degradation of Golden Orange II by the nickel-manganese-sulfur supported foam nickel composite material prepared in Example 1. As can be seen from the figure, the prepared nickel-manganese-sulfur supported foam nickel composite material still showed good degradation effect after 4 repetitions, indicating that the prepared composite material has stable catalytic effect and strong distribution of active components.

[0048] Example 2

[0049] (I) Preparation of nickel foam composites loaded with different elements

[0050] Preparation of nickel-manganese-supported nickel foam composite material (NiMn@NF): The precursor prepared by the same method as steps 1, 2 and 3 of Example 1 is the nickel-manganese-supported nickel foam composite material.

[0051] Preparation of nickel-sulfur supported nickel foam composite material (NiS@NF): Replace the potassium permanganate solution in step 3 of Example 1 with an equal volume of water, and the remaining steps are the same as in Example 1.

[0052] (II) Degradation of organic pollutants

[0053] The same organic pollutant treatment device as in Example 1 was constructed using the composite material prepared in this embodiment. An organic pollutant solution containing Golden Orange II (20 mg / L) and a periodate solution (1 mmol / L) were separately placed into an organic pollutant tank and an oxidant storage tank, respectively. These were then pumped into a mixing vessel at a 1:1 volume ratio using a centrifugal pump. After thorough mixing in the mixing vessel, the mixture was pumped into a degradation reaction tank. The periodate-containing organic pollutant solution flowed through a catalyst module. The nickel foam composite material loaded with different elements activated the periodate, decomposing it to generate highly reactive free radicals that mineralized the organic matter in the solution into CO2 and H2O. After the solution underwent oxidation treatment to meet the standards, it was discharged.

[0054] Figure 6 The figure shows a comparison of the degradation effects of the composite materials prepared in Example 1 and Example 2 on Golden Orange II. It can be seen from the figure that the prepared nickel-manganese-sulfur supported nickel foam composite material exhibits the best degradation effect.

[0055] Example 3

[0056] (I) Preparation of nickel-manganese-sulfur supported nickel foam composite material

[0057] In this embodiment, nickel-manganese-sulfur supported nickel foam composite material was prepared using the same method as in Example 1.

[0058] (II) Degradation of organic pollutants

[0059] The same organic pollutant treatment device as in Example 1 was constructed using the nickel-manganese-sulfur-supported nickel foam composite material prepared in this embodiment. An organic pollutant solution containing methylene blue (20 mg / L) and a periodate solution (1 mmol / L) were separately added to an organic pollutant tank and an oxidant storage tank, respectively. These were then pumped into a mixing vessel at a 1:1 volume ratio using a centrifugal pump. After thorough mixing in the mixing vessel, the solution was pumped into a degradation reaction tank. The periodate-containing organic pollutant solution flowed through a catalyst module. The nickel-manganese-sulfur-supported nickel foam composite material activated the periodate, generating highly reactive free radicals that mineralized the organic matter in the solution into CO2 and H2O. After the solution reached the required standards through the oxidation reaction, it was discharged. Testing showed that the final degradation rate of methylene blue was 100%.

[0060] Example 4

[0061] (I) Preparation of nickel-manganese-sulfur supported nickel foam composite material

[0062] In this embodiment, nickel-manganese-sulfur supported nickel foam composite material was prepared using the same method as in Example 1.

[0063] (II) Degradation of organic pollutants

[0064] The same organic pollutant treatment device as in Example 1 was constructed using the nickel-manganese-sulfur-supported nickel foam composite material prepared in this embodiment. An organic pollutant solution containing neutral red (20 mg / L) and a periodate solution (1 mmol / L) were separately added to an organic pollutant tank and an oxidant storage tank, respectively. These were then pumped into a mixing vessel at a 1:1 volume ratio using a centrifugal pump. After thorough mixing in the mixing vessel, the solution was pumped into a degradation reaction tank. The periodate-containing organic pollutant solution flowed through a catalyst module. The nickel-manganese-sulfur-supported nickel foam composite material activated the periodate, generating highly reactive free radicals that mineralized the organic matter in the solution into CO2 and H2O. After the solution reached the required standards through the oxidation reaction, it was discharged. Testing showed that the final degradation rate of neutral red was 100%.

[0065] Example 5

[0066] (I) Preparation of nickel-manganese-sulfur supported nickel foam composite material

[0067] In this embodiment, nickel-manganese-sulfur supported nickel foam composite material was prepared using the same method as in Example 1.

[0068] (II) Degradation of organic pollutants

[0069] The same organic pollutant treatment device as in Example 1 was constructed using the nickel-manganese-sulfur-supported nickel foam composite material prepared in this embodiment. A solution of organic pollutants containing tetracycline hydrochloride (20 mg / L) and a periodate solution (1 mmol / L) were separately placed into an organic pollutant tank and an oxidant storage tank, respectively. These were then pumped into a mixing vessel at a 1:1 volume ratio using a centrifugal pump. After thorough mixing in the mixing vessel, the solution was pumped into a degradation reaction tank. The periodate-containing organic pollutant solution flowed through a catalyst module. The nickel-manganese-sulfur-supported nickel foam composite material activated the periodate, decomposing it to generate highly reactive free radicals that mineralized the organic matter in the solution into CO2 and H2O. After the solution reached the required standards through the oxidation reaction, it was discharged. Testing showed that the final degradation rate of tetracycline hydrochloride was 100%.

[0070] Example 6

[0071] (I) Preparation of nickel-manganese-sulfur supported nickel foam composite material

[0072] In this embodiment, nickel-manganese-sulfur supported nickel foam composite material was prepared using the same method as in Example 1.

[0073] (II) Degradation of organic pollutants

[0074] The same organic pollutant treatment device as in Example 1 was constructed using the nickel-manganese-sulfur-supported nickel foam composite material prepared in this embodiment. An organic pollutant solution containing oxytetracycline hydrochloride (20 mg / L) and a periodate solution (1 mmol / L) were separately added to an organic pollutant tank and an oxidant storage tank, respectively. These were then pumped into a mixing vessel at a 1:1 volume ratio by a centrifugal pump. After thorough mixing in the mixing vessel, the solution was pumped into a degradation reaction tank. The periodate-containing organic pollutant solution flowed through a catalyst module. The nickel-manganese-sulfur-supported nickel foam composite material activated the periodate, generating highly reactive free radicals that mineralized the organic matter in the solution into CO2 and H2O. After the solution reached the required standards through the oxidation reaction, it was discharged. Testing showed that the final degradation rate of oxytetracycline hydrochloride was 100%.

[0075] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing a nickel-manganese-sulfur supported nickel foam composite material, characterized in that, Follow these steps: Step 1: Passivate the nickel foam material by calcining it in a muffle furnace at 300-400 ℃ for 6-12 h to form a nickel oxide coating; Step 2: Add the calcined nickel foam to a potassium permanganate solution with a concentration of 10-50 mmol / L, transfer it to a high-pressure reactor, and hydrothermally react at 120-180 ℃ for 1-6 h. The resulting product is washed with water and dried to obtain the precursor. Step 3: The precursor is transferred into a high-pressure reactor containing sodium sulfide solution and subjected to ion exchange reaction at 100-190 °C for 1-6 h. The product is washed with water and dried to obtain nickel-manganese-sulfur supported foam nickel composite material. The concentration of the sodium sulfide solution is 10-100 mmol / L.

2. The preparation method according to claim 1, characterized in that: In steps 2 and 3, the drying conditions are 60~80 ℃ for 6-10 h.

3. A nickel-manganese-sulfur-supported nickel foam composite material prepared by the preparation method of claim 1 or 2.

4. The application of the nickel-manganese-sulfur supported nickel foam composite material as described in claim 3 in heterogeneous activated periodate treatment of organic pollutants, characterized in that: The nickel-manganese-sulfur supported nickel foam composite material is used as a catalyst to activate periodate as an oxidant to degrade organic pollutants.

5. The application according to claim 4, characterized in that: An organic pollutant treatment device is constructed; multiple pieces of the nickel-manganese-sulfur supported foam nickel composite material are assembled into a catalyst module, and the catalyst module is used as a reaction unit in the organic pollutant treatment device. The mixed waste liquid containing organic pollutants and periodate flows through the catalyst module, activating periodate to generate active free radicals, thereby achieving complete degradation of organic pollutants. The organic pollutant treatment device consists of four parts: an oxidant storage tank, an organic pollutant tank, a mixing vessel, and a degradation reaction tank. The core component of the degradation reaction tank is a series of catalyst modules arranged along the flow direction and installed in the degradation reaction tank.

6. The application according to claim 5, characterized in that: The catalyst module has self-supporting capabilities, and its specifications and dimensions can be flexibly changed by increasing or decreasing the amount of nickel-manganese-sulfur-loaded nickel foam composite material without damaging the catalyst module.

7. The application according to claim 4 or 5, characterized in that: The periodate contains at least one of potassium periodate and sodium periodate.

8. The application according to claim 4 or 5, characterized in that: The organic pollutant is at least one of Golden Orange II, Methylene Blue, Neutral Red, Tetracycline Hydrochloride, and Oxytetracycline Hydrochloride.

Images