High-valence nickel catalytic material as well as preparation method and application thereof
High-valent nickel catalytic materials are prepared by homogeneous precipitation method and calcination method, and used in conjunction with peroxygen monosulfate (PMS), which solves the problems of low catalytic efficiency and high cobalt cost in the prior art, and achieves efficient degradation effect on organic pollutants.
Patent Information
- Application Number
- CN202510382249.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-28
- Publication Date
- 2025-06-06
AI Technical Summary
Among the existing advanced oxidation technologies, the catalytic efficiency of heterogeneous catalysts is low, and the transition metal cobalt is high cost and is easy to reduce at high temperatures, resulting in poor removal of organic pollutants under high temperature water systems.
The homogeneous precipitation method and calcination method are used to prepare high-valent nickel catalytic materials. Through the use of peroxy monosulfate (PMS), their activation ability is improved to efficiently remove organic pollutants.
The high-priced nickel catalytic material has a degradation rate of more than 80% for organic pollutants such as bisphenol A, carbamazepine, atrazine and benzoic acid within 30 minutes, especially the degradation rate of bisphenol A is as high as more than 95%, and maintains a good removal effect under different water conditions.
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Figure CN120094587A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of wastewater oxidation treatment, and specifically relates to a high-valent nickel catalytic material and a preparation method and application thereof. Background Art
[0002] With the rapid development of modern industry, the amount of wastewater discharged from pharmaceutical, papermaking, brewing and other industrial fields has shown a significant growth trend. Such wastewater generally contains high concentrations of synthetic organic pollutants, and their uncontrolled discharge has posed a serious threat to the ecological environment system and may endanger human health through enrichment in the food chain.
[0003] The treatment technology system for organic pollutants mainly includes three categories: physical treatment, biodegradation and chemical oxidation. 4 · - )'s persulfate advanced oxidation technology has shown significant application potential in the field of water pollution control due to its excellent oxidation ability, wide adaptability of reaction conditions, and good environmental stability. The mechanism of action of this technology is that the cleavage of the peroxide bond in the persulfate molecule triggers a chain reaction, generating sulfate radicals and other reactive oxygen species (ROS) with strong oxidizing ability, which efficiently mineralize organic pollutants into CO through electron transfer pathways. 2 and H 2 O.
[0004] Heterogeneous catalysis in advanced oxidation technology can effectively reduce the cost of use because the catalyst and reaction products are easy to separate, and the catalyst is easy to recycle and reuse. However, the catalytic efficiency of heterogeneous catalysis is low, so transition metals and heteroelements are used to dope and then change the electronic structure of the active center to improve the catalytic activation effect. For example, patent CN114950435A discloses a preparation method of cobalt oxygen catalyst and its products and applications. The prepared DR-VoCo 3 O 4 The catalyst can efficiently activate peroxymonosulfate (PMS). However, the cost of transition metal cobalt is high, and the cobalt oxide catalyst is easily reduced to metallic cobalt at high temperatures, resulting in a reduction in active sites, which is not conducive to the removal of organic pollutants in high-temperature water systems. Therefore, the development of different metal oxide catalysts is of great significance for the treatment of organic wastewater in different environments. Summary of the invention
[0005] In order to improve the activation ability of peroxymonosulfate (PMS) so that the persulfate advanced oxidation technology can treat organic wastewater more efficiently and stably, the present invention provides a high-valent nickel catalytic material and a preparation method thereof, and the catalytic material is used in conjunction with the advanced oxidation technology to treat organic wastewater.
[0006] In order to achieve the above application purpose, the technical solution adopted in this application is as follows:
[0007] In a first aspect, the present invention provides a method for preparing a high-valent nickel catalytic material, which comprises the following steps: 2 6H 2 O and urea are mixed and reacted in water, and the obtained precipitate is filtered, dried, and then calcined to obtain.
[0008] Among them, NiCl 2 6H 2 O is mixed with urea in water to obtain a salt solution, wherein the molar ratio of the metal salt to urea in the salt solution is 1:15 to 25. Preferably, the molar ratio of the metal salt to urea is 1:20.
[0009] Among them, NiCl 2 6H 2 The reaction temperature of mixing O and urea in water is 70-90°C.
[0010] Among them, NiCl 2 6H 2 After O and urea are mixed in water, they are stirred and condensed under reflux in a water bath at 70-90°C for 13-16 hours.
[0011] The calcination temperature is 450-750°C. Preferably, the calcination temperature is 500°C.
[0012] Among them, the calcination time is 2.5 to 3.5 hours.
[0013] The specific reaction equation for material preparation is as follows:
[0014] Urea hydrolysis: Urea reacts with water at high temperature to produce ammonia (NH 3 ) and carbon dioxide (CO 2 ):
[0015] CO(NH 2 ) 2 +H 2 O→2NH 3 +CO 2 ↑
[0016] Dissociation of ammonia: NH 3 Combines with water to form NH 4 + and OH - Ions, increase the pH of the solution:
[0017]
[0018] Ni 2+ Precipitation: Ni 2+ With OH - Combined to form nickel hydroxide (Ni(OH)2 )precipitation:
[0019] Ni 2+ +2OH - →Ni(OH) 2 ↓
[0020] Dehydration decomposition: Under heating conditions, Ni(OH) 2 Decomposes into NiO and water:
[0021] Ni(OH) 2 →ΔNiO+H 2 O
[0022] In a second aspect, the present invention provides a high-valent nickel catalytic material prepared by the above method.
[0023] In a third aspect, the present invention provides the use of the above-mentioned high-valent nickel catalytic material in activating peroxymonosulfate to degrade organic wastewater.
[0024] Wherein, the organic wastewater contains at least one organic pollutant selected from bisphenol A, carbamazepine, atrazine and benzoic acid.
[0025] Wherein, in the application, the mass ratio of organic pollutant:catalyst:oxidant is 4:(150-250):(15-25).
[0026] Beneficial effects: The present invention utilizes a homogeneous precipitation method combined with calcination to obtain a high-valent nickel catalytic material. It has good adsorption and peroxymonosulfate (PMS) activation properties. Experimental results show that when the high-valent nickel catalytic material prepared by the present invention treats wastewater containing organic pollutants such as bisphenol A, carbamazepine, atrazine or benzoic acid, the degradation rates of these organic pollutants are all above 80% within 30 minutes, especially the degradation rate of bisphenol A is as high as more than 95%, and it can maintain a good pollutant removal effect under different water conditions. This shows that the high-valent nickel catalytic material of the present invention has a strong ability to treat organic pollutants, and has very good practical application prospects in the removal of pollutants in organic wastewater in conjunction with persulfate advanced oxidation technology. BRIEF DESCRIPTION OF THE DRAWINGS
[0027] Figure 1 This is a diagram of the oxygen transfer reaction of methyl phenyl sulfoxide (PMSO) in the NiOx / PMS system of the high-valent nickel catalytic material prepared by the present invention;
[0028] Figure 2 This is a PMSO oxygen transfer reaction diagram of the high-valent nickel catalytic material prepared by the present invention in a NiOx system;
[0029] Figure 3 This is the XRD pattern of the high-valent nickel catalytic material prepared in Example 1 of the present invention;
[0030] Figure 4 This is a SEM image of the high-valent nickel catalytic material prepared in Example 1 of the present invention;
[0031] Figure 5 TEM image of the high-valent nickel catalytic material prepared in Example 1 of the present invention;
[0032] Figure 6 This is a graph showing the degradation performance of the high-valent nickel catalytic material prepared in Experimental Example 1 of the present invention for different organic pollutants;
[0033] Figure 7 This is a graph showing the degradation performance of the high-valent nickel catalytic material prepared in Experimental Example 2 of the present invention for BPA in different water bodies;
[0034] Figure 8 This is a degradation performance diagram of different catalyst dosages in Test Example 3 of the present invention;
[0035] Fig. 9 This is a degradation performance diagram of different oxidant dosages in Test Example 3 of the present invention. DETAILED DESCRIPTION
[0036] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application more clear, the present application is further described in detail below in combination with the implementation methods. Unless otherwise defined, all scientific and technological terms used herein have the same meanings as understood by ordinary technicians in the field.
[0037] The applicant found that NiO has excellent PMS activation ability due to its high specific surface area, flaky structure, fast charge transport and other characteristics. Therefore, a high-valent nickel catalytic material was obtained by homogeneous precipitation and calcination, and its adsorption and activation performance for PMS was verified through experiments.
[0038] It was found that Ni, which has strong oxidizing properties, &+ Methyl phenyl sulfoxide (PMSO) can be oxidized to methyl phenyl sulfone (PMSO) by O-transfer reaction. 2 ). PMSO was introduced into the reaction system as a pollutant to detect PMSO 2 The product signal confirmed the presence of high-valent nickel in the system. As the reaction proceeded, the peak area of PMSO at 4.6 min gradually decreased, accompanied by the peak area of PMSO at 7.2 min. 2 The signal gradually increases ( Figure 1 , Figure 2 ). That is, in NiO x PMSO in the / PMS system is oxidized to generate PMSO 2 , and PMSO in NiO x / PMS system converted to PMSO2 The efficiency is 99%.
[0039] Specific examples will be listed below to explain the scheme of the present invention. It will be appreciated by those skilled in the art that the following examples are only used to illustrate the present invention and should not be considered as limiting the scope of the present invention. Where specific techniques or conditions are not indicated in the examples, the techniques or conditions described in the literature in this area or the product instructions are used. Reagents or instruments used that do not indicate manufacturers are all conventional products that can be obtained commercially.
[0040] Example 1 Preparation of high-valent nickel catalytic material
[0041] 9.9167 g of NiCl 2 6H 2 O and 50g urea were dissolved in 500mL deionized water (the molar ratio of urea to metal salt was 20:1). Then, the salt solution was placed in a beaker sealed with a plastic film, stirred and condensed in a 90°C water bath for 13h. The green precipitate was then washed and filtered three times with deionized water. The obtained light green precipitate was dried in an oven at 60°C overnight. The dried sample was calcined in a muffle furnace for 3h, maintaining a heating rate of 15°C min -1 , until the temperature rises to 500℃ and maintains for 3h. Finally, the gray-black nanoparticle catalyst was successfully obtained and named NiO x . Figure 3 It is the high-valent nickel material NiO x XRD patterns of different times of use. Diffraction peaks at 37.1°, 43.1°, 62.6°, 75.0°, and 79.0° were detected, belonging to NiO x The (111), (200), (220), (311), and (222) crystal planes (JCPDS No.65-2901). Figure 3 It can be seen that the average peak of the diffraction peak can match the standard diffraction peak, that is, the purity of the prepared catalyst is relatively high.
[0042] Figure 4 , Figure 5 The prepared high-valent nickel material NiO x The SEM and TEM images show that the prepared catalyst is a clustered flake structure formed by sintering.
[0043] Test Example 1
[0044] 150 mg of the catalyst prepared in Example 1 was weighed and added into 200 mL of 20 mg·L -1 15 mg KHSO was added to the bisphenol A (BPA) solution. 5Powder solid, the degradation experiment was carried out at a reaction temperature of 30 ° C. 1 mL of the experimental solution was sampled at regular intervals, the sample was filtered through a 0.22 μm polyethersulfone filter membrane, and then 20 μL of 0.1 mM Na 2 S 2 O 3 The free radicals were quenched and the reaction was terminated. The residual amount of BPA in the experimental water at different times was determined by high performance liquid chromatography. The results showed that the removal rate of BPA reached more than 95% within 30 minutes.
[0045] 150 mg of the catalyst prepared in Example 1 was weighed and added into 200 mL of 20 mg·L -1 15 mg KHSO was added to the carbamazepine solution. 5 Powder solid, the degradation experiment was carried out at a reaction temperature of 30 ° C. 1 mL of the experimental solution was sampled at regular intervals, the sample was filtered through a 0.22 μm polyethersulfone filter membrane, and then 20 μL of 0.1 mM Na 2 S 2 O 3 The free radicals were quenched and the reaction was terminated. The residual amount of carbamazepine in the experimental water at different times was determined by high performance liquid chromatography. The results showed that the removal rate of carbamazepine was more than 85% within 30 minutes.
[0046] 150 mg of the catalyst prepared in Example 1 was weighed and added into 200 mL of 20 mg·L -1 15 mg KHSO was added to the atrazine solution. 5 Powder solid, the degradation experiment was carried out at a reaction temperature of 30 ° C. 1 mL of the experimental solution was sampled at regular intervals, the sample was filtered through a 0.22 μm polyethersulfone filter membrane, and then 20 μL of 0.1 mM Na 2 S 2 O 3 The free radicals were quenched and the reaction was terminated. The residual amount of atrazine in the experimental water at different times was determined by high performance liquid chromatography. The results showed that the removal rate of atrazine could reach more than 94% within 30 minutes.
[0047] 150 mg of the catalyst prepared in Example 1 was weighed and added into 200 mL of 20 mg·L -1 15 mg KHSO was added to the benzoic acid solution. 5 Powder solid, the degradation experiment was carried out at a reaction temperature of 30 ° C. 1 mL of the experimental solution was sampled at regular intervals, the sample was filtered through a 0.22 μm polyethersulfone filter membrane, and then 20 μL of 0.1 mM Na 2 S 2 O3 The free radicals were quenched and the reaction was terminated. The residual amount of benzoic acid in the experimental water at different times was determined by high performance liquid chromatography. The results showed that the removal rate of benzoic acid could reach more than 94% within 30 minutes.
[0048] Test Example 2
[0049] 150 mg of the catalyst prepared in Example 1 was weighed and added into 200 mL of 20 mg·L -1 15 mg KHSO was added to the BPA solution dissolved in filtered lake water. 5 Powder solid, the degradation experiment was carried out at a reaction temperature of 30 ° C. 1 mL of the experimental solution was sampled at regular intervals, the sample was filtered through a 0.22 μm polyethersulfone filter membrane, and then 20 μL of 0.1 mM Na 2 S 2 O 3 The free radicals were quenched and the reaction was terminated. The residual amount of BPA in the experimental water at different times was determined by high performance liquid chromatography. The results showed that the removal rate of BPA reached more than 82% within 30 minutes.
[0050] 150 mg of the catalyst prepared in Example 1 was weighed and added into 200 mL of 20 mg·L -1 15 mg KHSO was added to the BPA solution dissolved in filtered river water. 5 Powder solid, the degradation experiment was carried out at a reaction temperature of 30 ° C. 1 mL of the experimental solution was sampled at regular intervals, the sample was filtered through a 0.22 μm polyethersulfone filter membrane, and then 20 μL of 0.1 mM Na 2 S 2 O 3 The free radicals were quenched and the reaction was terminated. The residual amount of BPA in the experimental water at different times was determined by high performance liquid chromatography. The results showed that the removal rate of BPA reached more than 89% within 30 minutes.
[0051] 150 mg of the catalyst prepared in Example 1 was weighed and added into 200 mL of 20 mg·L -1 To the BPA solution dissolved in filtered tap water, add 15 mg KHSO 5 Powder solid, the degradation experiment was carried out at a reaction temperature of 30 ° C. 1 mL of the experimental solution was sampled at regular intervals, the sample was filtered through a 0.22 μm polyethersulfone filter membrane, and then 20 μL of 0.1 mM Na 2 S 2 O 3The free radicals were quenched and the reaction was terminated. The residual amount of BPA in the experimental water at different times was determined by high performance liquid chromatography. The results showed that the removal rate of BPA reached more than 92% within 30 minutes.
[0052] Test Example 3
[0053] Effect of different catalyst dosages: 50-250 mg of the catalyst prepared in Example 1 was weighed and added into 200 mL of 20 mg·L -1 15 mg KHSO was added to the BPA solution. 5 Powder solid, the degradation experiment was carried out at a reaction temperature of 30 ° C. 1 mL of the experimental solution was sampled at regular intervals, the sample was filtered through a 0.22 μm polyethersulfone filter membrane, and then 20 μL of 0.1 mM Na 2 S 2 O 3 The free radicals were quenched and the reaction was terminated. The residual amount of BPA in the experimental water at different times was determined by high performance liquid chromatography. The results showed that with the increase in the amount of catalyst, the removal rate of BPA within 30 minutes increased from 46.20% to 98.02%.
[0054] Effect of different oxidant dosages: 150 mg of the catalyst prepared in Example 1 was weighed and added into 200 mL of 20 mg·L -1 Add 5.0-25 mg KHSO to the BPA solution 5 Powder solid, the degradation experiment was carried out at a reaction temperature of 30 ° C. 1 mL of the experimental solution was sampled at regular intervals, the sample was filtered through a 0.22 μm polyethersulfone filter membrane, and then 20 μL of 0.1 mM Na 2 S 2 O 3 The free radicals were quenched and the reaction was terminated. The residual amount of BPA in the experimental water at different times was determined by high performance liquid chromatography. The results showed that with the increase in the amount of oxidant, the removal rate of BPA increased from 0.96% to 96.79% within 30 minutes.
[0055] From the above results, it can be seen that the high-valent nickel catalytic material prepared by the present invention in conjunction with the advanced oxidation technology has a relatively significant effect on treating difficult-to-degrade organic pollutants such as bisphenol A, carbamazepine, atrazine, benzoic acid, etc. in water bodies, and its application in different actual water bodies also has a significant treatment effect; and with the increase in the amount of catalyst and oxidant used, the removal rate of organic pollutants is significantly improved.
Claims
1. A method for preparing a high-valent nickel catalytic material, characterized in that: The following steps are involved: After NiCl2·6H2O and urea are mixed and reacted in water, the obtained precipitate is filtered, dried, and then calcined to obtain the product.
2. The method for preparing a high-valent nickel catalytic material according to claim 1, characterized in that: NiCl2·6H2O and urea are mixed in water to obtain a salt solution, wherein the molar ratio of the metal salt to urea in the salt solution is 1:15-25; preferably, the molar ratio of the metal salt to urea is 1:
20.
3. The method for preparing a high-valent nickel catalytic material according to claim 1 or 2, characterized in that: The reaction temperature of NiCl2·6H2O and urea mixed in water is 70-90℃.
4. The method for preparing a high-valent nickel catalytic material according to any one of claims 1 to 3, characterized in that: After NiCl2·6H2O and urea are mixed in water, they are stirred and condensed under reflux in a water bath at 70-90°C for 13-16 hours.
5. The method for preparing a high-valent nickel catalytic material according to any one of claims 1 to 4, characterized in that: The calcination temperature is 450-750°C; preferably, the calcination temperature is 500°C.
6. The method for preparing a high-valent nickel catalytic material according to any one of claims 1 to 5, characterized in that: The calcination time is 2.5 to 3.5 hours.
7. A high-valent nickel catalytic material prepared by the method according to any one of claims 1 to 6.
8. Use of the high-valent nickel catalytic material according to claim 7 in activating peroxymonosulfate to degrade organic wastewater.
9. The use according to claim 8, characterized in that: The organic wastewater contains at least one organic pollutant selected from the group consisting of bisphenol A, carbamazepine, atrazine and benzoic acid.
10. The use according to claim 8 or 9, characterized in that: The mass ratio of organic pollutants: catalyst: oxidant is 4: (150-250): (15-25).