Ferric oxyhydroxide modified electrolytic manganese residue catalyst as well as preparation method and application thereof

Abstract

The invention provides an iron oxyhydroxide modified electrolytic manganese residue catalyst as well as a preparation method and application thereof, and belongs to the technical field of environmental pollution treatment. The preparation method comprises the following steps: by taking electrolytic manganese residues as a raw material, pretreating the electrolytic manganese residues, adding a ferric nitrate solution to prepare a catalyst mud blank, and putting the catalyst mud blank into a reaction kettle for hydrothermal reaction to obtain the catalyst. The catalyst is prepared by modifying the electrolytic manganese residues with the iron oxyhydroxide, the catalyst can effectively remove phenylarsonic acid pollution in a water body, meanwhile, resource utilization of the manganese residues is achieved, environmental pollution is reduced, and a new technical approach is provided for water body pollution treatment.

Description

Technical Field

[0001] The present invention relates to the technical field of environmental pollution treatment, and particularly relates to a hydroxyl iron oxide modified electrolytic manganese slag catalyst, a preparation method thereof, and an application thereof. Background Art

[0002] With the acceleration of the industrialization process, the problem of water pollution has become increasingly serious. In particular, wastewater containing phenylarsonic acid (PPA) poses a threat to the environment and human health. Phenylarsonic acid is an organic arsenic compound with high toxicity, bioaccumulation, and environmental persistence, posing a serious threat to aquatic organisms and human health. It mainly comes from the use of pesticides and veterinary drugs and emissions during industrial production processes. Phenylarsonic acid is difficult to degrade naturally in water bodies and is easily accumulated in organisms, leading to the death of aquatic organisms and humans ingesting toxic substances through the food chain, thereby triggering various diseases such as nervous system damage and liver diseases. Traditional treatment methods such as chemical precipitation, adsorption, and biodegradation have problems such as low efficiency, high cost, and complex operation, and it is difficult to meet the actual needs of water pollution treatment. For example, the chemical precipitation method requires the addition of a large amount of chemical reagents, generates a large amount of sludge, has a high treatment cost, and is prone to secondary pollution; although the adsorption method is simple to operate, the regeneration and treatment of the adsorbent also face certain challenges; the biodegradation method has a long treatment cycle, high requirements for environmental conditions, and poor treatment effects on high-concentration phenylarsonic acid wastewater. Therefore, it is of great significance to develop a highly efficient, low-cost, and easy-to-operate catalyst to remove phenylarsonic acid pollution in water bodies.

[0003] Manganese slag is the main by-product generated during the production of electrolytic manganese, and its characteristics have an important impact on the environment and resource utilization. The phase composition and sintering characteristics of manganese slag have also been studied, and it is found that manganese slag mainly contains quartz (SiO 2 ) and gypsum (CaSO 4 ·2H 2 O), and the components are mainly oxides such as Al 2 O 3 , Fe 2 O 3 , MgO, and MnO. The comprehensive utilization of electrolytic manganese slag mainly focuses on the recovery of manganese, the preparation of building materials such as paving bricks, and the use as soil fertilizers. Manganese slag contains a large amount of SiO 2 , Al 2 O 3 , Fe 2 O 3Substances such as these can have their latent activities activated after being calcined at a certain temperature, and subsequent high-efficiency resource utilization can be carried out. For example, the calcined manganese slag can be used to prepare building materials such as cement and concrete to improve their strength and durability; it can also be used as a soil conditioner to improve soil structure and fertility. The calcination treatment of manganese slag has many advantages compared with other methods. During the calcination process, harmful substances in the electrolytic manganese slag will be removed, and the generated gas can be recycled to prepare sulfuric acid, achieving resource recycling and environmental sustainable development.

[0004] However, there are relatively few current studies on the treatment of water pollution with manganese slag, especially there are few reports on the study of using modified manganese slag to remove phenylarsonic acid pollution in water. Manganese slag itself has certain adsorption properties, but its adsorption capacity and selectivity are limited, making it difficult to meet the requirements for efficient removal of phenylarsonic acid. Therefore, how to improve the catalytic performance of manganese slag through modification methods to make it play a greater role in removing phenylarsonic acid pollution has become an urgent problem to be solved. The present invention aims to provide a hydroxyl iron oxide modified electrolytic manganese slag catalyst and its preparation method to effectively remove phenylarsonic acid pollution in water, while realizing the resource utilization of manganese slag, reducing environmental pollution, and providing a new technical approach for water pollution treatment. Summary of the Invention

[0005] The purpose of the present invention is to provide a hydroxyl iron oxide modified electrolytic manganese slag catalyst and its preparation method and application to solve the above technical problems.

[0006] In order to achieve the above invention purpose, the present invention provides the following technical solutions:

[0007] The present invention provides a preparation method of a hydroxyl iron oxide modified electrolytic manganese slag catalyst, comprising the following steps:

[0008] 1) Add manganese slag powder into water for ultrasonic treatment, and then add ferric nitrate solution for mixing to obtain a catalyst embryo;

[0009] 2) Place the catalyst embryo in a reaction kettle for hydrothermal reaction to obtain a catalyst;

[0010] The mass concentration of the ferric nitrate solution is 0.025 - 0.2 g / mL.

[0011] Furthermore, the particle size of the manganese slag powder is 120 - 200 μm.

[0012] Furthermore, the mass ratio of the manganese slag powder to ferric nitrate in the ferric nitrate solution is 1:0.5 - 4;

[0013] The mass-volume ratio of the manganese slag powder to water is 1 g:30 - 50 mL.

[0014] Further, the time of the ultrasonic treatment is 20 to 40 min.

[0015] Further, the temperature of the hydrothermal reaction is 150 to 170 °C, and the time of the hydrothermal reaction is 14 to 18 h.

[0016] Further, the mixing is carried out under stirring, the rotation speed of the stirring is 500 to 700 rpm, and the time of the stirring is 1 to 3 h.

[0017] The present invention also provides a catalyst of iron oxyhydroxide modified electrolytic manganese residue.

[0018] The present invention provides an application of a catalyst of iron oxyhydroxide modified electrolytic manganese residue in removing phenylarsonic acid pollution in water body. The catalyst of iron oxyhydroxide modified electrolytic manganese residue and peroxydisulfate are used in combination and put into the wastewater polluted by phenylarsonic acid;

[0019] The dosage of the catalyst of iron oxyhydroxide modified electrolytic manganese residue in the wastewater polluted by phenylarsonic acid is 0.2 to 0.8 g / L; the dosage of the peroxydisulfate is 0.1 to 0.4 g / L.

[0020] The beneficial effects of the present invention:

[0021] The catalyst of the present invention can efficiently remove phenylarsonic acid pollution in water body; the preparation process of the method of the present invention is simple and the cost is low; the catalyst has good stability and can be reused. Description of the drawings

[0022] Figure 1 It is a graph showing the influence of catalysts with different metal loadings on the removal of phenylarsonic acid (PAA);

[0023] Figure 2 It is a graph showing the influence of different catalyst dosages on the removal of phenylarsonic acid (PAA);

[0024] Figure 3 It is an XRD pattern of the catalyst of iron oxyhydroxide modified electrolytic manganese residue prepared in Example 1;

[0025] Figure 4 It is a graph showing the influence of different dosages of peroxydisulfate (PDS) oxidant on the removal of phenylarsonic acid (PAA). Detailed implementation manners

[0026] The present invention provides a preparation method of a catalyst of iron oxyhydroxide modified electrolytic manganese residue, comprising the following steps:

[0027] 1) Adding manganese slag powder into water for ultrasonic treatment, and then adding ferric nitrate solution for mixing to obtain a catalyst embryo;

[0028] 2) Place the catalyst mud embryo in a reaction kettle for hydrothermal reaction to obtain the catalyst;

[0029] The mass concentration of the ferric nitrate solution is 0.025 - 0.2 g / mL.

[0030] In the present invention, the mass concentration of the ferric nitrate solution is preferably 0.05 - 0.2 g / mL, and more preferably 0.1 - 0.2 g / mL.

[0031] In the present invention, the preparation of the manganese slag powder is as follows: Wash the electrolytic manganese slag with distilled water to remove impurities, and then dry it in an oven at 60 °C for 24 h; Crush the dried electrolytic manganese slag to a particle size of 120 - 200 μm, preferably 150 μm.

[0032] In the present invention, the mass ratio of the distilled water to the electrolytic manganese slag is preferably 4:1.

[0033] In the present invention, the mass ratio of the manganese slag powder to ferric nitrate in the ferric nitrate solution is 1:0.5 - 4, preferably 1:1 - 3, and more preferably 1:2 - 3.

[0034] In the present invention, the mass - to - volume ratio of the manganese slag powder to water is 1 g: 30 - 50 mL, preferably 1 g: 40 mL.

[0035] In the present invention, the time of the ultrasonic treatment is 20 - 40 min, preferably 30 min.

[0036] In the present invention, the temperature of the hydrothermal reaction is 150 - 170 °C, preferably 155 - 165 °C, and more preferably 160 °C; The time of the hydrothermal reaction is 14 - 18 h, preferably 16 h.

[0037] In the present invention, the mixing is carried out under stirring, the rotation speed of the stirring is 500 - 700 rpm, preferably 600 rpm; The time of the stirring is 1 - 3 h, preferably 2 h.

[0038] The present invention also provides a hydroxyl iron oxide - modified electrolytic manganese slag catalyst.

[0039] The present invention provides an application of the hydroxyl iron oxide - modified electrolytic manganese slag catalyst in removing phenylarsonic acid pollution in water bodies. The hydroxyl iron oxide - modified electrolytic manganese slag catalyst and peroxydisulfate are used in combination and put into the phenylarsonic acid - polluted wastewater;

[0040] The dosage of the hydroxyl iron oxide - modified electrolytic manganese slag catalyst in the phenylarsonic acid - polluted wastewater is 0.2 - 0.8 g / L; The dosage of the peroxydisulfate is 0.1 - 0.4 g / L.

[0041] In the present invention, the dosage of the iron oxyhydroxide-modified electrolytic manganese residue catalyst in the phenylarsonic acid-polluted wastewater is preferably 0.3 - 0.5 g / L, and more preferably 0.4 g / L.

[0042] In the present invention, the dosage of the persulfate in the phenylarsonic acid-polluted wastewater is 0.1 - 0.4 g / L, and preferably 0.3 g / L.

[0043] The technical solutions provided by the present invention will be described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0044] Example 1

[0045] The preparation method of the iron oxyhydroxide-modified electrolytic manganese residue catalyst includes the following steps:

[0046] (1) Pretreatment of electrolytic manganese residue

[0047] Washing manganese residue: Wash the electrolytic manganese residue with distilled water to remove impurities (mass ratio, water:manganese residue = 4:1), and then dry it in an oven at 60 °C for 24 h.

[0048] Grinding electrolytic manganese residue: Crush the electrolytic manganese residue to 100 mesh (150 μm) and then set aside.

[0049] (2) Preparation of catalyst embryo

[0050] Preparation of iron salt solution: Add 3 g of ferric nitrate nonahydrate to 20 mL of water to prepare a ferric nitrate solution.

[0051] Dispersion and impregnation of manganese residue: Put 1 g of manganese residue powder into 40 mL of water, ultrasonically treat it for 30 min, and add the ferric nitrate solution and stir at 550 rpm for 2 h.

[0052] (3) Preparation of catalyst

[0053] Hydrothermal reaction: Place the catalyst embryo in a polytetrafluoroethylene inner liner and carry out a hydrothermal reaction at 160 °C for 16 h to form the active components and stable structure of the catalyst.

[0054] Example 2

[0055] The preparation method of the iron oxyhydroxide-modified electrolytic manganese residue catalyst includes the following steps:

[0056] (1) Pretreatment of electrolytic manganese residue

[0057] Washing manganese residue: Wash the electrolytic manganese residue with distilled water to remove impurities (mass ratio, water:manganese residue = 4:1), and then dry it in an oven at 60 °C for 24 h.

[0058] Pretreatment of electrolytic manganese residue: The electrolytic manganese residue is crushed to 100 mesh (150 μm) and then reserved for use.

[0059] (2) Preparation of catalyst green body

[0060] Preparation of iron salt solution: 1 g of ferric nitrate nonahydrate is added to 20 mL of water to prepare a ferric nitrate solution.

[0061] Dispersion and impregnation of manganese residue: 1 g of manganese residue powder is put into 40 mL of water, ultrasonically treated for 30 min, and then the ferric nitrate solution is added and stirred at 550 rpm for 2 h.

[0062] (3) Preparation of catalyst

[0063] Hydrothermal reaction: The catalyst green body is placed in a polytetrafluoroethylene inner liner and subjected to hydrothermal reaction at 160 °C for 16 h to form the active components and stable structure of the catalyst.

[0064] Example 3

[0065] A preparation method of a hydroxyl iron oxide modified electrolytic manganese residue catalyst, comprising the following steps:

[0066] (1) Pretreatment of electrolytic manganese residue

[0067] Washing manganese residue: The electrolytic manganese residue is washed with distilled water to remove impurities (mass ratio, water: manganese residue = 4:1), and then dried in an oven at 60 °C for 24 h.

[0068] Pretreatment of electrolytic manganese residue: The electrolytic manganese residue is crushed to 100 mesh (150 μm) and then reserved for use.

[0069] (2) Preparation of catalyst green body

[0070] Preparation of iron salt solution: 0.5 g of ferric nitrate nonahydrate is added to 20 mL of water to prepare a ferric nitrate solution.

[0071] Dispersion and impregnation of manganese residue: 1 g of manganese residue powder is put into 40 mL of water, ultrasonically treated for 30 min, and then the ferric nitrate solution is added and stirred at 550 rpm for 2 h.

[0072] (3) Preparation of catalyst

[0073] Hydrothermal reaction: The catalyst green body is placed in a polytetrafluoroethylene inner liner and subjected to hydrothermal reaction at 160 °C for 16 h to form the active components and stable structure of the catalyst.

[0074] Example 4

[0075] A preparation method of a hydroxyl iron oxide modified electrolytic manganese residue catalyst, comprising the following steps:

[0076] (1) Pretreatment of electrolytic manganese residue

[0077] Washed manganese slag: Wash the electrolytic manganese slag with distilled water to remove impurities (mass ratio, water: manganese slag = 4:1), and then dry it in an oven at 60 °C for 24 h.

[0078] Grinding of electrolytic manganese slag: Crush the electrolytic manganese slag to 100 mesh (150 μm) and then set aside.

[0079] (2) Preparation of catalyst green body

[0080] Preparation of iron salt solution: Add 3 g of ferric nitrate nonahydrate to 20 mL of water to prepare a ferric nitrate solution.

[0081] Dispersion and impregnation of manganese slag: Put 1 g of manganese slag powder into 40 mL of water, ultrasonically treat for 30 min, and add the ferric nitrate solution and stir at 600 rpm for 2 h.

[0082] (3) Preparation of catalyst

[0083] Hydrothermal reaction: Place the catalyst green body in a polytetrafluoroethylene inner liner and carry out a hydrothermal reaction at 150 °C for 16 h to form the active components and stable structure of the catalyst.

[0084] Example 5

[0085] Preparation method of iron oxyhydroxide modified electrolytic manganese slag catalyst, comprising the following steps:

[0086] (1) Pretreatment of electrolytic manganese slag

[0087] Washed manganese slag: Wash the electrolytic manganese slag with distilled water to remove impurities (mass ratio, water: manganese slag = 4:1), and then dry it in an oven at 60 °C for 24 h.

[0088] Grinding of electrolytic manganese slag: Crush the electrolytic manganese slag to 100 mesh (150 μm) and then set aside.

[0089] (2) Preparation of catalyst green body

[0090] Preparation of iron salt solution: Add 3 g of ferric nitrate nonahydrate to 20 mL of water to prepare a ferric nitrate solution.

[0091] Dispersion and impregnation of manganese slag: Put 1 g of manganese slag powder into 40 mL of water, ultrasonically treat for 30 min, and add the ferric nitrate solution and stir at 500 rpm for 3 h.

[0092] (3) Preparation of catalyst

[0093] Hydrothermal reaction: Place the catalyst green body in a polytetrafluoroethylene inner liner and carry out a hydrothermal reaction at 170 °C for 14 h to form the active components and stable structure of the catalyst.

[0094] Application Example 1

[0095] Measure 200 mL of deionized water in a conical flask, add phenylarsonic acid, control the concentration of phenylarsonic acid to 10 mg / L, divide it into 4 equal parts, and then add modified electrolytic manganese slag catalysts with different loadings of iron hydroxide (0 g, 0.5 g, 1 g, 3 g) at 0.4 g / L respectively. The adsorption stage is controlled for 1 hour, and then peroxydisulfate PDS is added, with a dosage of 0.3 g / L. Sampling is carried out at time points of adsorption time 0 min, 10 min, 30 min, 60 min and degradation time 0 min, 5 min, 15 min, 30 min, 60 min, 90 min, 120 min. The comparison shows that the more the iron loading, the better the removal activity (such as Figure 1 ).

[0096] Application Example 2

[0097] Measure 200 mL of deionized water in a conical flask, add phenylarsonic acid, control the concentration of phenylarsonic acid to 10 mg / L, divide it into 3 equal parts, and then add modified electrolytic manganese slag catalysts prepared in Example 1 at 0.2 g / L, 0.3 g / L, and 0.4 g / L respectively. The adsorption stage is controlled for 1 hour, and then peroxydisulfate PDS is added, with a dosage of 0.3 g / L. Sampling is carried out at time points of adsorption time 0 min, 10 min, 30 min, 60 min and degradation time 0 min, 10 min, 30 min, 60 min, 90 min, 120 min. As Figure 2 shown, the figure shows pre-adsorption from -60 to 0 minutes and degradation from 0 to 120 minutes. It can be seen that with the increase of the catalyst dosage, the removal efficiency of phenylarsonic acid increases simultaneously. The effect is the best when the dosage is 1 g. When the catalyst addition amount reaches 0.4 g / L, phenylarsonic acid is completely removed within 180 min. Considering the cost, the optimal addition amount of the catalyst can be determined to be 0.4 g / L.

[0098] Application Example 3

[0099] Measure 200 mL of deionized water in a conical flask, add phenylarsonic acid, control the concentration of phenylarsonic acid to 10 mg / L, divide it into 4 equal parts, and then add modified electrolytic manganese slag catalysts prepared in Example 1 at 0.4 g / L respectively. The adsorption stage is controlled for 1 hour, and then PDS is added, with dosages of 0.1 g / L, 0.2 g / L, 0.3 g / L, and 0.4 g / L respectively. Sampling is carried out at time points of adsorption time 0 min, 10 min, 30 min, 60 min and degradation time 0 min, 10 min, 30 min, 60 min, 90 min, 120 min. According to the experimental results, when the oxidant dosage reaches 0.3 g / L, continuing to increase the oxidant, the growth rate of the removal rate is not obvious. The optimal addition amount of the oxidant can be determined to be 0.3 g / L (such as Figure 4 ).

[0100] Figure 3 XRD pattern of the iron oxyhydroxide modified electrolytic manganese residue catalyst prepared in Example 1. As can be seen from the figure, the Fe on the catalyst is mainly α-FeOOH, and the main component of the electrolytic manganese residue carrier is silica. From the perspective of materials science, the XRD analysis results reveal that the substance loaded on the manganese residue in the hydrothermally synthesized material is mainly α-FeOOH, and this discovery is crucial for understanding the source of the catalyst's activity. α-FeOOH plays a key role in catalytic oxidation reactions due to its unique structure and chemical properties.

[0101] As can be seen from the above examples, the present invention provides an iron oxyhydroxide modified electrolytic manganese residue catalyst, its preparation method and application. The catalyst is prepared by modifying electrolytic manganese residue with iron oxyhydroxide. The catalyst can effectively remove phenylarsonic acid pollution in water, simultaneously realize the resource utilization of manganese residue, reduce environmental pollution, and provide a new technical approach for water pollution treatment.

[0102] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can be made, and these improvements and refinements should also be regarded as the protection scope of the present invention.

Claims

1. A method for preparing an iron oxyhydroxide modified electrolytic manganese slag catalyst, characterized in that: The following steps are involved: 1) adding manganese slag powder into water for ultrasonic treatment, and then adding ferric nitrate solution for mixing to obtain catalyst mud embryo; 2) placing the catalyst clay embryo in a reactor for hydrothermal reaction to obtain a catalyst; The mass concentration of the ferric nitrate solution is 0.025-0.2 g / mL.

2. The method for preparing the iron oxyhydroxide modified electrolytic manganese slag catalyst according to claim 1, characterized in that: The particle size of the manganese slag powder is 120-200 μm.

3. The method for preparing the iron oxyhydroxide modified electrolytic manganese slag catalyst according to claim 1 or 2, characterized in that: The mass ratio of the manganese slag powder to the ferric nitrate in the ferric nitrate solution is 1:0.5-4; The mass volume ratio of the manganese slag powder to water is 1g:30-50mL.

4. The method for preparing the iron oxyhydroxide modified electrolytic manganese slag catalyst according to claim 1, characterized in that: The ultrasonic treatment time is 20 to 40 minutes.

5. The method for preparing the iron oxyhydroxide modified electrolytic manganese slag catalyst according to claim 1, 2 or 4, characterized in that: The temperature of the hydrothermal reaction is 150-170° C., and the time of the hydrothermal reaction is 14-18 hours.

6. The method for preparing the iron oxyhydroxide modified electrolytic manganese slag catalyst according to claim 5, characterized in that: The mixing is performed under stirring, the stirring speed is 500-700 rpm, and the stirring time is 1-3 hours.

7. The iron oxyhydroxide modified electrolytic manganese slag catalyst prepared by the preparation method according to any one of claims 1 to 6.

8. The use of the iron oxyhydroxide modified electrolytic manganese slag catalyst according to claim 7 in removing phenylarsonic acid pollution in water, characterized in that: The electrolytic manganese slag catalyst modified by ferric oxyhydroxide and peroxodisulfate are used together and added into the wastewater contaminated by phenylarsonic acid; The dosage of the iron oxyhydroxide modified electrolytic manganese slag catalyst in the wastewater contaminated by phenylarsonic acid is 0.2-0.8 g / L; the dosage of the peroxodisulfate is 0.1-0.4 g / L.

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