Method for preparing catalytic material from copper slag and application thereof

Abstract

The application discloses a method for preparing a catalytic material from copper slag, which comprises the following steps: placing the copper slag in a dilute acid solution, stirring and reacting at 70-80 DEG C, and separating the solid from the liquid; placing the filtered residue in a muffle furnace for calcination, cooling, and placing the calcined product in the filtrate for sufficient stirring; then adding a reducing agent to the filtrate with pH 1.5-5 under a nitrogen atmosphere, stirring and reacting, and then standing under a nitrogen atmosphere, and separating the solid from the liquid; and washing and vacuum drying the solid to obtain the catalytic material; the prepared catalyst material can be used for degrading methylene blue, rhodamine B, methyl orange and hexavalent chromium, and can efficiently catalyze the degradation and removal of methylene blue, rhodamine B, methyl orange and hexavalent chromium, so as to achieve the purpose of treating waste with waste and fully utilizing resources, and the social and economic benefits are remarkable; and the method has the characteristics of simple process, low cost, high resource utilization rate and no special requirement for equipment, and is suitable for industrial production and market promotion and utilization.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of copper residue resource utilization, and particularly relates to a method for preparing a catalytic material from copper residue and application thereof. BACKGROUND

[0002] Copper residue is a solid waste generated in the process of copper production by pyrometallurgy of copper sulfide minerals, which is composed of glass body and part of magnetite. The domestic treatment of copper residue is mainly landfill, which not only occupies a large amount of land, but also causes great harm to the environment and human health due to the infiltration of heavy metals in the residue into nature. Therefore, proper treatment of copper residue is necessary. On the other hand, copper residue is rich in Fe (30-45%), and its grade is higher than that of many iron ores, which has obvious resource properties and great development value, especially the application field of iron resources is wide, such as iron-based catalyst as a mature catalyst system, which has been widely used in various catalytic reactions, such as MB degradation, methane decomposition, and catalytic degradation of various antibiotics, etc. At the same time, iron-based catalyst has a relatively fast catalytic efficiency, which is concerned by researchers. Therefore, it is very important to develop a method for efficient recycling of copper residue.

[0003] The prior art 202310082042.3 discloses a method for simultaneously recycling iron resources and silicon resources in copper residue, which mixes copper residue and molten salt in a CO2 atmosphere for oxidation roasting, and finally obtains iron concentrate and silicon leaching solution through alkali leaching and magnetic separation. The prior art 202310140097.5 discloses a harmless secondary utilization method of copper residue, which obtains high-grade copper concentrate through multiple grinding, magnetic separation and separation of copper residue. These processes mainly aim at the extraction of valuable elements in copper residue, and the treatment process is relatively complicated, the equipment requirement is high, the cost is high, the extraction rate of iron is low, and the added value of the product is low. Therefore, it is necessary to develop a copper residue treatment process with low consumption, high efficiency and high added value of the product. SUMMARY

[0004] The application provides a method for preparing a catalytic material from copper residue, which not only realizes a high extraction rate of iron elements in copper residue, but also provides a new idea for high-value resource utilization of copper residue, efficiently decomposes methylene blue, rhodamine B, methyl orange and hexavalent chromium, and relieves the harm of copper residue, methylene blue, rhodamine B, methyl orange and hexavalent chromium to the environment, thereby obtaining good economic, social and environmental benefits.

[0005] In the application, the copper residue is electric furnace slag generated in the process of copper production by pyrometallurgy of copper sulfide minerals, and the copper residue comprises Fe 30-45%, Si 11-17%, Cu 0.5-2.7%, Pb 0.1-1.02% and As 0.04-0.4%.

[0006] The method for preparing a catalytic material from copper residue according to the application is as follows:

[0007] 1, the copper residue is put into a dilute acid solution, heated and stirred in a water bath, and solid-liquid separation is carried out to obtain a filtrate and a filter residue;

[0008] The dilute acid solution is hydrochloric acid or sulfuric acid with a volume concentration of 20-25%, the heating temperature is 70-80 DEG C, and the stirring time is 4-5 h;

[0009] 2, the filter residue is placed in a muffle furnace for heat treatment, and the heat-treated residue is obtained after cooling;

[0010] The heating temperature is 1000-1200 DEG C, the heating rate is 15-20 DEG C / min, and the holding time is 1-2 h;

[0011] 3, the filtrate is diluted to adjust the pH value to 1.5-5, and then mixed with the heat-treated residue and stirred;

[0012] The dilution and pH adjustment of the filtrate is achieved by adding distilled water to the filtrate to obtain a filtrate with a pH of 1.5-5;

[0013] 4, under a nitrogen atmosphere, a reducing agent is added to the filtrate of step 3, and the reaction is stirred until the reaction solution becomes colorless, and then the reaction solution is left to stand under a nitrogen atmosphere for 8-12 h, and then solid-liquid separation is carried out, and the solid is washed and vacuum dried to obtain the catalytic material;

[0014] The vacuum drying temperature is 60-70 DEG C, and the reducing agent is KBH4.

[0015] Another object of the present application is to apply the catalytic material prepared by the above method to catalytic degradation of methylene blue, rhodamine B, methyl orange and hexavalent chromium.

[0016] The present application has the following technical effects:

[0017] The present application uses copper residue as the iron source, not only achieving the purpose of harmless treatment of copper residue, but also realizing fine and high-value-added comprehensive utilization of copper residue, and providing a cheap raw material for the preparation of catalyst materials; the raw material is simple and easy to obtain, the cost is low, it is suitable for large-scale production, and it is environmentally friendly; the catalyst material prepared by the present application can catalytically degrade methylene blue, rhodamine B, methyl orange and hexavalent chromium, and can efficiently remove methylene blue, rhodamine B, methyl orange and hexavalent chromium, achieving the purpose of waste treatment and fully utilizing resources, and the social and economic benefits are significant; and the catalyst prepared by the method of the present application has high dispersion and is not prone to agglomeration compared to ordinary catalysts; and the method of the present application has the characteristics of simple process, low cost, high resource utilization rate, no special requirements for equipment, and is suitable for industrial production and market promotion and utilization. DETAILED DESCRIPTION

[0018] The further description of the present application is made below in conjunction with the specific embodiments, which are not intended to limit the protection scope of the present application, but to illustrate the principles of the present application together with the embodiments of the present application, and are not intended to limit the scope of the present application.

[0019] The copper slag selected in the following examples is the electric furnace slag of a certain factory in Yunnan, with a particle size less than 0.425 mm (40 mesh), Fe 44.36%, Si 12.9%, Cu 1.89%, Pb 0.58%, As 0.22%, S 1.13%, and Al 2.94%; the dilute acid solution is dilute hydrochloric acid solution, the reducing agent is KBH4, and the chemical pure reagent. Example 1

[0020] The copper slag 10 g was mixed with 100 mL of dilute hydrochloric acid with a concentration of 5%, 10%, 15%, 20%, and 25%, respectively, and stirred at 70℃ for 4 h, and then centrifuged to obtain the filtrate; the contents of Fe, As, and Pb in the filtrate were determined by ICP, and the experimental results showed that the leaching rates of Fe in 10 g of copper slag in different concentrations of dilute hydrochloric acid were 22.82% (1.01 g), 55.74% (2.47 g), 70.18% (3.11 g), 81.44% (3.61 g), and 76.42% (3.39 g), respectively; the leaching rates of As in the copper slag were 6.93% (1.53 mg), 24.16% (5.33 mg), 32.95% (7.27 mg), and 34.28% (7.57 mg), respectively; and the leaching rates of Pb in the copper slag were 30.28% (17.67 mg), 71.38% (41.65 mg), 84.83% (49.5 mg), 89.17% (52.03 mg), and 82.17% (47.95 mg), respectively.

[0021] The filter residue obtained by centrifugation was placed in a muffle furnace, heated to 1000℃ at a rate of 16℃ / min and kept for 2 h, and then cooled to obtain a heat-treated slag; 5 mL of the filtrate was diluted with water to 30 mL (pH greater than 1.5), and then the heat-treated slag was fully stirred in the diluted filtrate; 20 mL of a solution containing 1 g of KBH4 was added to the diluted solution under a nitrogen atmosphere, and stirred for 60 min; after standing for 12 h under a nitrogen atmosphere, the solid-liquid was separated by centrifugation, and the solid was washed with distilled water and ethanol for 3 times, respectively, and then vacuum dried at 70℃ to obtain a catalytic material;

[0022] 2. 10 mg of the catalytic material prepared in the above examples, 100 μL of H2O2, and 100 mL of methylene blue solution with a concentration of 50 mg / L and a pH value of 4.5 were added, and the degradation of methylene blue was detected at 1 min, 5 min, 10 min, 15 min, 20 min, and 25 min, respectively;

[0023] The results show that when the concentration of dilute hydrochloric acid is 5%, the degradation rate of methylene blue is 7.13%, 12.72%, 15.99%, 16.09%, 16.18%, and 16.67%; when the concentration of dilute hydrochloric acid is 10%, the degradation rate of methylene blue is 4.59%, 8.22%, 14.44%, 14.63%, 14.72%, and 17.97%; and when the concentration of dilute hydrochloric acid is 20%, the degradation rate of methylene blue is 17.34%, 53.17%, 64.52%, 74.17%, 82.69%, and 83.25%, respectively.

[0024] In Example 2, 10 g of copper slag was mixed with 100 mL of 20% dilute hydrochloric acid, and stirred at 40°C for 4 h. After centrifugal separation, 5 mL of filtrate was obtained, diluted with water to 30 mL (pH>1.5), and the filter residue obtained by centrifugal separation was placed in a muffle furnace, heated to 1100°C at a rate of 16°C / min and kept for 1 h. After cooling, the filter residue was fully stirred in the diluted filtrate, and 20 mL of a solution containing 1 g of KBH4 was added to the diluted filtrate under a nitrogen atmosphere. After stirring for 60 min, the mixture was left standing for 8 h under a nitrogen atmosphere, and then centrifugal solid-liquid separation was performed. The solid was washed with distilled water and ethanol for 3 times, respectively, and then vacuum dried at 65°C to obtain a catalytic material.

[0025] In Example 2, 10 g of copper slag was mixed with 100 mL of 20% dilute hydrochloric acid, and stirred at 40°C for 4 h. After centrifugal separation, 5 mL of filtrate was obtained, diluted with water to 30 mL (pH>1.5), and the filter residue obtained by centrifugal separation was placed in a muffle furnace, heated to 1100°C at a rate of 16°C / min and kept for 1 h. After cooling, the filter residue was fully stirred in the diluted filtrate, and 20 mL of a solution containing 1 g of KBH4 was added to the diluted filtrate under a nitrogen atmosphere. After stirring for 60 min, the mixture was left standing for 8 h under a nitrogen atmosphere, and then centrifugal solid-liquid separation was performed. The solid was washed with distilled water and ethanol for 3 times, respectively, and then vacuum dried at 65°C to obtain a catalytic material.

[0026] In Example 3, the preparation method of the catalytic material is the same as that in Example 1.

[0027] In Example 3, the preparation method of the catalytic material is the same as that in Example 1.

[0028] The catalytic material was used to treat 100 mL of a methyl orange solution with a concentration of 20 mg / L and a pH value of 4.5, and the degradation rate of the methyl orange solution was 80% at 25 min.

[0029] The catalytic material was used to treat 100 mL of a solution containing hexavalent chromium with a concentration of 5 mg / L and a pH value of 3, and the degradation rate of the hexavalent chromium was 94% at 10 min.

Claims

1. The use of a catalytic material prepared from copper slag in the catalytic degradation of methylene blue, rhodamine B, methyl orange, hexavalent chromium, characterized in that: The catalytic material is prepared by placing copper residue in a dilute acid solution, stirring and reacting at 70-80 ℃, solid-liquid separation, placing the filtered residue in a muffle furnace for calcination, cooling, placing the calcined product in the filtrate for stirring, then adding a reducing agent in the filtrate with pH 1.5-5 under a nitrogen atmosphere, stirring and reacting, standing under a nitrogen atmosphere, solid-liquid separation, washing the solid, and vacuum drying to obtain the catalytic material. The dilute acid solution is hydrochloric acid or sulfuric acid with a volume concentration of 20-25%.

2. Use according to claim 1, characterized in that: The calcination temperature is 1000-1200 ℃, and the time is 1-2 h.

3. Use according to claim 1, characterized in that: The standing time is 8-12 h.

4. Use according to claim 1, characterized in that: The reducing agent is KBH4.