Method for preparing porous ceramic filter balls from electrolytic manganese residues

Abstract

The invention discloses a method for preparing a porous ceramic filter ball from electrolytic manganese residues, and relates to the technical field of environmental protection and ceramic materials, and the method comprises the following steps: (1) raw material treatment: crushing the electrolytic manganese residues into particles of 2-3 cm, drying by using a dryer, and after drying, carrying out ball milling and sieving on the electrolytic manganese residues by using a planetary ball mill to obtain a raw material; (2) weighing and proportioning raw materials: weighing and proportioning the raw materials in percentage by weight: 50-80% of electrolytic manganese residues, 20-50% of calcined kaolin, 0-10% of an additional cosolvent and 0-10% of a pore-forming agent; (3) mixing the raw materials; and (4) granulating and aging the mixture. According to the method for preparing the porous ceramic filter balls from the electrolytic manganese residues, a brand new path is developed for comprehensive utilization of the electrolytic manganese residues, the path enables the utilization rate of the electrolytic manganese residues to be greatly increased, the path becomes an extremely effective path for consuming the electrolytic manganese residues, the electrolytic manganese residues can be fully utilized due to the characteristic of high utilization rate, and efficient cyclic utilization of resources is achieved.

Description

Technical Field

[0001] The invention relates to the technical field of environmental protection and ceramic materials, and in particular to a method for preparing porous ceramic filter balls by electrolyzing manganese slag. Background Art

[0002] Electrolytic manganese slag is the waste residue produced after solid-liquid separation in the filter pressing process during the electrolytic production of metallic manganese. It is black in appearance, with fine particles and a density between 2-3g / cm. When discharged directly, the moisture content is high. When piled in the open air, the moisture content will be higher due to the storage of rainwater, and it may even be in a slurry state. After long-term air drying in the open air, the particles will agglomerate together. The heavy metal elements in electrolytic manganese slag are highly bioaccumulative and toxic in the natural environment. The heavy metal elements may enter the water body through surface runoff, groundwater and atmospheric deposition, causing water pollution and causing serious harm to aquatic organisms. Heavy metal elements may also enter the human body through the food chain, posing a potential threat to human health. People who are exposed to high-concentration heavy metal pollution for a long time may experience symptoms of chronic poisoning. Nowadays, the treatment of stockpiled electrolytic manganese slag has become a key breakthrough for green development.

[0003] Different approaches have been proposed for the treatment of electrolytic manganese slag at home and abroad. Physical separation and chemical separation can be used to collect valuable metals in electrolytic manganese slag, and some components in electrolytic manganese slag can be used to make functional materials, or electrolytic manganese slag can be directly used. Using electrolytic manganese slag to prepare porous ceramics is an important way to utilize electrolytic manganese slag resources. This method has a large treatment capacity for manganese slag, is simple, low cost, uses less materials, and has a good fixation effect on toxic substances in electrolytic manganese slag, and will not cause secondary pollution to the environment.

[0004] Patent publication number CN102584316 A discloses a method for preparing porous ceramics using electrolytic manganese slag. The above method uses a high content of pore-forming agent and requires a binder during preparation, and the process is cumbersome and increases costs. Therefore, we propose a method for preparing porous ceramic filter balls using electrolytic manganese slag. Summary of the invention

[0005] The technical problem to be solved by the present invention is to overcome the existing defects and provide a method for preparing porous ceramic filter balls from electrolytic manganese slag. The consumption of electrolytic manganese slag is large. By consuming a large amount of electrolytic manganese slag, the problem of electrolytic manganese slag storage that has long troubled people can be effectively solved. The process is simple and does not require complicated and tedious operating procedures, which greatly reduces the difficulty of implementation. At the same time, the cost is extremely low and will not bring a heavy economic burden to the producer, which can effectively solve the problems in the background technology.

[0006] To achieve the above object, the present invention provides the following technical solution: a method for preparing porous ceramic filter balls from electrolytic manganese slag, comprising the following steps: (1) Raw material processing: crush the electrolytic manganese slag into particles of 2 to 3 cm, dry them in a dryer, and then use a planetary ball mill to ball mill and sieve the electrolytic manganese slag to obtain the raw material; (2) Raw material weighing and proportioning: weigh and proportion the raw materials by weight percentage: 50-80% electrolytic manganese slag, 20-50% calcined kaolin, 0-10% additional solvent, and 0-10% pore-forming agent; (3) Raw material mixing: using a planetary ball mill to mix the raw materials to obtain a mixed material; (4) Granulation and aging of the mixture: The mixture is granulated to prepare a blank with a certain particle size, and the blank is aged after granulation; (5) Preparation of ceramic filter ball embryos: The aged embryos are formed by a granulator to obtain ceramic filter ball embryos; (6) Preparation of ceramic filter balls: The ceramic filter ball embryos are dried in a dryer at 100-105°C for 2-4 hours, and then sintered in a sintering furnace to obtain porous ceramic filter balls.

[0007] Furthermore, the added auxiliary solvent in step (2) is one of ZnO, Na2O or K2O.

[0008] Furthermore, the pore-forming agent in step (2) is wood chips or carbon powder.

[0009] Furthermore, the particle size of the ceramic filter ball embryo prepared in step (5) is 1 cm.

[0010] Furthermore, the porous ceramic filter ball in step (6) is naturally cooled to below 100° C. in the sintering furnace and then taken out.

[0011] Furthermore, in step (1), the drying temperature is 80 to 95° C., and the drying time is 6 to 12 hours.

[0012] Furthermore, in step (3), the rotation speed of the planetary ball mill is 450 r / min, and the mixing is performed for 3 to 5 minutes.

[0013] Furthermore, in step (4), the aging time of the blank is more than 1 day.

[0014] Furthermore, in step (6), the sintering temperature is between 1000°C and 1250°C.

[0015] Furthermore, in step (1), the ball milling time is 3 to 5 minutes, and then the raw material is sieved through a 200-mesh sieve to obtain the raw material.

[0016] Compared with the prior art, the invention has the following beneficial effects: the method for preparing porous ceramic filter balls from electrolytic manganese slag has the following advantages: 1. A new path has been opened up for the comprehensive utilization of electrolytic manganese slag, which greatly improves the utilization rate of electrolytic manganese slag and becomes an extremely effective way to consume electrolytic manganese slag. The high utilization rate allows electrolytic manganese slag to be fully utilized, reduces the negative impact on the environment, and realizes the efficient recycling of resources.

[0017] 2. The cost of raw materials is low, which can reduce production investment and save money; there are fewer types of raw materials, which is easy to purchase and manage, reducing complex operations and potential risks; the sample preparation process is simple and convenient, without the need for complex equipment and cumbersome steps, which improves work efficiency. High-quality samples can be quickly prepared in the laboratory and actual production, providing strong support for subsequent research and application.

[0018] 3. The porous ceramic filter balls produced have high strength, high porosity and uniform distribution, and most of the pores are through holes generated by gas volatilization, providing good conditions for adsorption and loading of catalysts.

[0019] 4. Mullite and zinc spinel are generated during firing, which improves the strength, wear resistance, acid and alkali resistance of porous ceramics, increases service life, and makes it better suitable for different types of sewage.

[0020] 5. High utilization rate of components in electrolytic manganese slag: NH4+-N and CaO4 in electrolytic manganese slag are used to volatilize and form pores, Al203 in the slag is used to form spinel, SiO2 generated by kaolin in the slag is used to form glass to wrap and fix the Mn element in the slag, and Mn will also enter the crystal lattice of the formed crystal for fixation. Part of the metal oxidation in the manganese slag can also play a fluxing effect to reduce the sintering temperature.

[0021] 6. Porous ceramic filter balls have good performance and can use their characteristics to absorb and treat sewage and filter impurities, providing a new method for the treatment of electrolytic manganese slag. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 This is the SEM picture of electrolytic manganese slag and calcined kaolin at 1170°C of the present invention.

[0023] Figure 2 This is the SEM picture of electrolytic manganese slag, calcined kaolin, ZnO and pore-forming agent at 1170°C of the present invention. DETAILED DESCRIPTION

[0024] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0025] See also Figure 1-2 The present invention provides a technical solution: a method for preparing porous ceramic filter balls by electrolyzing manganese slag, comprising the following steps: (1) Raw material processing: crush the electrolytic manganese slag into particles of 2 to 3 cm, dry it in a dryer at a temperature of 80 to 95°C for 6 to 12 hours, and then use a planetary ball mill to ball mill and sieve the electrolytic manganese slag to obtain the raw material for 3 to 5 minutes, and then pass it through a 200-mesh sieve; The present invention adopts manganese carbonate electrolytic manganese slag, and mainly utilizes SiO2, Al2O3, NH4+-N, CaSO4.2H2O and other components in the electrolytic manganese slag.

[0026] (2) Raw material weighing and proportioning: weigh and proportion the raw materials by weight percentage: 50-80% electrolytic manganese slag, 20-50% calcined kaolin, 0-10% additional solvent, and 0-10% pore-forming agent; The purpose of adding calcined kaolin is to generate mullite when calcining kaolin at high temperature to improve the mechanical properties of ceramics, improve the thermal stability of ceramics, and enhance the chemistry of ceramics. The generated mullite can increase the porosity of ceramics.

[0027] The added co-solvent is one of ZnO, Na2O or K2O, and the pore-forming agent is sawdust or carbon powder; The amount of ZnO added is 0-10%. At 600℃, zinc spinel will be generated in aluminum-rich raw materials. As the temperature rises, zinc spinel gradually grows. It can reduce the firing temperature of ceramics in the ligand, and can help the nucleation and growth of crystals. The electrolytic manganese slag contains SiO2 phase, and the kaolin generates mullite. It forms a complex phase of SiO2-mullite-zinc spinel-calcite above 1000℃. Since zinc spinel can help nucleation and growth, mullite will be generated and grow rapidly above 1000 degrees Celsius. Mullite and zinc spinel are both refractory materials that can increase the sintering range of the embryo, that is, increase the sintering temperature. And above 1000℃, CaSO4 in the electrolytic manganese slag decomposes to form gas, and the embryo is in the form of solid-liquid coexistence. As the gas volatilizes, the embryo self-foams and the embryo volume expands, increasing the porosity of the embryo.

[0028] (3) Raw material mixing: The raw materials are mixed using a planetary ball mill to obtain a mixed material. The speed of the planetary ball mill is 450 r / min and the mixing time is 3 to 5 minutes. (4) Granulation and aging of the mixture: The mixture is granulated to prepare a blank with a certain particle size. After granulation, the blank is aged for more than 1 day. (5) Preparation of ceramic filter ball embryos: The aged embryos are formed into ceramic filter ball embryos using a granulator. The particle size of the ceramic filter ball embryos is 1 cm. (6) Preparation of ceramic filter balls: Dry the ceramic filter ball embryos in a dryer at 100-105°C for 2-4 hours, and then sinter them in a sintering furnace to obtain porous ceramic filter balls at a sintering temperature of 1000-1250°C. Cool them naturally in the sintering furnace to below 100°C and take them out; During sintering, start from room temperature and heat at 5℃ / min to the pore-forming temperature of the pore-forming agent, keep warm for 30 minutes, continue to heat to 1000℃ at 5℃ / min, keep warm for 30 minutes to allow the crystals to fully nucleate and grow, continue to heat to the sintering temperature of 1170℃ at 5℃ / min, keep warm for 2 hours to allow CaO4 to fully decompose. Example

[0029] A method for preparing porous ceramic filter balls by electrolyzing manganese slag comprises the following steps: (1) Raw material processing: The electrolytic manganese slag is crushed into particles of 2 to 3 cm, and dried in a dryer at a drying temperature of 90°C for 12 hours. After drying, the electrolytic manganese slag is ball-milled and sieved in a planetary ball mill to obtain the raw material. The speed of the planetary ball mill is 450 r / min, the ball-milling time is 5 min, and then the raw material is sieved through a 200-mesh sieve; (2) Raw material weighing and proportioning: weigh and proportion the raw materials by weight percentage: the ratio of electrolytic manganese slag to calcined kaolin is 1:1, and ZnO is 5%; (3) Raw material mixing: The raw materials are mixed using a planetary ball mill to obtain a mixed material. The speed of the planetary ball mill is 450 r / min and the mixing time is 3 min. (4) Granulation and aging of the mixture: The mixture is granulated to prepare a blank with a certain particle size. After granulation, the blank is aged for 1 day. (5) Preparation of ceramic filter ball embryos: The aged embryos are formed into ceramic filter ball embryos using a granulator. The particle size of the ceramic filter ball embryos is 1 cm. (6) Preparation of ceramic filter balls: Dry the ceramic filter ball embryos in a dryer at 100-105°C for 2-4 hours, then sinter them in a sintering furnace. Raise the temperature at 5°C / min at room temperature to 1000°C and keep it for 30 min. Raise the temperature at 5°C / min to 1170°C and keep it for 2 h. Cool naturally in the sintering furnace to below 100°C and take them out. Example

[0030] A method for preparing porous ceramic filter balls by electrolyzing manganese slag comprises the following steps: (1) Raw material processing: The electrolytic manganese slag is crushed into particles of 2 to 3 cm, and dried in a dryer at a drying temperature of 95°C for 12 hours. After drying, the electrolytic manganese slag is ball-milled and sieved in a planetary ball mill to obtain the raw material. The speed of the planetary ball mill is 450 r / min, the ball-milling time is 5 min, and then the raw material is sieved through a 200-mesh sieve; (2) Raw material weighing and proportioning: weigh and proportion the raw materials by weight percentage: the ratio of electrolytic manganese slag to calcined kaolin is 1:1, ZnO is 5%, and sawdust is 10%; (3) Raw material mixing: The raw materials are mixed using a planetary ball mill to obtain a mixed material. The speed of the planetary ball mill is 450 r / min and the mixing time is 3 min. (4) Granulation and aging of the mixture: The mixture is granulated to prepare a blank with a certain particle size. After granulation, the blank is aged for 1 day. (5) Preparation of ceramic filter ball embryos: The aged embryos are formed into ceramic filter ball embryos using a granulator. The particle size of the ceramic filter ball embryos is 1 cm. (6) Preparation of ceramic filter balls: Dry the ceramic filter ball embryos in a dryer at 100-105°C for 2-4 hours, then sinter them in a sintering furnace. Raise the temperature at 5°C / min at room temperature to 1000°C and keep it for 30 min. Raise the temperature at 5°C / min to 1170°C and keep it for 2 h. Cool naturally in the sintering furnace to below 100°C and take them out. Example

[0031] A method for preparing porous ceramic filter balls by electrolyzing manganese slag comprises the following steps: (1) Raw material processing: The electrolytic manganese slag is crushed into particles of 2 to 3 cm, and dried in a dryer at a drying temperature of 95°C for 12 hours. After drying, the electrolytic manganese slag is ball-milled and sieved in a planetary ball mill to obtain the raw material. The speed of the planetary ball mill is 450 r / min, the ball-milling time is 5 min, and then the raw material is sieved through a 200-mesh sieve; (2) Raw material weighing and proportioning: weigh and proportion the raw materials by weight percentage: the ratio of electrolytic manganese slag to calcined kaolin is 1:1, ZnO is 5%, and carbon powder is 10%; (3) Raw material mixing: The raw materials are mixed using a planetary ball mill to obtain a mixed material. The speed of the planetary ball mill is 450 r / min and the mixing time is 3 min. (4) Granulation and aging of the mixture: The mixture is granulated to prepare a blank with a certain particle size. After granulation, the blank is aged for 1 day. (5) Preparation of ceramic filter ball embryos: The aged embryos are formed into ceramic filter ball embryos using a granulator. The particle size of the ceramic filter ball embryos is 1 cm. (6) Preparation of ceramic filter balls: Dry the ceramic filter ball embryos in a dryer at 100-105°C for 2-4 hours, then sinter them in a sintering furnace. Raise the temperature at 5°C / min at room temperature to 1000°C and keep it for 30 min. Raise the temperature at 5°C / min to 1170°C and keep it for 2 h. Cool naturally in the sintering furnace to below 100°C and take them out. Example

[0032] A method for preparing porous ceramic filter balls by electrolyzing manganese slag comprises the following steps: (1) Raw material processing: The electrolytic manganese slag is crushed into particles of 2 to 3 cm, and dried in a dryer at a drying temperature of 95°C for 12 hours. After drying, the electrolytic manganese slag is ball-milled and sieved in a planetary ball mill to obtain the raw material. The speed of the planetary ball mill is 450 r / min, the ball-milling time is 5 min, and then the raw material is sieved through a 200-mesh sieve; (2) Raw material weighing and proportioning: weigh and proportion the raw materials by weight percentage: the ratio of electrolytic manganese slag to calcined kaolin is 1:1, ZnO is 5%, carbon powder is 5%, and sawdust is 5%; (3) Raw material mixing: The raw materials are mixed using a planetary ball mill to obtain a mixed material. The speed of the planetary ball mill is 450 r / min and the mixing time is 3 min. (4) Granulation and aging of the mixture: The mixture is granulated to prepare a blank with a certain particle size. After granulation, the blank is aged for 1 day. (5) Preparation of ceramic filter ball embryos: The aged embryos are formed into ceramic filter ball embryos using a granulator. The particle size of the ceramic filter ball embryos is 1 cm. (6) Preparation of ceramic filter balls: Dry the ceramic filter ball embryos in a dryer at 100-105°C for 2-4 hours, then sinter them in a sintering furnace. Raise the temperature at 5°C / min at room temperature to 1000°C and keep it for 30 min. Raise the temperature at 5°C / min to 1170°C and keep it for 2 h. Cool naturally in the sintering furnace to below 100°C and take them out.

[0033] The above descriptions are merely embodiments of the present invention and are not intended to limit the patent scope of the present invention. Any equivalent structure or equivalent process transformation made using the contents of the present invention specification and drawings, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. A method for preparing porous ceramic filter balls by electrolytic manganese slag, characterized in that: The following steps are involved: (1) Raw material processing: crush the electrolytic manganese slag into particles of 2 to 3 cm, dry them in a dryer, and then use a planetary ball mill to ball mill and sieve the electrolytic manganese slag to obtain the raw material; (2) Raw material weighing and proportioning: weigh and proportion the raw materials by weight percentage: 50-80% electrolytic manganese slag, 20-50% calcined kaolin, 0-10% additional solvent, and 0-10% pore-forming agent; (3) Raw material mixing: using a planetary ball mill to mix the raw materials to obtain a mixed material; (4) Granulation and aging of the mixture: The mixture is granulated to prepare a blank with a certain particle size, and the blank is aged after granulation; (5) Preparation of ceramic filter ball embryos: The aged embryos are formed into ceramic filter ball embryos by a granulator; (6) Preparation of ceramic filter balls: The ceramic filter ball embryos are dried in a dryer at 100-105°C for 2-4 hours, and then sintered in a sintering furnace to obtain porous ceramic filter balls.

2. The method for preparing porous ceramic filter balls from electrolytic manganese slag according to claim 1, characterized in that: The added auxiliary solvent in step (2) is one of ZnO, Na2O or K2O.

3. The method for preparing porous ceramic filter balls from electrolytic manganese slag according to claim 1, characterized in that: The pore-forming agent in step (2) is wood chips or carbon powder.

4. The method for preparing porous ceramic filter balls from electrolytic manganese slag according to claim 1, characterized in that: The particle size of the ceramic filter ball embryo prepared in step (5) is 1 cm.

5. The method for preparing porous ceramic filter balls from electrolytic manganese slag according to claim 1, characterized in that: The porous ceramic filter ball in step (6) is naturally cooled to below 100° C. in the sintering furnace and then taken out.

6. The method for preparing porous ceramic filter balls from electrolytic manganese slag according to claim 1, characterized in that: In step (1), the drying temperature is 80 to 95° C. and the drying time is 6 to 12 hours.

7. The method for preparing porous ceramic filter balls from electrolytic manganese slag according to claim 1, characterized in that: In step (3), the rotation speed of the planetary ball mill is 450 r / min, and mixing is performed for 3 to 5 minutes.

8. The method for preparing porous ceramic filter balls from electrolytic manganese slag according to claim 1, characterized in that: In step (4), the aging time of the blank is more than 1 day.

9. The method for preparing porous ceramic filter balls from electrolytic manganese slag according to claim 1, characterized in that: In step (6), the sintering temperature is between 1000°C and 1250°C.

10. The method for preparing porous ceramic filter balls from electrolytic manganese slag according to claim 1, characterized in that: In step (1), the ball milling time is 3 to 5 minutes, and then the raw material is sieved through a 200-mesh sieve to obtain the raw material.

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