CN110668466A - Harmless treatment method for electrolytic manganese slag - Google Patents
Harmless treatment method for electrolytic manganese slag Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/022—Preparation of aqueous ammonia solutions, i.e. ammonia water
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/026—Preparation of ammonia from inorganic compounds
- C01C1/028—Preparation of ammonia from inorganic compounds from ammonium sulfate or sulfite
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/14—Cements containing slag
- C04B7/147—Metallurgical slag
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Abstract
The invention discloses a harmless treatment method of electrolytic manganese slag, which comprises the steps of cutting the electrolytic manganese slag into fine particles, putting the fine particles into a stirring device 1, reacting the fine particles with quicklime powder to obtain mixed manganese slag 1, reacting the mixed manganese slag with a composite aqueous solution to obtain mixed manganese slag 2, spraying a potassium silicate aqueous solution to the mixed manganese slag to obtain mixed manganese slag 3, spraying a sodium carbonate aqueous solution to the mixed manganese slag to obtain mixed manganese slag 4, finally screening and crushing, and continuously putting unqualified products into the quicklime for cyclic reaction to obtain the improved manganese slag. The improved manganese slag prepared by the method can be put into cement production to realize resource utilization; meanwhile, ammonia nitrogen collected in the reaction process can be reused for industry or agriculture. The method has the advantages of excellent effect of treating the electrolytic manganese slag, simple process route, low cost, high product strength and good durability, eliminates the environmental pollution caused by the traditional stacking of the electrolytic manganese slag, reduces the slag treatment cost of enterprises, and realizes the purposes of harmless treatment and resource utilization of the electrolytic manganese slag.
Description
Technical Field
The invention belongs to the field of resource recycling, and particularly relates to an electrolytic manganese slag harmless treatment method, improved manganese slag prepared by the method and application thereof, ammonia nitrogen gas collected by the method and application thereof.
Background
In modern industries, manganese and compounds thereof are applied to a plurality of fields, such as the steel industry, the chemical industry (manufacturing various manganese-containing salts), the light industry (for batteries, printing paints and the like), the building material industry (coloring agents and fading agents of glass and ceramics), the defense industry, the electronic industry, environmental protection, agriculture and animal husbandry and the like, wherein the steel industry is the most important field, and accounts for 90 percent of ~ 95 percent of the total manganese content, and the rest 5 percent of ~ 10 percent of manganese is applied to the fields of colored metallurgy, chemical electronics, batteries, agriculture and the like, so that the manganese metal is an important basic substance in national economy.
According to the feedback information of electrolytic manganese enterprises, the grade of manganese ore used for production is generally low, and factors such as laggard electrolytic manganese production process technology are adopted, so that about 8 ~ 12t of electrolytic manganese slag is generated for producing 1t of electrolytic manganese metal on average2+、NH3N and trace heavy metal ions such As Cu, Zn, Cd, As and the like, and if the toxic and harmful substances are not effectively cured or removed, the toxic and harmful substances are very easy to bring serious hidden danger of ecological environment pollution to surrounding areas of enterprises, and can not be recycled.
The harmfulness of the electrolytic manganese slag is mainly caused by a large amount of heavy metal elements and ammonia nitrogen contained in the slag. The electrolytic manganese residue is measured by a spectrophotometry method, the soluble manganese content of the dried electrolytic manganese residue is 20771.93mg/kg, the ammonia nitrogen content is 6147.10mg/kg, the concentrations of the electrolytic manganese residue and the ammonia nitrogen content exceed the national standard by 453 times and 26 times respectively, and the harm is great. Soluble heavy metals with higher concentration are continuously transferred and transformed in nature, and from the beginning, soil and surface water are polluted, and underground water is gradually influenced. The traditional simple and extensive stacking treatment mode not only occupies a large amount of limited land resources and is very easy to cause landslide and geological disasters, but also pollutes surface water and underground water and destroys the surrounding ecological balance; not only has adverse effect on human health, but also can cause social contradiction, and hinder the stable development of society. Although two main pollutants such as soluble manganese, ammonia nitrogen and the like in the electrolytic manganese slag exceed the highest limit value of the integrated wastewater discharge standard (GB 8978-.
At present, manganese slag treatment modes of electrolytic manganese enterprises in China are basically landfill treatment, the key of the landfill treatment lies in the construction of storage and disposal sites, and a standard manganese slag storage and disposal site should be established for electrolytic manganese enterprises with the scale of 1 ten thousand tons/year according to the regulation of the general industrial solid waste storage and disposal site pollution control standard (GB 18599-2001). The seepage-proofing system and the percolate collecting system of the site consume at least more than ten million yuan, and in addition, the maintenance cost of the site is more than several million yuan per year, so that huge capital pressure is brought to electrolytic manganese enterprises and the maintenance cost is hard to bear. Therefore, when a slag warehouse is built in a plurality of domestic enterprises at present, the slag warehouse is not built according to the general industrial solid waste storage and disposal site pollution control standard (GB 18599) and the feasibility demonstration and the environmental impact evaluation of project site selection are not carried out, a certain valley is generally randomly selected as a stacking site, some of the valley even occupies cultivated land, no mark is arranged on the manganese slag stacking site, no management is carried out, most of manganese slag stacking sites have original stacking modes, some slag dams are even directly stacked by local stones, and the potential hazards of dam crossing and dam break of manganese slag are very serious; the bottom layer of the slag field has no anti-seepage measure, various pollutants in the manganese slag are easy to leak into the environment and far exceed the capacity of the local ecological environment, and the continuous and healthy development of the electrolysis industry is influenced and restricted.
Aiming at a series of problems of ecological environment and the like caused by electrolytic manganese slag, how to realize harmless treatment and resource utilization becomes a focus of attention of all circles of society, some research institutions or units make some exploratory tests on the comprehensive utilization of the electrolytic manganese slag, the electrolytic manganese slag is mainly applied to the building material industry, and although certain results are obtained, some problems still exist. The innovation is that the application of some new technologies is opened, and particularly in recent years, the innocent treatment of the electrolytic manganese slag is a new step. The Coukou forces have studied and utilized the method for producing gelled material after calcining electrolytic manganese slag, namely electrolytic manganese slag gelled material, and the Litanping et al also studied the research on the physicochemical characteristics and development and application of the electrolytic manganese slag, but the resource treatment method needs high-temperature calcination, and has high energy consumption, complex process route and high production cost. The feasibility of replacing gypsum with electrolytic manganese slag as a cement additive, namely the research on the production of the electrolytic manganese slag for cement setting retarder, has been studied by Von cloud, and due to the limitation of the properties of raw materials, the addition amount of the electrolytic manganese slag is less than 5% under the condition of not influencing the performance of cement. Wang Huai ' an once studied the method for producing the complete fertilizer by using the electrolytic manganese slag, namely the ' total quantity regulation and control method of the complete matrix for land treatment of the electrolytic manganese slag ', but because the market capacity is limited, and the improper application causes the soil hardening easily, the actual application of enterprises and the society is less, and the popularization and the application are difficult. Although the Chinese patent CN102161048A solves most of the problems and realizes harmless treatment of electrolytic manganese slag, the steps involved in the method need to dry the materials, and the energy consumption required by each ton of manganese slag in the treatment process is not a little great, so that the process does not realize complete low cost.
Based on the analysis, the harmless treatment process of the electrolytic manganese slag, which has the advantages of excellent treatment effect, simple process, good product performance and low cost, is urgently needed by the industry. Only by fundamentally solving and eliminating the environmental risk hidden trouble generated in the stacking process of the electrolytic manganese slag, the investment pressure of enterprises can be effectively reduced.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a technology for harmless treatment and resource utilization of electrolytic manganese residues, which has the advantages of wide raw material source, excellent treatment effect, simple process technology and good product performance, fundamentally solves and eliminates the environmental risk hidden trouble generated in the stacking process of the electrolytic manganese residues, reduces the investment pressure of enterprises, and can provide direction and help for the recycling of subsequent solid wastes.
In order to achieve the purpose, the invention adopts the following technical scheme:
a technology for harmless treatment and resource utilization of electrolytic manganese slag comprises the following steps:
(1) weighing 104 ~ 113 parts by weight of electrolytic manganese slag by a weighing device, conveying the electrolytic manganese slag into a cutting device, and cutting the manganese slag into blocks with the particle size of less than or equal to 2 cm;
(2) conveying the cut and formed electrolytic manganese slag to stirring equipment 1, adjusting the stirring speed to 60r/min, starting the stirring equipment 1 and a corresponding ammonia nitrogen collecting fan, simultaneously adding 8.32 ~ 9.04.04 parts by weight of quicklime powder into the electrolytic manganese slag by using weighing equipment, stirring for 60min, conveying to a standing bin 1, and standing to form mixed manganese slag 1;
(3) conveying the mixed manganese slag 1 into stirring equipment 2, adjusting the stirring speed to 60r/min, starting the stirring equipment 2 and a corresponding ammonia nitrogen collecting fan, spraying a composite aqueous solution prepared from 0.00052 ~ 0.000565 parts by weight of ferrous sulfate, 0.0013 ~ 0.0014125 parts by weight of ferrous chloride, 0.0003744 ~ 0.0004068 parts by weight of sodium carbonate and 0.208 ~ 0.226.226 parts by weight of water, stirring for 60min, conveying the mixed manganese slag to a standing bin 2, and standing to form the mixed manganese slag 2;
(4) conveying the mixed manganese slag 2 into a stirring device 3, adjusting the stirring speed to 60r/min, starting the stirring device 3 and a corresponding ammonia nitrogen collecting fan, simultaneously spraying a potassium silicate aqueous solution prepared from 0.0832 ~ 0.0904.0904 parts by weight of potassium silicate and 0.208 ~ 0.226.226 parts by weight of water, stirring for 60min, conveying the mixture into a standing bin 3, and standing to form the mixed manganese slag 3;
(5) conveying the mixed manganese slag 3 into a stirring device 4, adjusting the stirring speed to 60r/min, starting the stirring device 4 and a corresponding ammonia nitrogen collecting fan, simultaneously spraying a sodium carbonate aqueous solution prepared from 0.0002496 ~ 0.0002712 parts by weight of sodium carbonate and 0.208 ~ 0.226.226 parts by weight of water, stirring for 60min, conveying the mixture to a standing bin 4, and standing to form the mixed manganese slag 4;
(5) conveying the mixed manganese slag 3 into stirring equipment 4, adjusting the stirring speed to 60r/min, starting the stirring equipment 4 and a corresponding ammonia nitrogen collecting fan, simultaneously spraying an aqueous solution prepared by sodium carbonate (240 g for every 100t of electrolytic manganese slag) and water (200 kg for every 100t of electrolytic manganese slag), stirring for 60min, conveying to a standing bin 4, and standing to form the mixed manganese slag 4; a large amount of ammonia nitrogen gas volatilized at the stage is collected and utilized by a gas collecting system;
(6) conveying the mixed manganese slag 4 into a vibrating screening device with 75 meshes, starting the vibrating screening device and a corresponding ammonia nitrogen collecting fan, screening a large amount of fine materials to form improved manganese slag, directly conveying the improved manganese slag to a finished product warehouse, screening a small amount of coarse materials, returning to the step (2), and repeating the harmless treatment step again; a large amount of ammonia nitrogen gas volatilized at the stage is collected and utilized by a gas collecting system;
(7) naturally stacking the improved manganese slag formed in the step (6) in a finished product warehouse for at least 5 hours, and handing over the improved manganese slag to cement product enterprises to produce cement, so as to realize the purpose of resource utilization of electrolytic manganese slag;
(8) and (3) releasing the ammonia nitrogen collected in the step (2) ~ (6) into water with the ratio of 1:20 to form ammonia water, and delivering the ammonia water to an electrolytic manganese enterprise for recycling, or preparing organic ammonia fertilizer from the ammonia nitrogen collected in each process through ammonia fertilizer production equipment, and selling the organic ammonia fertilizer to a farming department.
In the step (1), the electrolytic manganese residues are cut into blocks with the particle size of less than or equal to 2cm, and a large amount of large blocks of electrolytic manganese residues are mainly smashed, so that the quicklime powder and the electrolytic manganese residues which are input in the step (2) can be fully fused and uniformly stirred.
The fineness of the quicklime powder in the step (2) is 120 meshes, and the screen residue is less than 5%. The effect of the quicklime powder on the manganese slag is as follows: firstly, increasing the PH value of manganese slag to increase the content of free ammonia, and promoting the evaporation of water and the volatilization of free ammonia due to the heat energy generated when quicklime meets water, so that the removal of ammonia nitrogen gas reaches 60%; secondly, soluble Mn in the manganese slag2+Oxidation to insoluble Mn under alkaline conditions4+The curing rate reaches about 80 percent, and the influence of free manganese ions on the environment is reduced; finally, calcium hydroxide is generated by combining quicklime with water, hydroxide ions provided by the calcium hydroxide are combined with free heavy metal element ions to react to generate insoluble solid (hydroxide compounds), and the influence of the free heavy metal elements on the environment is reduced.
The composite solution in the step (3) is mainly used for reducing heavy metal elements in the electrolytic manganese slag and continuously combining with hydroxide ions to generate insoluble solid (hydroxide), so that the pollution of heavy metals to the environment is further reduced, and the curing rate reaches 10%; and the sodium carbonate reacts with the ammonium sulfate in the electrolytic manganese slag to further volatilize ammonia nitrogen gas, and the removal rate reaches about 25 percent.
The potassium silicate water solution in the step (4) is mainly used for solidifying the heavy metal elements which are remained in the free state and are not solidified in the steps (2) and (3), and the solidification rate reaches 8%.
The sodium carbonate aqueous solution in the step (5) is mainly reacted with the residual ammonium sulfate to further volatilize ammonia nitrogen gas, and the removal rate reaches 10%.
The coarse material screened in the step (6) does not react with various solutions, so that the aim of harmlessness cannot be achieved, the material is conveyed to crushing equipment for strong crushing, and the crushed manganese slag is returned to the step (2) for repeated harmlessness treatment.
The invention has the beneficial effects that:
1、the invention dissolves the main pollutant soluble Mn in the electrolytic manganese slag2+Oxidation to insoluble Mn4+And (3) solidifying, namely removing and recycling ammonia nitrogen which is another main pollutant in the electrolytic manganese slag, reducing trace heavy metal in the electrolytic manganese slag through ferrous sulfate and ferrous chloride, and solidifying the trace heavy metal by utilizing potassium silicate to achieve the aim of controlling the source of the polluted environment, thereby finally realizing the environmental protection effect.
2. The chemical reagent and the quicklime selected by the invention have low price, good performance and wide sources; the chemical reagents are non-dangerous chemical reagents, are simple to protect when in use and are easy to purchase and store.
3. The invention mainly adopts physical and chemical methods to carry out innocent treatment on the electrolytic manganese slag, replaces the prior high-cost treatment method of high-temperature calcination, and realizes energy conservation and consumption reduction.
4. The electrolytic manganese slag treated by the method is a preferable mixed material for cement enterprises, so that resource utilization is realized, and the aim of changing waste into valuable is fulfilled.
5. After the achievement of the invention is converted, the simple and extensive stacking treatment mode of the electrolytic manganese slag is finished, the huge cost of enterprises due to building a slag warehouse and maintaining expenditure is saved, more importantly, the problem of environmental pollution caused by stacking of the electrolytic manganese slag is solved, the hidden danger of geological disasters caused by landslide easily caused by stacking of the electrolytic manganese slag is discharged, the social contradiction is effectively solved, and the continuous and rapid development of the electrolytic manganese industry is promoted.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The following is further described with reference to fig. 1 and the specific embodiments:
as shown in fig. 1, after cutting electrolytic manganese slag into blocks with a certain particle size in a cutting device, conveying the blocks into a stirring device 1, adding quicklime powder to the blocks, uniformly stirring the blocks, conveying the blocks to a standing bin 1 to stand, conveying the blocks to a stirring device 2, spraying a composite aqueous solution prepared by mixing ferrous sulfate, ferrous chloride, sodium carbonate and water to the stirring device, conveying the blocks to the standing bin 2 to stand, conveying the blocks to a stirring device 3, spraying an aqueous solution prepared by mixing potassium silicate and water to the standing bin 3 to stand, conveying the blocks to a stirring device 4, spraying an aqueous solution prepared by mixing sodium carbonate and water to the stirring device to uniformly stir, conveying the blocks to a standing bin 4 to stand, conveying the blocks to a screening device to screen, feeding the blocks into a finished product bin directly, naturally stacking the blocks, and then crushing the coarse materials into the stirring device 1 to perform harmless treatment again. The ammonia nitrogen generated in each process is collected by an ammonia nitrogen collecting system and then is recycled by electrolytic manganese enterprises.
Example 1
(1) Weighing 104 parts by weight of electrolytic manganese slag by using a weighing device, conveying the electrolytic manganese slag into a cutting device, and cutting the manganese slag into blocks with the particle size of less than or equal to 2 cm;
(2) conveying the cut and formed electrolytic manganese slag to stirring equipment 1, adjusting the stirring speed to 60r/min, starting the stirring equipment 1 and a corresponding ammonia nitrogen collecting fan, simultaneously adding 8.32 parts by weight of quicklime powder into the electrolytic manganese slag by using weighing equipment, stirring for 60min, conveying to a standing bin 1, and standing to form mixed manganese slag 1; a large amount of ammonia nitrogen gas volatilized at the stage is collected and utilized by a gas collecting system;
(3) conveying the mixed manganese slag 1 into stirring equipment 2, adjusting the stirring speed to 60r/min, starting the stirring equipment 2 and a corresponding ammonia nitrogen collecting fan, spraying a composite aqueous solution prepared from 0.00052 part by weight of ferrous sulfate, 0.0013 part by weight of ferrous chloride, 0.0003744 parts by weight of sodium carbonate and 0.208 part by weight of water, stirring for 60min, conveying to a standing bin 2, and standing to form the mixed manganese slag 2; a large amount of ammonia nitrogen gas volatilized at the stage is collected and utilized by a gas collecting system;
(4) conveying the mixed manganese slag 2 into a stirring device 3, adjusting the stirring speed to 60r/min, starting the stirring device 3 and a corresponding ammonia nitrogen collecting fan, spraying an aqueous solution prepared from 0.0832 parts by weight of potassium silicate and 0.208 part by weight of water, stirring for 60min, conveying to a standing bin 3, and standing to form the mixed manganese slag 3; a large amount of ammonia nitrogen gas volatilized at the stage is collected and utilized by a gas collecting system;
(5) conveying the mixed manganese slag 3 into a stirring device 4, adjusting the stirring speed to 60r/min, starting the stirring device 4 and a corresponding ammonia nitrogen collecting fan, spraying an aqueous solution prepared from 0.0002496 parts by weight of sodium carbonate and 0.208 part by weight of water, stirring for 60min, conveying to a standing bin 4, and standing to form the mixed manganese slag 4; a large amount of ammonia nitrogen gas volatilized at the stage is collected and utilized by a gas collecting system;
(6) conveying the mixed manganese slag 4 into 75-mesh vibration screening equipment, starting the vibration screening equipment and a corresponding ammonia nitrogen collecting fan, screening out a large amount of fine materials to form improved manganese slag, directly conveying the improved manganese slag to a finished product warehouse, conveying a small amount of coarse materials to crushing equipment for strong crushing, and returning the crushed manganese slag to the step (2) to repeat the harmless treatment step again;
(7) naturally stacking the improved manganese slag formed in the step (6) in a finished product warehouse for at least 5 hours, and handing over the improved manganese slag to cement product enterprises to produce cement, so as to realize the purpose of resource utilization of electrolytic manganese slag;
(8) and (3) releasing the ammonia nitrogen collected in the step (2) ~ (6) into water with the ratio of 1:20 to form ammonia water, and delivering the ammonia water to an electrolytic manganese enterprise for recycling, or preparing organic ammonia fertilizer from the ammonia nitrogen collected in each process through ammonia fertilizer production equipment, and selling the organic ammonia fertilizer to a farming department.
Example 2
(1) Weighing 106 parts by weight of electrolytic manganese slag by using a weighing device, conveying the electrolytic manganese slag into a cutting device, and cutting the manganese slag into blocks with the particle size of less than or equal to 2 cm;
(2) conveying the cut and formed electrolytic manganese slag to stirring equipment 1, adjusting the stirring speed to 60r/min, starting the stirring equipment 1 and a corresponding ammonia nitrogen collecting fan, simultaneously adding 8.48 parts by weight of quicklime powder into the electrolytic manganese slag by using weighing equipment, stirring for 60min, conveying to a standing bin 1, and standing to form mixed manganese slag 1;
(3) conveying the mixed manganese slag 1 into stirring equipment 2, adjusting the stirring speed to 60r/min, starting the stirring equipment 2 and a corresponding ammonia nitrogen collecting fan, spraying a composite aqueous solution prepared from 0.00053 part by weight of ferrous sulfate, 0.001325 parts by weight of ferrous chloride, 0.0003816 parts by weight of sodium carbonate and 0.212 part by weight of water, stirring for 60min, conveying to a standing bin 2, and standing to form the mixed manganese slag 2;
(4) conveying the mixed manganese slag 2 into a stirring device 3, adjusting the stirring speed to 60r/min, starting the stirring device 3 and a corresponding ammonia nitrogen collecting fan, spraying an aqueous solution prepared from 0.0848 part by weight of potassium silicate and 0.212 part by weight of water, stirring for 60min, conveying to a standing bin 3, and standing to form the mixed manganese slag 3;
(5) conveying the mixed manganese slag 3 into a stirring device 4, adjusting the stirring speed to 60r/min, starting the stirring device 4 and a corresponding ammonia nitrogen collecting fan, spraying an aqueous solution prepared from 0.0002544 parts by weight of sodium carbonate and 0.212 part by weight of water, stirring for 60min, conveying to a standing bin 4, and standing to form the mixed manganese slag 4;
(6) conveying the mixed manganese slag 4 into 75-mesh vibration screening equipment, starting the vibration screening equipment and a corresponding ammonia nitrogen collecting fan, screening out a large amount of fine materials to form improved manganese slag, directly conveying the improved manganese slag to a finished product warehouse, conveying a small amount of coarse materials to crushing equipment for strong crushing, and returning the crushed manganese slag to the step (2) to repeat the harmless treatment step again;
(7) naturally stacking the improved manganese slag formed in the step (6) in a finished product warehouse for at least 5 hours, and handing over the improved manganese slag to cement product enterprises to produce cement, so as to realize the purpose of resource utilization of electrolytic manganese slag;
(8) and (3) releasing the ammonia nitrogen collected in the step (2) ~ (6) into water with the ratio of 1:20 to form ammonia water, and delivering the ammonia water to an electrolytic manganese enterprise for recycling, or preparing organic ammonia fertilizer from the ammonia nitrogen collected in each process through ammonia fertilizer production equipment, and selling the organic ammonia fertilizer to a farming department.
Example 3
(1) Weighing 109.9 parts by weight of electrolytic manganese slag by using a weighing device, conveying the electrolytic manganese slag into a cutting device, and cutting the manganese slag into blocks with the particle size of less than or equal to 2 cm;
(2) conveying the cut and formed electrolytic manganese slag to stirring equipment 1, adjusting the stirring speed to 60r/min, starting the stirring equipment 1 and a corresponding ammonia nitrogen collecting fan, simultaneously adding 8.792 parts by weight of quicklime powder into the electrolytic manganese slag by using weighing equipment, stirring for 60min, conveying to a standing bin 1, and standing to form mixed manganese slag 1;
(3) conveying the mixed manganese slag 1 into stirring equipment 2, adjusting the stirring speed to 60r/min, starting the stirring equipment 2 and a corresponding ammonia nitrogen collecting fan, spraying a composite aqueous solution prepared from 0.0005495 parts by weight of ferrous sulfate, 0.00137375 parts by weight of ferrous chloride, 0.00039564 parts by weight of sodium carbonate and 0.2198 parts by weight of water, stirring for 60min, conveying to a standing bin 2, and standing to form the mixed manganese slag 2;
(4) conveying the mixed manganese slag 2 into a stirring device 3, adjusting the stirring speed to 60r/min, starting the stirring device 3 and a corresponding ammonia nitrogen collecting fan, spraying aqueous solution prepared from 0.08792 parts by weight of potassium silicate and 0.2198 parts by weight of water, stirring for 60min, conveying to a standing bin 3, and standing to form the mixed manganese slag 3;
(5) conveying the mixed manganese slag 3 into a stirring device 4, adjusting the stirring speed to 60r/min, starting the stirring device 4 and a corresponding ammonia nitrogen collecting fan, spraying an aqueous solution prepared from 0.00026376 parts by weight of sodium carbonate and 0.2198 parts by weight of water, stirring for 60min, conveying to a standing bin 4, and standing to form the mixed manganese slag 4;
(6) conveying the mixed manganese slag 4 into 75-mesh vibration screening equipment, starting the vibration screening equipment and a corresponding ammonia nitrogen collecting fan, screening out a large amount of fine materials to form improved manganese slag, directly conveying the improved manganese slag to a finished product warehouse, conveying a small amount of coarse materials to crushing equipment for strong crushing, and returning the crushed manganese slag to the step (2) to repeat the harmless treatment step again;
(7) naturally stacking the improved manganese slag formed in the step (6) in a finished product warehouse for at least 5 hours, and handing over the improved manganese slag to cement product enterprises to produce cement, so as to realize the purpose of resource utilization of electrolytic manganese slag;
(8) and (3) releasing the ammonia nitrogen collected in the step (2) ~ (6) into water with the ratio of 1:20 to form ammonia water, and delivering the ammonia water to an electrolytic manganese enterprise for recycling, or preparing organic ammonia fertilizer from the ammonia nitrogen collected in each process through ammonia fertilizer production equipment, and selling the organic ammonia fertilizer to a farming department.
Example 4
(1) Weighing 111 parts by weight of electrolytic manganese slag by using a weighing device, conveying the electrolytic manganese slag into a cutting device, and cutting the manganese slag into blocks with the particle size of less than or equal to 2 cm;
(2) conveying the cut and formed electrolytic manganese slag to stirring equipment 1, adjusting the stirring speed to 60r/min, starting the stirring equipment 1 and a corresponding ammonia nitrogen collecting fan, simultaneously adding 8.88 parts by weight of quicklime powder into the electrolytic manganese slag by using weighing equipment, stirring for 60min, conveying to a standing bin 1, and standing to form mixed manganese slag 1;
(3) conveying the mixed manganese slag 1 into stirring equipment 2, adjusting the stirring speed to 60r/min, starting the stirring equipment 2 and a corresponding ammonia nitrogen collecting fan, spraying a composite aqueous solution prepared from 0.000555 parts by weight of ferrous sulfate, 0.0013875 parts by weight of ferrous chloride, 0.00035997 parts by weight of sodium carbonate and 0.222 part by weight of water, stirring for 60min, conveying to a standing bin 2, and standing to form the mixed manganese slag 2;
(4) conveying the mixed manganese slag 2 into a stirring device 3, adjusting the stirring speed to 60r/min, starting the stirring device 3 and a corresponding ammonia nitrogen collecting fan, spraying an aqueous solution prepared from 0.0888 weight part of potassium silicate and 0.222 weight part of water, stirring for 60min, conveying to a standing bin 3, and standing to form the mixed manganese slag 3;
(5) conveying the mixed manganese slag 3 into a stirring device 4, adjusting the stirring speed to 60r/min, starting the stirring device 4 and a corresponding ammonia nitrogen collecting fan, spraying an aqueous solution prepared from 0.0002664 parts by weight of sodium carbonate and 0.222 part by weight of water, stirring for 60min, conveying to a standing bin 4, and standing to form the mixed manganese slag 4;
(6) conveying the mixed manganese slag 4 into 75-mesh vibration screening equipment, starting the vibration screening equipment and a corresponding ammonia nitrogen collecting fan, screening out a large amount of fine materials to form improved manganese slag, directly conveying the improved manganese slag to a finished product warehouse, conveying a small amount of coarse materials to crushing equipment for strong crushing, and returning the crushed manganese slag to the step (2) to repeat the harmless treatment step again;
(7) naturally stacking the improved manganese slag formed in the step (6) in a finished product warehouse for at least 5 hours, and handing over the improved manganese slag to cement product enterprises to produce cement, so as to realize the purpose of resource utilization of electrolytic manganese slag;
(8) and (3) releasing the ammonia nitrogen collected in the step (2) ~ (6) into water with the ratio of 1:20 to form ammonia water, and delivering the ammonia water to an electrolytic manganese enterprise for recycling, or preparing organic ammonia fertilizer from the ammonia nitrogen collected in each process through ammonia fertilizer production equipment, and selling the organic ammonia fertilizer to a farming department.
Example 5
(1) Weighing 111 parts by weight of electrolytic manganese slag by using a weighing device, conveying the electrolytic manganese slag into a cutting device, and cutting the manganese slag into blocks with the particle size of less than or equal to 2 cm;
(2) conveying the cut and formed electrolytic manganese slag to stirring equipment 1, adjusting the stirring speed to 60r/min, starting the stirring equipment 1 and a corresponding ammonia nitrogen collecting fan, simultaneously adding 8.32 ~ 9.04.04 parts by weight of quicklime powder into the electrolytic manganese slag by using weighing equipment, stirring for 60min, conveying to a standing bin 1, and standing to form mixed manganese slag 1;
(3) conveying the mixed manganese slag 1 into stirring equipment 2, adjusting the stirring speed to 60r/min, starting the stirring equipment 2 and a corresponding ammonia nitrogen collecting fan, spraying a composite aqueous solution prepared from 0.00052 ~ 0.000565 parts by weight of ferrous sulfate, 0.0013 ~ 0.0014125 parts by weight of ferrous chloride, 0.0003744 ~ 0.0004068 parts by weight of sodium carbonate and 0.208 ~ 0.226.226 parts by weight of water, stirring for 60min, conveying the mixed manganese slag to a standing bin 2, and standing to form the mixed manganese slag 2;
(4) conveying the mixed manganese slag 2 into a stirring device 3, adjusting the stirring speed to 60r/min, starting the stirring device 3 and a corresponding ammonia nitrogen collecting fan, simultaneously spraying aqueous solution prepared from 0.0832 ~ 0.0904.0904 parts by weight of potassium silicate and 0.208 ~ 0.226.226 parts by weight of water, stirring for 60min, conveying the mixture into a standing bin 3, and standing to form the mixed manganese slag 3;
(5) conveying the mixed manganese slag 3 into stirring equipment 4, adjusting the stirring speed to 60r/min, starting the stirring equipment 4 and a corresponding ammonia nitrogen collecting fan, simultaneously spraying aqueous solution prepared from 0.0002496 ~ 0.0002712 parts by weight of sodium carbonate and 0.208 ~ 0.226.226 parts by weight of water, stirring for 60min, conveying the mixture into a standing bin 4, and standing to form the mixed manganese slag 4;
(6) conveying the mixed manganese slag 4 into 75-mesh vibration screening equipment, starting the vibration screening equipment and a corresponding ammonia nitrogen collecting fan, screening out a large amount of fine materials to form improved manganese slag, directly conveying the improved manganese slag to a finished product warehouse, conveying a small amount of coarse materials to crushing equipment for strong crushing, and returning the crushed manganese slag to the step (2) to repeat the harmless treatment step again;
(7) naturally stacking the improved manganese slag formed in the step (6) in a finished product warehouse for at least 5 hours, and handing over the improved manganese slag to cement product enterprises to produce cement, so as to realize the purpose of resource utilization of electrolytic manganese slag;
(8) and (3) releasing the ammonia nitrogen collected in the step (2) ~ (6) into water with the ratio of 1:20 to form ammonia water, and delivering the ammonia water to an electrolytic manganese enterprise for recycling, or preparing organic ammonia fertilizer from the ammonia nitrogen collected in each process through ammonia fertilizer production equipment, and selling the organic ammonia fertilizer to a farming department.
Test example 1
The electrolytic manganese slag treated in the example 1 is taken as a sample to carry out 'building material radioactive nuclear quantity limit' detection, and the result is qualified and accords with the building main body material by contrasting the standard of 'building material radioactive nuclear quantity limit' (GB 6566-. The specific results are detailed in table 1.
Sample condition: powder form
To sample number: 2kg of
And (3) checking date: 2019-08-09 to 2019-08-13
The inspection basis is as follows: GB 6566-
TABLE 1
Test example 2
The electrolytic manganese slag treated in the example 1 is taken as a sample to be tested in a leaching toxicity test, and the toxicity value of the test result is within the required safety range of 'hazardous waste identification standard leaching toxicity' (GB 5085.3-2007). The results of the numerical values of the leaching toxicity are qualified according to the requirements of Integrated wastewater discharge Standard (GB 8978-1996).
The modified manganese slag sample (sample in example 1) is tested according to the standards of GB8978 and 1996 integrated wastewater discharge Standard, and the tested items meet the requirements of the standard regulation. The results are detailed in Table 2.
TABLE 2
Test example 3
The electrolytic manganese slag treated in the example 1 is taken as a sample and delivered to a cement enterprise as a mixed material added in cement production, and a large-grinding test and a small-grinding test are carried out, so that the strength and the activity of the cement are not influenced, the strength and the activity of the cement are improved, the production cost of the cement enterprise is saved, and the yield is improved.
A mill test report on the activity of modified manganese slag to replace a portion of the water mix.
Test cement variety and mixed material variety
Ordinary silicate water p.o42.5 (domestic bagged); example 1 a manganese slag sample was modified.
Second, the test formula and results are shown in tables 3-4
TABLE 3
Note: adding three ten-thousandth grinding aid
TABLE 4
Note: adding three ten-thousandth grinding aid
Third, test results
1. The table shows that the strength of the cement added with the improved manganese slag is higher than the national standard;
2. the table shows that after the improved manganese slag replaces part of cement mixed materials, the grinding performance is good, the grinding time can be shortened, the unit power consumption is reduced, and the unit yield of the grinding machine is improved;
3. the cement with the improved manganese slag is added, so that the water consumption of the standard consistency is reduced, the water demand ratio is reduced, and the fluidity of cement mortar is effectively improved;
4. the improved manganese slag is used as a mixed material of cement, the reference of other mixed materials is reduced, and the production cost is obviously reduced.
Fourth, conclusion of the experiment
The improved manganese slag is used as a mixed material for cement production, has obvious advantages and ideal results, and the M2 proportioning scheme is recommended in actual production and in consideration of price.
Comparison experiment report of small mill and large mill for replacing partial cement mixed material with improved manganese slag
Comparison test of cement variety and mixed material variety
Ordinary silicate water p.o42.5 (domestic bagged); example 1 a manganese slag sample was modified.
Second, purpose of comparative experiment
And (3) the improved manganese slag is used for replacing part of the cement mixed material to be applied to a large-mill test for production, the result of a small-mill test is verified, and the feasibility of replacing part of the mixed material with the improved manganese slag is further checked.
Thirdly, the formula and the results of the comparative test are shown in tables 5 to 6
TABLE 5
Note: adding three ten-thousandth grinding aid
TABLE 6
Fourth, test results
According to the large grinding test number, 5% of improved manganese slag is added to replace sintered manganese slag in the production process, so that the strength is improved in 1 day, 3 days and 28 days. In addition, from the production record, the quantity of the mill is not increased, the cement cost is reduced, and all project indexes of the cement finished product completely meet the national standard. Through large and small grinding tests, the modified manganese slag is completely feasible to replace part of cement mixed materials to produce cement.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The harmless treatment method of the electrolytic manganese slag is characterized by comprising the following steps:
(1) conveying 104 ~ 113 parts by weight of electrolytic manganese slag to cutting equipment to cut the manganese slag into blocks with the particle size of less than or equal to 2 cm;
(2) conveying the cut and formed electrolytic manganese slag to stirring equipment 1, starting the stirring equipment 1 and an ammonia nitrogen collecting fan 1, adding 8.32 ~ 9.04.04 parts by weight of quicklime powder into the electrolytic manganese slag, stirring at a low speed for 60min, conveying to a standing bin 1, standing to form mixed manganese slag 1, and collecting ammonia nitrogen gas;
(3) conveying the mixed manganese slag 1 into a stirring device 2, starting the stirring device 2 and an ammonia nitrogen collecting fan 2, spraying 0.0539344 ~ 0.0586018 parts of composite aqueous solution, stirring at a low speed for 60min, conveying to a standing bin 2, standing to form mixed manganese slag 2, and collecting ammonia nitrogen gas;
(4) conveying the mixed manganese slag 2 into a stirring device 3, starting the stirring device 3 and an ammonia nitrogen collecting fan 3, spraying 18.72 ~ 20.34.34 parts of potassium silicate aqueous solution, stirring at a low speed for 60min, conveying to a standing bin 3, standing to form mixed manganese slag 3, and collecting ammonia nitrogen gas;
(5) conveying the mixed manganese slag 3 into a stirring device 4, starting the stirring device 4 and an ammonia nitrogen collecting fan 4, spraying 10.42496 ~ 11.32712 parts of sodium carbonate aqueous solution, stirring at a low speed for 60min, conveying to a standing bin 4, standing to form mixed manganese slag 4, and collecting ammonia nitrogen gas;
(6) and (3) conveying the mixed manganese slag 4 to 75-mesh vibration screening equipment, starting the vibration screening equipment and an ammonia nitrogen collecting fan 5, conveying screened fine materials to the improved manganese slag, conveying screened coarse materials to the crushing equipment for strong crushing, then returning to the step (2) for repeated harmless treatment, and collecting ammonia nitrogen gas.
2. The electrolytic manganese slag innocent treatment and resource utilization technology of claim 1, wherein the particle size of the quicklime powder in the step (2) is 120 meshes, and the screen allowance is less than 5%.
3. The method as claimed in claim 1, wherein the composite aqueous solution in step (3) is prepared by mixing 0.00052 ~ 0.000565 parts of ferrous sulfate, 0.0013 ~ 0.0014125 parts of ferrous chloride, 0.0003744 ~ 0.0004068 parts of sodium carbonate and 0.208 ~ 0.226.226 parts of water uniformly according to the weight parts to obtain the composite aqueous solution.
4. The method of claim 1, wherein the aqueous solution of potassium silicate obtained in step (4) is prepared by mixing 0.0832 ~ 0.0904.0904 parts by weight of potassium silicate and 0.208 ~ 0.226.226 parts by weight of water to obtain the aqueous solution of potassium silicate.
5. The method according to claim 1, wherein the aqueous solution of sodium carbonate in step (4) is prepared by uniformly mixing 0.0002496 ~ 0.0002712 parts of sodium carbonate and 0.208 ~ 0.226.226 parts of water by weight to obtain the aqueous solution of sodium carbonate.
6. The method of claim 1, wherein the screened fine to coarse mass ratio of step (6) is 75 ~ 85: 15 ~ 25.
7. The modified manganese slag obtained by the method according to claim 1 ~ 6, wherein the modified manganese slag has a water content of 10% ~ 12%.
8. Use of the modified manganese slag according to claim 7 in cement production after natural stacking for at least 5 hours.
9. An ammoniacal nitrogen gas produced by any one of the methods of claim 1 ~ 6.
10. Use of the ammonian gas according to claim 9 in industrial or agricultural recycling.
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| CN113582598A (en) * | 2021-08-23 | 2021-11-02 | 广西凭祥市恒宇水泥有限公司 | Premixed mortar and preparation method thereof |
| CN113603377A (en) * | 2021-08-23 | 2021-11-05 | 广西凭祥市恒宇水泥有限公司 | Cement produced by utilizing electrolytic manganese slag and production method thereof |
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