CN115028434A - Electrolytic manganese slag sintered brick and preparation method thereof - Google Patents
Electrolytic manganese slag sintered brick and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
- C04B33/132—Waste materials; Refuse; Residues
- C04B33/135—Combustion residues, e.g. fly ash, incineration waste
- C04B33/1352—Fuel ashes, e.g. fly ash
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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
- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/04—Clay; Kaolin
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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
- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
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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
- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
- C04B33/132—Waste materials; Refuse; Residues
- C04B33/138—Waste materials; Refuse; Residues from metallurgical processes, e.g. slag, furnace dust, galvanic waste
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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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
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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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
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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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
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Abstract
The invention relates to the technical field of environmental protection, in particular to an electrolytic manganese slag sintered brick and a preparation method thereof. The preparation method comprises the following steps: the method comprises the steps of preparing a green brick by taking electrolytic manganese slag as a raw material, drying the green brick, preheating at 300-550 ℃, and roasting at 950-1050 ℃ to prepare the electrolytic manganese slag sintered brick. According to the invention, harmful heavy metal elements in the electrolytic manganese slag are solidified in the product through a chemical reaction in a mode of preheating firstly and then roasting, so that the prepared sintered brick is stable, environment-friendly and harmless in the later use process; the harmful gas NH is treated by preheating and then roasting 3 And SO 2 Can be respectively collected and reused in the preheating and roasting processes, and simultaneously,the preheating can improve the strength of the final sintered brick, reduce the temperature required by roasting and save energy consumption.
Description
Technical Field
The invention relates to the technical field of environmental protection, in particular to an electrolytic manganese slag sintered brick and a preparation method thereof.
Background
Manganese is a very important raw material for industrial production and is widely used in the steel industry. The production method of the metal manganese mainly adopts an electrolytic method, namely, the metal manganese is prepared by electrolyzing a manganese sulfate solution. The whole process for producing electrolytic manganese metal comprises ore leaching, impurity removal, electrolysis and strippingAnd collecting, wherein the electrolytic manganese slag is filtered waste slag generated by preparing manganese electrolyte after leaching manganese ore. The main harmful substance in the electrolytic manganese slag is soluble Mn 2+ 、NH 4 + N, heavy metals and the like, and has the hazards of environmental pollution, influence on human health, land occupation and the like.
The production of electrolytic manganese belongs to the three-high industry with high energy consumption, high material consumption and high pollution. Therefore, the realization of harmless treatment and resource utilization of the electrolytic manganese slag to the maximum extent becomes an urgent problem to be solved in the electrolytic manganese industry.
In the prior art, a plurality of scholars at home and abroad research the harmless treatment and comprehensive resource utilization of electrolytic manganese slag, mainly comprising the steps of directly recovering various valuable elements from the electrolytic manganese slag and preparing various industrial and agricultural materials by using the electrolytic manganese slag, and summarizing the main harmless treatment and comprehensive utilization modes as follows.
1. Recovery of valuable metals
Because manganese element remains in the electrolytic manganese slag, the dissolution of the manganese element can be enhanced by adopting modes of acid leaching, water washing precipitation, microbial leaching and the like, and the efficient utilization of manganese resources is promoted. The acid leaching method is that the electrolytic manganese slag fully reacts with acid leaching liquid or leaching auxiliary agent, and a manganese sulfate product is obtained after ultrasonic treatment and impurity removal; researchers adopt a method combining 'washing slag and ammonium salt precipitation' to treat the manganese slag, the recovery rate can reach over 99%, and the manganese content in the recovered precipitate can reach 30%; the microbiological method is to extract manganese metal by leaching electrolytic manganese slag through microorganisms, and researches show that sulfur oxidizing bacteria and Fusarium sp bacteria can obtain higher leaching rate which can reach 93 percent.
Although the extraction efficiency of the acid leaching method and the water washing precipitation method is high, the process is complex, the cost is high, and secondary pollution is caused, so that the application of the two processes is limited. The microbial leaching technology has good economic value, high manganese slag treatment efficiency and environmental friendliness, but the method has complex strain cultivation process, high requirement on strain leaching conditions and generally long leaching time, and limits the large-scale use of the method.
2. Preparation of various materials
(1) Electrolytic manganese slag as cement additive
The main mineral of the electrolytic manganese slag is dihydrate gypsum which is a good raw material for preparing cement, so the research on the use of the electrolytic manganese slag as a cement additive has been started for a long time, and the development of the preparation process is quite mature. Research results show that the electrolytic manganese slag can be used as a cement admixture, a retarder of cement, a lightweight aggregate of a cement additive, a mineralizer and the like. However, although the electrolytic manganese slag can be used as a substitute for adding into cement to prepare industrial products, compared with natural gypsum, the product prepared by the former can meet basic requirements, but is still inferior to cement produced by adding natural gypsum in aspects of retardation performance, product strength and the like.
(2) Electrolytic manganese slag used as roadbed material
The electrolytic manganese slag has fine particle size and multiple active material components, can be doped into concrete mortar, improves the application performance of the concrete in all aspects, and can realize the resource utilization of the electrolytic manganese slag by using the cement concrete doped with the electrolytic manganese slag as a paving material. However, the electrolytic manganese slag-cement gel system is on NH 4 + N has a limited ability to stabilize on curing, which will release NH slowly during use 3 The secondary pollution to the surrounding environment will be caused, so the technology still stays in a laboratory or a small-scale experiment stage.
In the aspect of preparing the sintered brick by using the electrolytic manganese slag, Zhang Jinlong and the like adopt the electrolytic manganese slag, shale and fly ash to prepare the sintered brick (Zhang Jinlong, Pengpen, Chaihuanyuan, Wangjia, Wans. the research on the electrolytic manganese slag-shale-fly ash sintered brick [ J ], environmental science and technology, 2011,34 (1): 144-one 147), and research results show that the proportion of the electrolytic manganese slag, the shale and the fly ash is 4: 5: 1. the sintering temperature is 1000 ℃, the heat preservation time is 2h, the optimal sintering process condition is adopted, under the condition, the compressive strength of the brick body can reach 22.64MPa, and the concentration of manganese in the leaching solution is reduced from 451.08mg/L to 0.6763 mg/L. It can be seen that the concentration of manganese in the sintered green brick leaching solution prepared by the method is greatly reduced, but the consumption of electrolytic manganese slag is still low and is only 40%. Songchini et al also sintered electrolytic manganese slag, shale and fly ash, studied the sintering properties of electrolytic manganese slag-shale-fly ash green bodies (Songchini, Zhangjie, Yanhuan, Zhongpo, Zhangqingjie. research on the sintering properties of electrolytic manganese slag-shale-fly ash green bodies [ J ] novel building materials, 2019: 133-137), and the research results show that the samples fired at 1060 ℃ -1075 ℃ according to the formula of 90% of manganese slag, 5% -10% of shale and 0% -5% of fly ash have higher bending strength (24.34MPa-30.72MPa), and can be used for preparing sintered bricks for buildings. From the research results, although the method improves the consumption of the electrolytic manganese slag to 90%, the toxic leaching condition of the sintered green brick is not found in the report.
(3) Preparation of ceramic material from electrolytic manganese slag
The electrolytic manganese slag contains a large amount of elements such as silicon, aluminum, iron and the like, and is good ceramic aggregate. The electrolytic manganese slag is utilized to prepare the ceramic, so that the consumption of natural mineral raw materials of the ceramic can be reduced, and the electrolytic manganese slag can be consumed simultaneously. The method has the defects that the mixing amount of the electrolytic manganese slag is low, and the electrolytic manganese slag cannot be consumed in a large scale.
(4) Preparation of agricultural fertilizer by electrolyzing manganese slag
The electrolytic manganese slag is rich in a large amount of nutrient elements, secondary elements and trace elements required by plants, such as manganese, selenium, potassium, sodium, iron, boron and the like, has the characteristics of soil improvement in a field, stable fertilizer efficiency and the like, and can enhance the capabilities of disease resistance, insect resistance, drought resistance, lodging resistance and the like of crops and improve the yield of the crops. However, the use of electrolytic manganese residues as fertilizers does not allow for large-scale application of this technical approach due to the ecological risks associated with the use of electrolytic manganese residues as fertilizers due to the long-term effects of soil heavy metals accumulated on the organism through the food chain.
Although researchers have carried out a large amount of experimental researches on harmless treatment and resource utilization of the electrolytic manganese slag, the solidification effect of harmful substances in the electrolytic manganese slag in a laboratory is good, the solid content is low, the leaching rate of heavy metals is high in a severe environment, meanwhile, in the solidification process, soluble ammonium salt and free ammonia nitrogen in the electrolytic manganese slag are released in the form of ammonia gas, the physical and chemical properties of the fixed electrolytic manganese slag are not stable enough, and a solidified body is easy to carbonize, so that the structural damage is caused, and the secondary pollution hidden danger exists. Therefore, a new way for stabilizing and comprehensively utilizing the electrolytic manganese slag is needed to achieve the purposes of effective solidification and resource utilization.
Disclosure of Invention
The invention provides a preparation method of an electrolytic manganese slag sintered brick, which comprises the following steps: the method comprises the steps of preparing a green brick by taking electrolytic manganese slag as a raw material, drying the green brick, preheating at 300-550 ℃, and roasting at 950-1050 ℃ to prepare the electrolytic manganese slag sintered brick.
The invention discovers that harmful heavy metal elements in the electrolytic manganese slag raw material can be effectively solidified in a product through chemical reaction after the electrolytic manganese slag raw material is preheated and roasted; simultaneously, preheating treatment is carried out at 300-550 ℃, and then roasting is carried out at 950-1050 ℃ so as to lead harmful gas NH 3 And SO 2 Can be respectively collected in the preheating and roasting processes, thus better realizing the harmless treatment of the electrolytic manganese slag and the maximum utilization of resources. In addition, crystal water and easily decomposed minerals contained in the dry blank after the preheating treatment are discharged in a gas form, and the density of a baked blank block in a baking stage can be improved, so that the strength of a final baked brick is improved, the temperature required by baking is reduced, and the energy consumption is saved.
Furthermore, the inventor combines the research and study of the literature to realize that the harmful substances in the electrolytic manganese slag can still be dissociated or escaped in the later period and still cause harm to the environment if the conventional solidification mode is adopted, such as the production of cement raw materials, baking-free bricks and the like. Therefore, the invention adopts a roasting mode to solidify harmful heavy metal elements in the electrolytic manganese slag.
As a preferred embodiment of the invention, the content of the electrolytic manganese residue is 40-70% by mass of the total mass of the raw materials.
The method can fully recycle the electrolytic manganese slag, and the doping amount of the electrolytic manganese slag reaches 70 percent.
As a preferred embodiment of the present invention, the feedstock further comprises shale, lime and fly ash. The sintered brick is prepared by combining shale, limestone resources and waste fly ash generated by a power plant, so that various production wastes can be used cooperatively, and the resource utilization effect of the wastes is improved jointly.
Furthermore, based on previous experiments and literature research, the inventor finds that when the mixture of the electrolytic manganese slag, the shale, the lime and the fly ash is heated at the temperature of less than 550 ℃, the gas mainly generates ammonia gas, and SO is not simultaneously generated 2 The gas makes the produced gas complicated and difficult to separate. And SO 2 The gas can be formed and released at the high temperature of over 900 ℃, and can be separately separated and collected.
As a preferred embodiment of the present invention, the raw materials further comprise shale, lime and fly ash; the mass ratio of the electrolytic manganese slag, the shale, the lime and the fly ash is 4-7: 1-4: 1-2: 0.5-1.
As a preferred embodiment of the present invention, in the raw material, the mass ratio of the lime, the shale and the fly ash is 1: 1-3: 0.5 to 1.
Under the mass proportion, the strength of the sintered brick prepared by the method is higher, and the leaching toxicity of the sintered brick also meets the GB8978-1996 sewage comprehensive discharge standard.
As a preferred embodiment of the present invention, the preheating time is 20min to 40 min.
As a preferred embodiment of the present invention, during the preheating, ammonia gas is collected; during the calcination process, sulfur dioxide is collected.
As a preferred embodiment of the present invention, the time for the calcination is 90min to 120 min.
As a more preferred embodiment of the present invention, the preparation method comprises the steps of:
(1) crushing electrolytic manganese slag, shale, lime and fly ash to be below 100 meshes;
(2) mixing electrolytic manganese slag, shale, lime, fly ash and water to prepare a green brick, and drying the green brick to prepare a dry blank;
(3) preheating the dry blank at 300-550 ℃ for 20-40 min; then roasting the preheated dry blank at 950-1050 ℃ for 90-120 min to obtain the baked brick.
Preferably, the electrolytic manganese slag, the shale, the lime and the fly ash are crushed to be below 150 meshes.
In the specific implementation process, the green brick is dried at the temperature of 100 +/-5 ℃ to constant weight to obtain a dry green brick.
In practice, the preheating and firing are carried out in, but not limited to, a box electric furnace or a tunnel kiln.
In the specific implementation process, the raw materials are uniformly mixed according to the mixture ratio of the raw materials provided by the invention and then are pressed and formed on special brick making equipment, and the obtained green bricks are dried and then are sent into a kiln body to be preheated and roasted to obtain the electrolytic manganese slag sintered brick.
Further, the invention also provides a baked brick which is prepared by any one of the embodiments.
The compression strength of the sintered brick prepared by the invention is more than 25MPa, the compressive strength index of MU25 of the sintered common brick is reached, and the leaching toxicity of the sintered brick also meets the GB 25-1996 sewage comprehensive discharge standard.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, harmful heavy metal elements in the electrolytic manganese slag are solidified in the product through a chemical reaction in a mode of preheating firstly and then roasting, so that the prepared sintered brick is stable, environment-friendly and harmless in the later use process. The harmful gas NH is generated by preheating and roasting treatment 3 And SO 2 The sintering furnace can be respectively collected and recycled in the preheating and roasting processes, and meanwhile, the preheating can improve the strength of the final sintered brick, reduce the temperature required by roasting and save energy consumption.
In addition, the preparation method can fully recycle the electrolytic manganese slag, the doping amount of the electrolytic manganese slag reaches 70 percent, and the prepared electrolytic manganese slag solid waste sintered brick can replace clay bricks, reduce the exploitation and utilization of clay resources and is beneficial to protecting cultivated land and natural environment.
Detailed Description
The following examples are intended to illustrate the invention, but are not intended to limit the scope of the invention.
The examples, where no specific techniques or conditions are indicated, are all conventional or performed according to the techniques or conditions described in the literature of the art or according to the product specifications. The reagents and instruments used are conventional products which are available from normal commercial vendors, not indicated by manufacturers.
In the following examples, wet green bricks prepared from electrolytic manganese slag, shale, lime and fly ash are dried to constant weight at 100 ℃ to obtain dry green bricks, the compressive strength of the sintered bricks is measured by using a WE-300B hydraulic universal tester, the toxicity leaching of metal ions of the sintered bricks is implemented by referring to a standard HJ299-2007, and the toxicity leaching of inorganic ions is implemented by referring to HJ 557-2010.
The raw material electrolytic manganese slag is tested by adopting the test mode, and the toxicity leaching result is as follows (the following units are mg/L): 0.1151 As, 0.0019 Cd, 1.2574 Co, Cr: 0.0483, 0.0645 of Cu, 0.1676 of Fe, 0.0002 of Hg, 1439.3631 of Mn, 0.7133 of Ni, 0.0058 of Pb, 0.1303 of Se, 0.7303 of Zn, ammonia nitrogen: 613.2, sulfate: 10280, it can be seen that the electrolytic manganese residue is not treated, and the contents of heavy metals and ammonia nitrogen in the leachate exceed the GB8978-1996 sewage discharge standard, and further exceed the GB3838-2002 surface water environmental quality standard.
Example 1
The embodiment provides a preparation method of an electrolytic manganese slag sintered brick, which comprises the following specific steps:
respectively crushing and grinding the electrolytic manganese slag, the shale, the lime and the fly ash to be below 100 meshes. And uniformly mixing the finely ground electrolytic manganese slag, shale, lime and fly ash, wherein the electrolytic manganese slag, the shale, the lime and the fly ash respectively account for 70%, 10% and 10% of the total mixture. And adding water pressure into the mixture to prepare a briquette, preheating a dry blank obtained after drying the wet blank in a tunnel kiln at the temperature of 300 ℃ for 20min, and further roasting the preheated green brick at the temperature of 950 ℃ for 90min to obtain the sintered brick.
The test shows that the compression strength of the baked brick is 25.06Mpa, and the toxicity leaching result is as follows: as: 0.0581, Cd: 0.0003, Co: 0.0026, Cr: 0.0014, Cu: 0.0025, Fe: 0.2878, Hg: 0.0014, Mn: 0.3146, Ni: 0.0641, Pb: 0.0036, Se: 0.0120, Zn: 0.0479, ammonia nitrogen: 0.05, sulfate: 1250, the indexes of the leaching solution of the baked brick all reach the GB8978-1996 sewage discharge standard.
Example 2
The embodiment provides a preparation method of an electrolytic manganese slag sintered brick, which comprises the following specific steps:
respectively crushing and grinding the electrolytic manganese slag, the shale, the lime and the fly ash to be below 120 meshes. And uniformly mixing the finely ground electrolytic manganese slag, shale, lime and fly ash, wherein the electrolytic manganese slag, the shale, the lime and the fly ash respectively account for 65%, 20%, 10% and 5% of the total mixture. And adding water into the mixture to prepare a green brick, putting the dried green brick obtained by drying the wet green brick into a tunnel kiln to preheat at 400 ℃ for 30min, and further roasting the preheated green brick at 1050 ℃ for 100min to obtain the sintered brick.
The test shows that the compression strength of the baked brick is 28.94Mpa, and the toxicity leaching result is as follows: as: 0.0003, Cd: 0.0003, Co: 0.0051, Cr: 0.0212, Cu: 0.0207, Fe: 0.4876, Hg: 0.0001, Mn: 0.0201, Ni: 0.1302, Pb: 0.0092, Se: 0.0272, Zn: 0.0267, ammonia nitrogen: 0.06, sulfate: 1232, it can be seen that all indexes in the leachate of the baked brick reach the GB8978-1996 sewage discharge standard.
Example 3
The embodiment provides a preparation method of an electrolytic manganese slag sintered brick, which comprises the following specific steps:
respectively crushing and grinding the electrolytic manganese slag, the shale, the lime and the fly ash to below 140 meshes. And uniformly mixing the finely ground electrolytic manganese slag, shale, lime and fly ash, wherein the electrolytic manganese slag, the shale, the lime and the fly ash respectively account for 60%, 20%, 10% and 10% of the total mixture. And adding water pressure into the mixture to prepare a briquette, putting a dry briquette obtained by drying the wet briquette into a tunnel kiln for preheating at 500 ℃ for 30min, and further roasting the preheated briquette at 1000 ℃ for 100min to obtain the sintered brick.
The test shows that the compression strength of the baked brick is 29.65Mpa, and the toxicity leaching result is as follows: as: 0.0297, Cd: 0.0004, Co: 0.0024, Cr: 0.0018, Cu: 0.0004, Fe: 0.2615, Hg: 0.0013, Mn: 0.0162, Ni: 0.0463, Pb: 0.0006, Se: 0.0109, Zn: 0.0650, ammonia nitrogen: 0.04, sulfate group: 1282, it can be seen that each index in the leachate of the sintered brick reaches the GB8978-1996 sewage discharge standard.
Example 4
The embodiment provides a preparation method of an electrolytic manganese slag sintered brick, which comprises the following specific steps:
respectively crushing and grinding the electrolytic manganese slag, the shale, the lime and the fly ash to be below 150 meshes. And uniformly mixing the finely ground electrolytic manganese slag, shale, lime and fly ash, wherein the electrolytic manganese slag, the shale, the lime and the fly ash respectively account for 50%, 30%, 10% and 10% of the total mixture. And adding water into the mixture to prepare a green brick, putting the dried green brick obtained by drying the wet green brick into a tunnel kiln to preheat at 550 ℃ for 40min, and further roasting the preheated green brick at 1050 ℃ for 120min to obtain the sintered brick.
The test shows that the compression strength of the baked brick is 35.15Mpa, and the toxicity leaching result is as follows: as: 0.0268, Cd: 0.0005, Co: 0.0021, Cr: 0.0032, Cu: 0.0041, Fe: 0.2285, Hg: 0.0012, Mn: 0.0074, Ni: 0.0533, Pb: 0.0017, Se: 0.0069, Zn: 0.0882, ammonia nitrogen: 0.01, sulfate: 1156, it can be seen that each index in the leachate of the baked brick reaches the GB8978-1996 sewage discharge standard.
Comparative example 1
The comparative example provides a preparation method of an electrolytic manganese slag sintered brick, which comprises the following specific steps of: and (2) directly roasting the dry blank obtained by drying the wet blank, wherein the method comprises the following specific steps:
respectively crushing and grinding the electrolytic manganese slag, the shale, the lime and the fly ash to be below 100 meshes. And uniformly mixing the finely ground electrolytic manganese slag, shale, lime and fly ash, wherein the electrolytic manganese slag, the shale, the lime and the fly ash respectively account for 70%, 10% and 10% of the total mixture. And adding water into the mixture to prepare a green brick, drying the wet green brick to obtain a dry green brick, and preheating the dry green brick in a tunnel kiln at 950 ℃, wherein the roasting time is 90min, so that the sintered brick can be obtained.
The test shows that the compression strength of the baked brick is 18.28Mpa, and the toxicity leaching result is as follows: as: 0.0255, Cd: 0.0006, Co: 0.0051, Cr: 0.1289, Cu: 0.0207, Fe: 0.4867, Hg: 0.0009, Mn: 0.0201, Ni: 0.1302, Pb: 0.0092, Se: 0.0272, Zn: 0.0267, ammonia nitrogen: 0.06, sulfate: 1232, it can be seen that all indexes in the leachate of the baked brick reach the GB8978-1996 sewage discharge standard.
However, it can be seen from comparative example 1 that the dry green body is directly baked without being preheated, and the compressive strength of the prepared baked brick is lower than that of the baked brick prepared by preheating and then baking. In addition, the NH generated during calcination is not preheated 3 And SO 2 The mixed tail gas is required to be separated and reused if the tail gas is required to be recycled in the later period, and a gas separation step is added.
Comparative example 2
The comparative example provides a preparation method of an electrolytic manganese slag sintered brick, which comprises the following specific steps of: preheating a dry blank at 200 ℃, and specifically comprising the following steps:
respectively crushing and grinding the electrolytic manganese slag, the shale, the lime and the fly ash to be below 100 meshes. And uniformly mixing the finely ground electrolytic manganese slag, shale, lime and fly ash, wherein the electrolytic manganese slag, the shale, the lime and the fly ash respectively account for 70%, 10% and 10% of the total mixture. And adding water into the mixture to prepare a green brick, putting the dried green brick obtained by drying the wet green brick into a tunnel kiln to preheat at the temperature of 200 ℃ for 20min, and further roasting the preheated green brick at the temperature of 950 ℃ for 90min to obtain the sintered brick.
The test shows that the compression strength of the baked brick is 17.64Mpa, and the toxicity leaching result is as follows: as: 0.0339, Cd: 0.0005, Co: 0.0078, Cr: 0.0025, Cu: 0.0033, Fe: 0.1942, Hg: 0.0004, Mn: 0.5124, Ni: 0.0885, Pb: 0.0065, Se: 0.0113, Zn: 0.0856, ammonia nitrogen: 0.06, sulfate: 1689, it can be seen that all indexes of the leachate of the baked brick reach the GB8978-1996 wastewater discharge standard. However, as can be seen from comparative example 1, the dry green brick is preheated at 200 ℃, and the green brick cannot form better strength at low temperature due to lower preheating temperature, so that the reaction and consolidation of various materials in the green brick in the roasting process are influenced, and the compressive strength of the sintered brick is finally influenced.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, it is intended that all such modifications and alterations be included within the scope of this invention as defined in the appended claims.
Claims (9)
1. The preparation method of the electrolytic manganese slag sintered brick is characterized by comprising the following steps: the method comprises the steps of preparing a green brick by taking electrolytic manganese slag as a raw material, drying the green brick, preheating at 300-550 ℃, and roasting at 950-1050 ℃ to prepare the electrolytic manganese slag sintered brick.
2. The preparation method according to claim 1, wherein the content of the electrolytic manganese slag is 40 to 70% based on the total mass of the raw materials.
3. The method of claim 1 or 2, wherein the raw materials further comprise shale, lime and fly ash;
the mass ratio of the electrolytic manganese slag, the shale, the lime and the fly ash is 4-7: 1-4: 1-2: 0.5-1.
4. The preparation method according to claim 3, wherein the mass ratio of the lime, the shale and the fly ash in the raw materials is 1: 1-3: 0.5 to 1.
5. The method according to claim 4, wherein the preheating time is 20 to 40min in the raw material.
6. The production method according to any one of claims 1 to 5, characterized in that, during the preheating, ammonia gas is collected; during the calcination process, sulfur dioxide is collected.
7. The preparation method according to any one of claims 1 to 6, wherein the roasting time is 90min to 120 min.
8. The method according to any one of claims 1 to 7, comprising the steps of:
(1) crushing electrolytic manganese slag, shale, lime and fly ash to be below 100 meshes;
(2) mixing electrolytic manganese slag, shale, lime, fly ash and water to prepare a green brick, and drying the green brick to prepare a dry blank;
(3) preheating the dry blank at 300-550 ℃ for 20-40 min; and then roasting the preheated dry blank at 950-1050 ℃ for 90-120 min to prepare the electrolytic manganese slag sintered brick.
9. A baked brick produced by the production method according to any one of claims 1 to 8.
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