CN110642560A - Electrolytic manganese slag non-sintered brick and preparation method thereof - Google Patents

Electrolytic manganese slag non-sintered brick and preparation method thereof Download PDF

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CN110642560A
CN110642560A CN201911149327.4A CN201911149327A CN110642560A CN 110642560 A CN110642560 A CN 110642560A CN 201911149327 A CN201911149327 A CN 201911149327A CN 110642560 A CN110642560 A CN 110642560A
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manganese slag
brick
electrolytic manganese
viscosity breaking
slag
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石晶
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B28WORKING CEMENT, CLAY, OR STONE
    • B28BSHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B3/00Producing shaped articles from the material by using presses; Presses specially adapted therefor
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01CAMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00Ammonia; Compounds thereof
    • C01C1/02Preparation, purification or separation of ammonia
    • C01C1/026Preparation of ammonia from inorganic compounds
    • C01C1/028Preparation of ammonia from inorganic compounds from ammonium sulfate or sulfite
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/04Portland cements
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00017Aspects relating to the protection of the environment

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention discloses an electrolytic manganese slag non-sintered brick and a preparation method thereof, and relates to the technical field of waste slag resource utilization. The electrolytic manganese slag non-sintered brick comprises the following raw materials in parts by weight: electrolytic manganese slag: 61-73%, alkaline viscosity breaking curing agent: 5.8-7.5%, aggregate: 11-21%, modified gel: 7.2-12%, and other components: 1 to 2.8 percent. Firstly, an alkaline viscosity breaking curing agent is adopted to cure the residual water-soluble manganese, heavy metal and the like in the manganese slag, and meanwhile, ammonia of ammonium sulfate in the manganese slag is promoted to be converted into ammonia gas to be recycled as an electrolytic manganese raw material; the waste residue after solidification is used as a building raw material, and is pressed and molded by adding aggregate and modified gelling agent, and finally, the building brick or other building materials which meet the quality standard of the building brick are produced through gelation and maintenance.

Description

Electrolytic manganese slag non-sintered brick and preparation method thereof
Technical Field
The invention belongs to the technical field of industrial waste residue resource utilization, and particularly relates to an electrolytic manganese residue non-sintered brick and a preparation method thereof.
Background
The electrolytic manganese is widely applied to various fields of steel smelting, electronic technology, chemical industry, environmental protection, food sanitation, electric welding industry, aerospace industry and the like. After the electrolytic manganese technology in China is developed for more than 60 years, the production capacity reaches about 188 ten thousand tons/year till now, the production capacity accounts for 98 percent of the total global capacity, and the electrolytic manganese technology becomes the first major country for the production and export of electrolytic manganese metal in the world. The electrolytic manganese industry develops at a high speed and simultaneously generates a large amount of waste residues, each 1 ton of electrolytic manganese is produced according to the requirement of the secondary index of the clean production of the electrolytic manganese to generate 6.43 tons of electrolytic manganese leaching residues, nearly 1200 ten thousand tons of manganese residues are produced every year, the manganese residues are mainly treated by a large amount of stacking and burying at present, and under the action of long-term weathering leaching, large-scale cultivated land and surface underground water sources are polluted, so that the ecological environment is seriously damaged. How to change waste into valuables, recycle the manganese slag comprehensively, reduce the harm of manganese slag to the utmost extent, become the focus of manganese-related enterprises and local governments.
The resource utilization of the electrolytic manganese slag mainly comprises autoclaved brick making, fertilizer making, paving materials, cement retarders, cement production and the like, but is limited by various product qualities or technologies, and industrial application is limited in various aspects, so that the resource utilization of the electrolytic manganese slag is limited. The resource utilization approach of the manganese slag is comprehensively considered, and the preparation of cement by using the electrolytic manganese slag is considered to be an important breakthrough for solving the stacking problem of the electrolytic manganese slag, but the electrolytic manganese slag can be massively used for producing cement only by high-temperature calcination and desulfurization, and equipment for performing front-end treatment on the manganese slag, including manganese slag desulfurization, deamination, high-temperature calcination and the like, inevitably causes high investment and increases the production cost.
Disclosure of Invention
In order to solve the problems, the invention provides an electrolytic manganese slag non-sintered brick which comprises the following raw materials in parts by weight: 61-73% of electrolytic manganese slag, and an alkaline viscosity breaking curing agent: 5.8-7.5%, aggregate: 11-21%, modified gel: 7.2-12%, and other components: 1 to 2.8 percent.
The alkaline viscosity breaking and curing agent is at least composed of one of quicklime, slaked lime, sodium hydroxide, potassium hydroxide and carbide slag, and can be used in combination or independently;
the further aggregate is at least composed of one of river sand, rock salt, fly ash and boiler slag, and can be used in combination or independently;
the other components at least comprise one of a surface modifier, an activator and a dispersant.
The invention also provides a preparation method of the electrolytic manganese slag non-sintered brick, which adopts an alkaline viscosity breaking curing agent to cure the residual water-soluble manganese, heavy metal and the like in the electrolytic manganese slag, and simultaneously promotes the ammonia of the ammonium sulfate in the manganese slag to be converted into ammonia gas for recycling; the solidified waste residue is used as a building raw material, and is pressed and formed by adding aggregate and modified gelling agent, and finally, the brick conforming to the requirement is produced through gelation and curing.
The further method comprises the following specific steps:
1) shredding pasty electrolytic manganese slag with water content of 18-30 wt% by a four-shaft shredder, accurately metering and feeding the shredded electrolytic manganese slag into a viscosity breaking reactor, simultaneously adding an alkaline viscosity breaking curing agent into the viscosity breaking reactor, wherein the dosage of the alkaline viscosity breaking curing agent is 4-5.5% of the weight of the manganese slag, stirring for the first time, and intensively recycling ammonia gas generated in the viscosity breaking and curing process;
the electrolytic manganese slag in the step can be manganese slag stored in a slag warehouse or fresh manganese slag, and generally, the electrolytic manganese slag in the invention is characterized in that the particles are fine and are distributed intensively, the particles smaller than 30um account for 83.33%, nearly half of the particles are concentrated between 15 and 30um, the water content is 18 to 30%, the manganese slag becomes a muddy body in the transportation process, the pretreatment is difficult, the resource utilization of the manganese slag is difficult, and the muddy manganese slag can be accurately measured and broken on the premise that a four-shaft shredder is adopted to shred the muddy manganese slag.
2) The manganese slag which is subjected to primary stirring and viscosity breaking passes through a double-roller crusher, the manganese slag is crushed until the particle size is smaller than 2.0mm, the manganese slag is conveyed to a stirrer by a lifter, an alkaline viscosity breaking and solidifying agent is added for secondary stirring, the moisture content in the material of the stirrer is maintained between 24 and 28 percent, the alkaline viscosity breaking and solidifying agent is 1.1 to 2.5 percent of the weight of the manganese slag, and ammonia gas generated in the viscosity breaking and solidifying process is intensively recycled;
3) then lifting the materials to a digestion bin, standing for digestion for 8-11 hours, so that unreacted ammonium sulfate in the manganese slag is completely decomposed, and soluble heavy metals such as manganese and the like are fully solidified;
4) feeding the digested material for 8-11 hours into an ammonia collector of a warm box by using a bucket elevator, turning the material for multiple times, heating to 85-90 ℃, evaporating more than 95% of ammonia gas in the material, and intensively recycling the evaporated ammonia gas; the materials from the ammonia collector of the incubator are sent into a storage bin which is used alternately through a bucket elevator, so that the manganese slag is finally aged and activated.
5) Feeding the material discharged from the storage bin into a planetary grinder, simultaneously adding aggregate, modified gelling agent and other components according to proportion, adding strong brine to control the water content of the mixed material to be 14-18%, carrying out third stirring in the planetary grinder, fully mixing the materials, screening out qualified brick making material with the particle size of less than 2.0mm by a roller screen, and conveying the qualified brick making material to a brick making process; returning the unqualified materials on the screen to the viscosity breaking process.
The qualified rate of the material particles smaller than 2.0mm after the treatment of the working procedure is high, the unqualified materials on the screen are 0.2-0.8 percent after the material particles are screened by the roller screen, the rework rate is low, and the cost and the working procedure are reduced.
6) And (3) feeding the qualified brick making material into a forming process, performing compression forming on the brick to obtain a manganese slag non-sintered brick with a standard specification, oxidizing, deoxidizing, and then feeding the brick to an autoclave for autoclaving to form silicon gel from each material in the manganese slag brick, wherein ammonia gas generated in the autoclave is intensively recycled.
Further, the ammonia gas is intensively recycled in the method, the ammonia gas is subjected to closed negative pressure water washing and absorption to produce ammonia water, and the produced ammonia water is used for electrolytic manganese.
Further non-sintered bricks according to the invention are building, municipal and road bricks.
The invention has the beneficial effects that:
(1) the consumption of manganese slag in the proportioning is high, the utilization rate is high, the proportion of cement, alkaline adhesive breaking agent and additive is low, the produced electrolytic manganese slag brick has high strength, the cost of the produced brick is low, the process is simple, the application range is wide, and the method is suitable for producing bricks by using solid slag in different scales;
(2) a large amount of ammonia gas generated in the brick making process is intensively recycled, so that resource waste and environmental pollution are avoided;
(3) the method develops a comprehensive utilization technology of manganese slag resource and harmless recovery, solves the harm of manganese slag, and provides reliable technical support for manganese-related enterprises and local governments.
Detailed Description
The invention is further illustrated by the following examples:
example 1:
the raw materials of the electrolytic manganese slag non-sintered brick are proportioned according to the weight proportion as follows: 73%, alkaline viscosity breaking curing agent: 6%, aggregate: 12%, modified gelling agent: 8 percent, and other components: 1 percent.
The method for preparing the electrolytic manganese slag non-sintered brick comprises the following specific steps:
1) shredding muddy electrolytic manganese slag with water content of 24wt% by a four-shaft shredder, accurately metering the shredded electrolytic manganese slag by mass, feeding the shredded electrolytic manganese slag into a viscosity breaking reactor, simultaneously adding quicklime serving as an alkaline viscosity breaking curing agent into the viscosity breaking reactor, stirring for the first time, and intensively recycling ammonia gas generated in the viscosity breaking and curing process, wherein the usage amount of the quicklime is 4.0% of that of the manganese slag;
2) the manganese slag which is subjected to primary stirring and viscosity breaking passes through a double-roller crusher, the manganese slag is crushed until the particle size is smaller than 2.0mm, the manganese slag is conveyed to a stirrer by a lifter, quicklime with the usage amount of 2.0 percent of the manganese slag is added for secondary stirring, the moisture content in the materials is kept between 24 and 28 percent in the stirring process, and ammonia gas generated in the viscosity breaking and solidifying process is intensively recycled;
3) then lifting the materials to a digestion bin, standing for digestion for 8 hours to completely decompose unreacted ammonium sulfate in the manganese slag, and fully solidifying the soluble heavy metals;
4) feeding the digested material into an ammonia collector of a warm box by using a bucket elevator, turning the material for many times, heating to 85 ℃, evaporating more than 95% of ammonia gas in the material, and intensively recycling the evaporated ammonia gas; the materials from the ammonia collector of the incubator are sent into a storage bin which is used alternately through a bucket elevator, so that the manganese slag is finally aged and activated, and the quality of the finished brick is ensured.
5) Feeding the material discharged from the storage bin into a planetary gear grinder for grinding and stirring, simultaneously adding 12% of aggregate river sand, 8% of modified gelling agent cement and 1% of other components in the original proportion, adding strong brine to control the water content of the mixed material to be 14-18%, carrying out third stirring in the planetary gear grinder, fully mixing the materials, screening out qualified brick making material with the particle size of less than 2.0mm by a roller screen, and sending the qualified brick making material to a brick making process; returning the unqualified materials on the screen to the viscosity breaking process.
Wherein: 1% of other components are 0.5% activator and 0.5% dispersant.
6) And (3) feeding the qualified brick making material into a forming process, performing compression forming to obtain manganese slag non-sintered bricks with standard specifications, oxidizing, deoxidizing, and then feeding the manganese slag non-sintered bricks into an autoclave for autoclaving to form silica gel from various materials in the manganese slag bricks, so that bricks meeting the building specification and used for buildings, municipal works and roads are produced, and ammonia gas generated in the autoclave is recycled in a centralized manner.
The ammonia gas is intensively recycled in each step, namely the ammonia gas is subjected to closed negative pressure water washing and absorption to produce ammonia water which is used for electrolyzing manganese.
Example 2:
different from the embodiment 1, in the embodiment, the raw materials of the non-sintered electrolytic manganese slag brick are proportioned according to the weight ratio: 61%, alkaline viscosity breaking curing agent: 7.5%, aggregate: 21%, modified gelling agent: 9 percent, and other components: 1.5 percent.
The method for preparing the electrolytic manganese slag non-sintered brick comprises the following specific steps:
1) the method comprises the following steps of shredding muddy electrolytic manganese slag with water content of 30wt% through a four-shaft shredder, accurately metering the shredded electrolytic manganese slag by mass, feeding the shredded electrolytic manganese slag into a breaking reactor, simultaneously adding quicklime with the mass of 4% of manganese slag and slaked lime with the mass of 1% of manganese slag as alkaline breaking and sticking curing agents into the breaking reactor, and carrying out primary stirring;
2) the manganese slag which is subjected to primary stirring and viscosity breaking passes through a double-roller crusher, the manganese slag is crushed until the particle size is smaller than 2.0mm, the manganese slag is conveyed to a stirrer by a lifter, quicklime with the usage amount of 2.5 percent of the manganese slag is added for secondary stirring, the moisture content in the materials is kept between 24 and 26 percent in the stirring process, and ammonia gas generated in the viscosity breaking and solidifying process is intensively recycled;
3) then lifting the materials to a digestion bin, standing for digestion for 11 hours, so that unreacted ammonium sulfate in the manganese slag is completely decomposed, and soluble heavy metals are fully solidified;
4) feeding the digested material into an ammonia collector of a warm box by using a bucket elevator, turning the material for many times, heating to 87 ℃, evaporating more than 95% of ammonia gas in the material, and intensively recycling the evaporated ammonia gas; the materials from the ammonia collector of the incubator are sent into a storage bin which is used alternately through a bucket elevator, so that the manganese slag is finally aged and activated, and the quality of the finished brick is ensured.
5) Feeding the material discharged from the storage bin into a planetary gear grinder for grinding and stirring, simultaneously adding 21% of aggregate, 9% of modified gelling agent and 1.5% of other components, adding strong brine to control the water content of the mixed material to be 17-18%, stirring for the third time in the planetary gear grinder, fully mixing the materials, screening out qualified brick making material with the particle size of less than 1.5mm by a roller screen, and sending the qualified brick making material to a brick making process; returning the unqualified materials on the screen to the viscosity breaking process.
Wherein: 21% of aggregate is a mixture of rock, fly ash and boiler slag, and each accounts for 7%;
9% of the modified gel is portland cement;
1.5% of other components are three kinds of surface modifier, activator and dispersant, each of which accounts for 0.5%.
6) And (3) feeding the qualified brick making material into a forming process, performing compression forming to obtain manganese slag non-sintered bricks with standard specifications, oxidizing, deoxidizing, and then feeding the manganese slag non-sintered bricks into an autoclave for autoclaving to form silica gel from various materials in the manganese slag bricks, so that bricks meeting the building specification and used for buildings, municipal works and roads are produced, and ammonia gas generated in the autoclave is recycled in a centralized manner.
Example 3:
different from the embodiment 1, in the embodiment, the raw materials of the non-sintered electrolytic manganese slag brick are proportioned according to the weight ratio: 66%, alkaline viscosity breaking curing agent: 7%, aggregate: 17%, modified gelling agent: 7.2 percent, and other components: 2.8 percent.
The method for preparing the electrolytic manganese slag non-sintered brick comprises the following specific steps:
1) the method comprises the following steps of shredding muddy electrolytic manganese slag containing 28wt% of water by a four-shaft shredder, accurately metering the shredded electrolytic manganese slag by mass, feeding the shredded electrolytic manganese slag into a viscosity breaking reactor, adding quicklime accounting for 3.5% of the manganese slag by mass and sodium hydroxide accounting for 1.5% of the manganese slag by mass as alkaline viscosity breaking curing agents into the viscosity breaking reactor, and stirring for the first time;
2) the manganese slag which is subjected to primary stirring and bonding breaking passes through a double-roller crusher, the manganese slag is crushed until the particle size is smaller than 1.2mm, the manganese slag is conveyed to a stirrer by a lifter, quicklime with the amount of 2% of the manganese slag is added for secondary stirring, the water content in the materials is maintained between 26% and 28% in the stirring process, and ammonia gas generated in the bonding breaking and curing process is intensively recycled;
3) then lifting the materials to a digestion bin, standing for digestion for 9 hours to completely decompose unreacted ammonium sulfate in the manganese slag, and fully solidifying the soluble heavy metals;
4) feeding the digested material into an ammonia collector of a warm box by using a bucket elevator, turning the material for multiple times, heating to 88 ℃, evaporating more than 95% of ammonia gas in the material, and intensively recycling the evaporated ammonia gas; the materials from the ammonia collector of the incubator are sent into a storage bin which is used alternately through a bucket elevator, so that the manganese slag is finally aged and activated, and the quality of the finished brick is ensured.
5) Feeding the material discharged from the storage bin into a planetary gear grinder for grinding and stirring, simultaneously adding 17% of aggregate, 7.2% of modified gelling agent and 2.8% of other components, adding strong brine to control the water content of the mixed material to be 16-18%, grinding the mixture in the planetary gear grinder for the third time, fully mixing the materials, screening out qualified brick making material with the particle size of less than 1.0mm by a roller screen, and sending the qualified brick making material to a brick making process; returning the unqualified materials on the screen to the viscosity breaking process.
Wherein: 17% of aggregate is a mixture of 12% of fly ash and 7% of boiler slag;
the modified gel is cement;
2.8% of the other components was a mixture of 1.2% of surface modifier, 0.9% by weight of activator and 0.7% of dispersant.
6) And (3) feeding the qualified brick making material into a forming process, performing compression forming to obtain manganese slag non-sintered bricks with standard specifications, oxidizing, deoxidizing, and then feeding the manganese slag non-sintered bricks into an autoclave for autoclaving to form silica gel from various materials in the manganese slag bricks, so that bricks meeting the building specification and used for buildings, municipal works and roads are produced, and ammonia gas generated in the autoclave is recycled in a centralized manner.
Example 4:
different from the embodiment 1, in the embodiment, the raw materials of the non-sintered electrolytic manganese slag brick are proportioned according to the weight ratio: 71%, alkaline viscosity breaking curing agent: 5.8%, aggregate: 11%, modified gelling agent: 10.2 percent, and other components: 2 percent.
The method for preparing the electrolytic manganese slag non-sintered brick comprises the following specific steps:
1) shredding muddy electrolytic manganese slag containing 18wt% of water by a four-shaft shredder, accurately metering the shredded electrolytic manganese slag by mass, feeding the shredded electrolytic manganese slag into a viscosity breaking reactor, adding quicklime serving as an alkaline viscosity breaking curing agent accounting for 4.2% of the manganese slag by mass into the viscosity breaking reactor, and stirring for the first time;
2) the manganese slag which is subjected to primary stirring and viscosity breaking passes through a double-roller crusher, the manganese slag is crushed until the particle size is smaller than 0.8mm, the manganese slag is conveyed to a stirrer by a lifter, quicklime with the dosage of 1.6 percent of that of the manganese slag is added for secondary stirring, the moisture content in the materials is kept between 25 and 27 percent in the stirring process, and ammonia gas generated in the viscosity breaking and solidifying process is intensively recycled;
3) then lifting the materials to a digestion bin, standing for digestion for 10 hours to completely decompose unreacted ammonium sulfate in the manganese slag, and fully solidifying the soluble heavy metals;
4) feeding the digested material into an ammonia collector of a warm box by using a bucket elevator, turning the material for many times, heating to 89 ℃, evaporating more than 95% of ammonia gas in the material, and intensively recycling the evaporated ammonia gas; the materials from the ammonia collector of the incubator are sent into a storage bin which is used alternately through a bucket elevator, so that the manganese slag is finally aged and activated, and the quality of the finished brick is ensured.
5) Feeding the material discharged from the storage bin into a planetary gear grinder for grinding and stirring, simultaneously adding aggregate with the raw material ratio of 11%, modified gelling agent with the raw material ratio of 10.2% and other components with the raw material ratio of 2%, adding strong brine to control the water content of the mixed material to be 16-18%, carrying out third stirring in the planetary gear grinder, fully mixing the materials, screening out qualified brick making material with the particle size of less than 1.0mm by a roller screen, and sending the qualified brick making material to a brick making process; returning the unqualified materials on the screen to the viscosity breaking process.
Wherein: 11% of the aggregate is river sand;
10.2% of the modified gelling agent is portland cement;
2% of the other components was a mixture of 1.0% activator and 1.0% dispersant. .
6) And (3) feeding the qualified brick making material into a forming process, performing compression forming to obtain manganese slag non-sintered bricks with standard specifications, oxidizing, deoxidizing, and then feeding the manganese slag non-sintered bricks into an autoclave for autoclaving to form silica gel from various materials in the manganese slag bricks, so that bricks meeting the building specification and used for buildings, municipal works and roads are produced, and ammonia gas generated in the autoclave is recycled in a centralized manner.
Example 5:
different from the embodiment 1, in the embodiment, the raw materials of the non-sintered electrolytic manganese slag brick are proportioned according to the weight ratio: 66%, alkaline viscosity breaking curing agent: 6.2%, aggregate: 14%, modified gelling agent: 12%, and other components: 1.8 percent.
The method for preparing the electrolytic manganese slag non-sintered brick comprises the following specific steps:
1) the method comprises the following steps of shredding muddy electrolytic manganese slag with water content of 26wt% by a four-shaft shredder, accurately metering the shredded electrolytic manganese slag by mass, feeding the shredded electrolytic manganese slag into a viscosity breaking reactor, adding carbide slag with the mass of 5.1% of that of the manganese slag as an alkaline viscosity breaking curing agent into the viscosity breaking reactor, and stirring for the first time;
2) the manganese slag which is subjected to primary stirring and viscosity breaking passes through a double-roller crusher, the manganese slag is crushed until the particle size is smaller than 1.1mm, the manganese slag is conveyed to a stirrer by a lifter, potassium hydroxide with the dosage of 1.1 percent of the manganese slag is added as an alkaline viscosity breaking curing agent for secondary stirring, the water content in the materials is kept between 25 and 28 percent in the stirring process, and ammonia gas generated in the viscosity breaking curing process is intensively recycled;
3) then lifting the materials to a digestion bin, standing for digestion for 9.2 hours to completely decompose unreacted ammonium sulfate in the manganese slag, and fully solidifying the soluble heavy metals;
4) feeding the digested material into an ammonia collector of a warm box by using a bucket elevator, turning the material for many times, heating to 90 ℃, evaporating more than 95% of ammonia gas in the material, and intensively recycling the evaporated ammonia gas; the materials from the ammonia collector of the incubator are sent into a storage bin which is used alternately through a bucket elevator, so that the manganese slag is finally aged and activated, and the quality of the finished brick is ensured.
5) Feeding the material discharged from the storage bin into a planetary gear grinder for grinding and stirring, simultaneously adding 14% of aggregate, 12% of modified gelling agent and 1.8% of other components, adding strong brine to control the water content of the mixed material to be 15-17%, stirring for the third time in the planetary gear grinder, fully mixing the materials, screening out qualified brick making material with the particle size of less than 1.3mm by a roller screen, and sending the qualified brick making material to a brick making process; returning the unqualified materials on the screen to the viscosity breaking process.
Wherein: 11% of aggregate is a mixture of rock nitrate and fly ash;
12% of the modified gelling agent is cement;
1.8% of other components was a mixture of 1.0% of activator and 0.8% of dispersant. .
6) And (3) feeding the qualified brick making material into a forming process, performing compression forming to obtain manganese slag non-sintered bricks with standard specifications, oxidizing, deoxidizing, and then feeding the manganese slag non-sintered bricks into an autoclave for autoclaving to form silica gel from various materials in the manganese slag bricks, so that bricks meeting the building specification and used for buildings, municipal works and roads are produced, and ammonia gas generated in the autoclave is recycled in a centralized manner.
The foregoing examples are to be understood as merely illustrative of the present invention in more detail and not restrictive thereof, and although some of the materials and acts used in the practice of the present invention are known in the art, the invention is described herein in as much detail as possible, unless otherwise specified.

Claims (8)

1. The electrolytic manganese slag non-sintered brick is characterized in that: the electrolytic manganese slag non-sintered brick comprises the following raw materials in percentage by weight: 61-73%, alkaline viscosity breaking curing agent: 5.8-7.5%, aggregate: 11-21%, modified gel: 7.2-12%, and other components: 1 to 2.8 percent.
2. The electrolytic manganese slag non-sintered brick according to claim 1, wherein: the alkaline viscosity breaking and curing agent at least comprises one of quicklime, slaked lime, sodium hydroxide, potassium hydroxide and carbide slag.
3. The electrolytic manganese slag non-sintered brick according to claim 1, wherein: the aggregate is at least composed of one of river sand, rock salt, fly ash and boiler slag.
4. The electrolytic manganese slag non-sintered brick according to claim 1, wherein: the other components at least comprise one of a surface modifier, an activator and a dispersant.
5. The preparation method of the electrolytic manganese slag non-sintered brick is characterized by comprising the following steps: the residual water-soluble manganese, heavy metal and the like in the electrolytic manganese slag are solidified by adopting an alkaline viscosity breaking curing agent, and meanwhile, the ammonia of ammonium sulfate in the manganese slag is promoted to be converted into ammonia gas for recycling; the solidified waste residue is used as a building raw material, and is pressed and formed by adding aggregate and modified gelling agent, and finally, the brick conforming to the requirement is produced through gelation and curing.
6. The method for preparing the electrolytic manganese slag non-sintered brick according to claim 5, wherein the method comprises the following steps: the method specifically comprises the following steps:
1) shredding pasty electrolytic manganese slag with water content of 18-30 wt% by a four-shaft shredder, accurately metering and feeding the shredded electrolytic manganese slag into a viscosity breaking reactor, simultaneously adding an alkaline viscosity breaking curing agent into the viscosity breaking reactor, wherein the dosage of the alkaline viscosity breaking curing agent is 4-5.5% of the weight of the manganese slag, stirring for the first time, and intensively recycling ammonia gas generated in the viscosity breaking and curing process;
2) crushing the manganese slag subjected to primary stirring and viscosity breaking by using a double-roller crusher until the particle size of the manganese slag is smaller than 2.0mm, conveying the manganese slag to a stirrer by using a lifter, adding an alkaline viscosity breaking and solidifying agent for secondary stirring, and simultaneously maintaining the moisture content in the material of the stirrer to be between 24 and 28 percent, wherein the alkaline viscosity breaking and solidifying agent is 1.1 to 2.5 percent of the weight of the manganese slag, and ammonia gas generated in the viscosity breaking and solidifying process is intensively recycled;
3) then lifting the materials to a digestion bin, standing for digestion for 8-11 hours, so that unreacted ammonium sulfate in the manganese slag is completely decomposed, and soluble heavy metals such as manganese and the like are fully solidified;
4) feeding the digested material for 8-11 hours into an ammonia collector of a warm box by using a bucket elevator, turning the material for multiple times, heating to 85-90 ℃, evaporating more than 95% of ammonia gas in the material, and intensively recycling the evaporated ammonia gas; the materials from the ammonia collector of the incubator are sent into a storage bin which is used alternately through a bucket elevator, so that the manganese slag is finally aged and activated;
5) feeding the material discharged from the storage bin into a planetary grinder, simultaneously adding aggregate, modified gelling agent and other components according to the raw material proportion, adding strong brine to control the water content of the mixed material to be 14-18%, carrying out third stirring in the planetary grinder, fully mixing the materials, screening out qualified brick making material with the particle size of less than 2.0mm by a roller screen, and sending the qualified brick making material to a brick making process; returning the unqualified materials on the screen to the viscosity breaking process;
6) and (3) feeding the qualified brick making material into a forming process, performing compression forming on the brick to obtain a manganese slag non-sintered brick with a standard specification, oxidizing, deoxidizing, and then feeding the brick to an autoclave for autoclaving to form silicon gel from each material in the manganese slag brick, wherein ammonia gas generated in the autoclave is intensively recycled.
7. The method for preparing the electrolytic manganese slag non-sintered brick as claimed in claim 6, wherein: the ammonia gas is intensively recycled by carrying out closed negative pressure water washing and absorption on the ammonia gas to produce ammonia water which is used for electrolytic manganese.
8. The electrolytic manganese slag non-sintered brick according to any one of claims 1 to 7, wherein said non-sintered brick is a brick for construction, municipal or road use.
CN201911149327.4A 2019-11-21 2019-11-21 Electrolytic manganese slag non-sintered brick and preparation method thereof Pending CN110642560A (en)

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CN111592260A (en) * 2020-05-08 2020-08-28 北京科技大学 Additive for removing ammonia nitrogen in electrolytic manganese slag and removing method thereof
CN112047702A (en) * 2020-09-01 2020-12-08 贵州城晖环保科技有限公司 Baking-free antique blue brick based on electrolytic manganese slag and preparation method and application thereof
CN114505323A (en) * 2022-03-10 2022-05-17 广西建筑材料科学研究设计院有限公司 Harmless treatment method and equipment for electrolytic manganese slag

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CN111592260A (en) * 2020-05-08 2020-08-28 北京科技大学 Additive for removing ammonia nitrogen in electrolytic manganese slag and removing method thereof
CN112047702A (en) * 2020-09-01 2020-12-08 贵州城晖环保科技有限公司 Baking-free antique blue brick based on electrolytic manganese slag and preparation method and application thereof
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