CN110642543A - Alkaline cementing material produced by electrolytic manganese slag - Google Patents
Alkaline cementing material produced by electrolytic manganese slag Download PDFInfo
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- CN110642543A CN110642543A CN201911151473.0A CN201911151473A CN110642543A CN 110642543 A CN110642543 A CN 110642543A CN 201911151473 A CN201911151473 A CN 201911151473A CN 110642543 A CN110642543 A CN 110642543A
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- manganese slag
- alkaline
- electrolytic manganese
- slag
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 135
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 130
- 239000011572 manganese Substances 0.000 title claims abstract description 130
- 239000002893 slag Substances 0.000 title claims abstract description 121
- 239000000463 material Substances 0.000 title claims abstract description 118
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 47
- 239000012190 activator Substances 0.000 claims abstract description 28
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 15
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 10
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 10
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 3
- 230000001737 promoting effect Effects 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 35
- 230000005284 excitation Effects 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 16
- 239000003349 gelling agent Substances 0.000 claims description 15
- 238000003860 storage Methods 0.000 claims description 14
- 239000004568 cement Substances 0.000 claims description 12
- 230000029087 digestion Effects 0.000 claims description 12
- 238000004064 recycling Methods 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000012216 screening Methods 0.000 claims description 9
- 239000000292 calcium oxide Substances 0.000 claims description 8
- 235000012255 calcium oxide Nutrition 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 239000012267 brine Substances 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 7
- 239000011398 Portland cement Substances 0.000 claims description 6
- 239000010881 fly ash Substances 0.000 claims description 5
- 239000010884 boiler slag Substances 0.000 claims description 4
- 239000003607 modifier Substances 0.000 claims description 4
- 239000004576 sand Substances 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- 235000002639 sodium chloride Nutrition 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 239000002699 waste material Substances 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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Classifications
-
- 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
- C04B7/153—Mixtures thereof with other inorganic cementitious materials or other activators
-
- 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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/006—Compositions 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 mineral polymers, e.g. geopolymers of the Davidovits type
-
- 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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions 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
- C04B28/04—Portland cements
-
- 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
- C04B7/153—Mixtures thereof with other inorganic cementitious materials or other activators
- C04B7/1535—Mixtures thereof with other inorganic cementitious materials or other activators with alkali metal containing activators, e.g. sodium hydroxide or waterglass
-
- 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
- C04B7/153—Mixtures thereof with other inorganic cementitious materials or other activators
- C04B7/17—Mixtures thereof with other inorganic cementitious materials or other activators with calcium oxide containing activators
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00017—Aspects relating to the protection of the environment
-
- 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
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
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- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses an alkaline cementing material produced by electrolytic manganese slag, and relates to the technical field of waste slag resource utilization. The alkaline cementing material produced by the electrolytic manganese slag comprises the following raw materials in parts by weight: electrolytic manganese slag: 61-73%, alkali activator: 5.8-7.5%, aggregate: 11-21%, modified gel: 7.2-12%, and other components: 1 to 2.8 percent. Firstly, exciting and solidifying the residual water-soluble manganese, heavy metal and the like in the electrolytic manganese slag by adopting an alkaline exciting agent, and simultaneously promoting the ammonia of ammonium sulfate in the manganese slag to be converted into ammonia gas to be recycled as the raw material of the electrolytic manganese; the method utilizes the waste to the maximum extent, has simple process, low cost and wide application range, and is suitable for producing gel materials by solid slag in different scales of industries.
Description
Technical Field
The invention belongs to the technical field of industrial waste residue resource utilization, and particularly relates to an alkaline cementing material produced by electrolytic manganese residues.
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 alkaline cementing material produced by electrolytic manganese slag, and the manufacturing method comprises the following steps: firstly, exciting and solidifying the residual water-soluble manganese, heavy metal and the like in the electrolytic manganese slag by adopting an alkaline exciting agent, and simultaneously promoting the ammonia of ammonium sulfate in the manganese slag to be converted into ammonia gas to be recycled as an electrolytic manganese raw material; adding aggregate, modified gel and other components into the excited and solidified electrolytic manganese slag, homogenizing and screening to obtain an alkaline gel material;
the method further comprises the following steps:
1) the method comprises the following steps of shredding muddy 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 activator with the weight of 5.0-10% of that of the manganese slag into an excitation reactor, carrying out primary stirring, and intensively recycling ammonia gas generated in the alkaline excitation process;
2) crushing the manganese slag subjected to the 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 activator accounting for 1-3wt% of the weight of the manganese slag for secondary stirring, maintaining the water content in the material between 24-28%, and intensively recycling ammonia gas generated in the excitation process;
3) then the materials are lifted to a digestion bin and stay for 8 to 11 hours, so that the unreacted ammonium sulfate in the manganese slag is almost completely decomposed, and soluble heavy metals such as manganese and the like are fully excited and solidified;
4) and (3) feeding the digested material for 8-11 hours into an ammonia collector of the incubator 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 feeding the material discharged from the ammonia collector of the incubator into a storage bin which is alternately used by using the bucket elevator to finally age and activate the manganese slag.
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 formed material to be 14-18%, grinding in the planetary grinder for the third time, fully mixing the materials, screening qualified gel material with the particle size of less than 2.0mm by a roller screen, and feeding the qualified gel material to a gel 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.
The alkaline cementing material produced by further electrolyzing manganese slag comprises the following raw materials in parts by weight: 61-73%, alkali activator: 5.8-7.5%, aggregate: 11-21%, modified gel: 7.2-12%, and other components: 1 to 2.8 percent.
Further, the alkali activator is at least one of quicklime, slaked lime, sodium hydroxide, potassium hydroxide or carbide slag.
The aggregate used further comprises at least one of river sand, rock salt, fly ash and boiler slag.
The modified gel is further composed of at least one of cement, ordinary portland cement and portland cement.
Further, other components used are at least one of a surface modifier, an activator and a dispersant.
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, an alkaline activator and an additive is low, the production cost is low, the process is simple, the application range is wide, and the method is suitable for producing gel materials by using industrial solid slag on different scales;
(2) 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.
Drawings
FIG. 1 is a schematic diagram of a process flow for producing alkaline cementing material by electrolytic manganese slag.
Detailed Description
The invention is further illustrated by the following examples:
example 1:
proportioning the raw materials of the alkaline cementing material produced by the electrolytic manganese slag according to the weight proportion: 73%, alkali activator: 6%, aggregate: 12%, modified gelling agent: 8 percent, and other components: 1 percent.
The preparation method of the alkaline cementing material produced by the electrolytic manganese slag comprises the following specific steps:
1) the method comprises the following steps of shredding muddy electrolytic manganese slag with 24wt% of water by a four-shaft shredder, accurately metering the shredded electrolytic manganese slag by mass, feeding the shredded electrolytic manganese slag into an excitation reactor, adding quicklime serving as an alkaline activator into the excitation reactor, stirring for the first time, and intensively recycling ammonia gas generated in the alkaline excitation process, wherein the usage amount of the quicklime is 4.0% of that of the manganese slag;
2) the manganese slag after the primary stirring excitation 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 excitation material with the dosage of 2.0 percent of the weight of the manganese slag is added for secondary stirring, the moisture content in the material is maintained between 24 and 28 percent in the stirring process, and ammonia gas generated in the alkaline excitation 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 exciting and curing 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.
5) Feeding the material discharged from the storage bin into a planetary gear grinder to carry out wheel 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 to fully mix the materials, screening out qualified gelling material with the particle size smaller than 2.0mm by a roller screen, and sending the qualified gelling material to a gelling process; returning the unqualified materials on the screen to the excitation process.
Wherein: 1% of other components are 0.5% activator and 0.5% dispersant.
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 alkaline cementing material produced from the electrolytic manganese slag is prepared by the following raw materials in parts by weight: 61%, alkali activator: 7.5%, aggregate: 21%, modified gelling agent: 9 percent, and other components: 1.5 percent.
The preparation method of the alkaline cementing material produced by the electrolytic manganese slag 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 an excitation reactor, simultaneously adding quicklime accounting for 4% of the manganese slag by mass and slaked lime accounting for 1% of the manganese slag by mass as alkaline activators into the excitation reactor, and stirring for the first time;
2) the manganese slag after the primary stirring and excitation 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 exciting agent with the dosage of 2.5 percent of that of the manganese slag is added for secondary stirring, the moisture content in the materials is maintained between 24 and 26 percent in the stirring process, and ammonia gas generated in the alkaline exciting 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 the soluble heavy metals are fully excited and 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.
5) Feeding the material discharged from the storage bin into a planetary grinder for grinding and stirring, simultaneously adding 21% of aggregate, 9% of modified gelling agent and 1.5% of other components according to the raw material proportion, adding strong brine to control the water content of the mixed material to be 17-18%, grinding the mixed material in the planetary grinder for the third time, fully mixing the materials, screening out qualified gelled material with the particle size of less than 1.5mm by a roller screen, and sending the qualified gelled material to a gelling process; returning the unqualified materials on the screen to the excitation 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%.
Example 3:
different from the embodiment 1, in the embodiment, the alkaline cementing material produced from the electrolytic manganese slag is prepared by the following raw materials in parts by weight: 66%, alkali activator: 7%, aggregate: 17%, modified gelling agent: 7.2 percent, and other components: 2.8 percent.
The preparation method of the alkaline cementing material produced by the electrolytic manganese slag 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 an excitation 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 activators into the excitation reactor, and stirring for the first time;
2) the manganese slag after the primary stirring and excitation 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, an alkaline exciting agent with the dosage of 2 percent of that of the manganese slag is added for secondary stirring, the water content in the materials is maintained between 26 and 28 percent in the stirring process, and ammonia gas generated in the alkaline exciting 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 exciting and curing 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.
5) Feeding the material discharged from the storage bin into a planetary gear grinder to carry out wheel 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%, carrying out third stirring in the planetary gear grinder to fully mix the materials, screening out qualified gelled material with the particle size smaller than 1.0mm by a roller screen, and sending the qualified gelled material to a gelling process; returning the unqualified materials on the screen to the excitation process.
Wherein: 17% of aggregate is a mixture of 12% of fly ash and 7% of boiler slag;
7.2% of the modified gelling agent 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.
Example 4:
different from the embodiment 1, in the embodiment, the alkaline cementing material produced from the electrolytic manganese slag is prepared by the following raw materials in parts by weight: 71%, alkaline activator: 5.8%, aggregate: 11%, modified gelling agent: 10.2 percent, and other components: 2 percent.
The preparation method of the alkaline cementing material produced by the electrolytic manganese slag comprises the following specific steps:
1) the method comprises the following steps of 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 an excitation reactor, adding quicklime serving as an alkaline activator accounting for 4.2% of the manganese slag by mass into the excitation reactor, and stirring for the first time;
2) the manganese slag after the primary stirring and excitation 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 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 alkaline excitation 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 exciting and curing 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.
5) Feeding the material discharged from the storage bin into a planetary 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%, stirring for the third time in the planetary grinder to fully mix the materials, screening out an alkaline gel material with the particle size of less than 1.0mm by a roller screen, and sending the alkaline gel material to a gelling process; returning the unqualified materials on the screen to the excitation 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. .
Example 5:
different from the embodiment 1, in the embodiment, the alkaline cementing material produced from the electrolytic manganese slag is prepared by the following raw materials in parts by weight: 66%, alkali activator: 6.2%, aggregate: 14%, modified gelling agent: 12%, and other components: 1.8 percent.
The method for preparing the alkaline cementing material produced by the electrolytic manganese slag 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 an excitation reactor, adding carbide slag with the mass of 5.1% of that of the manganese slag as an alkaline activator into the excitation reactor, and stirring for the first time;
2) the manganese slag which is subjected to the first 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 activator for second stirring, the water content in the materials is kept between 25 and 28 percent in the stirring process, and ammonia gas generated in the alkaline activation 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 exciting and curing 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.
5) Feeding the material discharged from the storage bin into a planetary 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 grinder to fully mix the materials, screening out qualified alkaline gel material with the particle size smaller than 1.3mm by a roller screen, and sending the qualified alkaline gel material to a gelling process; returning the unqualified materials on the screen to the excitation 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. .
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 (6)
1. The alkaline cementing material produced by electrolytic manganese slag is characterized by being prepared by the following method: firstly, exciting and solidifying the residual water-soluble manganese, heavy metal and the like in the electrolytic manganese slag by adopting an alkaline exciting agent, and simultaneously promoting the ammonia of ammonium sulfate in the manganese slag to be converted into ammonia gas to be recycled as an electrolytic manganese raw material; adding aggregate, modified gel and other components into the excited and solidified electrolytic manganese slag, homogenizing and screening to obtain an alkaline gel material;
the alkaline cementing material produced by electrolyzing manganese slag as claimed in claim 1, wherein said method comprises the following steps:
1) the method comprises the following steps of shredding muddy 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 an excitation reactor, adding an alkaline activator with the weight of 5.0-10% of that of the manganese slag into the excitation reactor, stirring for the first time, and intensively recycling ammonia gas generated in the alkaline excitation process;
2) crushing the manganese slag subjected to the 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 activator accounting for 1-3wt% of the weight of the manganese slag for secondary stirring, maintaining the water content in the material between 24-28%, and intensively recycling ammonia gas generated in the excitation process;
3) then the materials are lifted to a digestion bin and stay for 8 to 11 hours, so that the unreacted ammonium sulfate in the manganese slag is almost completely decomposed, and soluble heavy metals such as manganese and the like are fully excited and 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 feeding the material discharged from the ammonia collector of the warm box into a storage bin which is alternately used by using the bucket elevator to finally age and activate manganese slag;
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 formed material to be 14-18%, grinding in the planetary grinder for the third time, fully mixing the materials, screening qualified gel material with the particle size of less than 2.0mm by a roller screen, and feeding the qualified gel material to a gel process; returning the unqualified materials on the screen to the excitation process.
2. The alkaline cementing material produced by electrolytic manganese slag as claimed in claim 1 or 2, wherein the raw materials comprise, by weight: 61-73%, alkali activator: 5.8-7.5%, aggregate: 11-21%, modified gel: 7.2-12%, and other components: 1 to 2.8 percent.
3. The alkaline cement produced from electrolytic manganese slag according to claim 3, wherein: the alkali activator at least comprises one of quicklime, slaked lime, sodium hydroxide, potassium hydroxide or carbide slag.
4. The alkaline cementing material produced by electrolytic manganese slag according to claim 3, wherein the aggregate is at least one of river sand, rock salt, fly ash and boiler slag.
5. The alkaline binding material produced from electrolytic manganese residues according to claim 3, wherein the modified gelled body is composed of at least one of cement, ordinary portland cement and portland cement.
6. The alkaline cement produced from electrolytic manganese slag according to claim 3, wherein said other component is at least one of a surface modifier, an activator and a dispersant.
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