CN104725001B - A kind of composition containing electrolytic manganese residues and the application on electrolytic manganese residues double exempt from the building materials such as brick is prepared - Google Patents
A kind of composition containing electrolytic manganese residues and the application on electrolytic manganese residues double exempt from the building materials such as brick is prepared Download PDFInfo
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Abstract
The invention discloses a kind of composition containing electrolytic manganese residues, including levigate electrolytic manganese residues, aggregate chips, activity excitant.Described levigate electrolytic manganese residues are that the doped quick lime of original state electrolytic manganese residues is neutralized, stands, dried, and are milled to specific surface area more than 500m2The electrolytic manganese residues of/kg.The largest particles particle diameter of aggregate chips be 10mm, and 10mm to 5mm, 5mm, 1.25mm particle diameter mixture.Activity excitant includes alkaline excitation material and surfactant, wherein, alkaline excitation material includes one or more in clinker, sodium metaaluminate, metakaolin, red mud, quick lime, and surfactant includes one or more in naphthalenesulfonate formaldehyde condensation compound, sulfonated melamine compound condensation polymer, wooden sodium sulfonate.The electrolytic manganese residues composition is applied to prepare electrolytic manganese residues double exempt from the building materials such as brick by the present invention.Obtained double exempt from the building materials such as brick is more than MU15 grades, and process is simple, energy-conserving and environment-protective, market prospects are wide, electrolytic manganese slag brick better performances.
Description
Technical field
The present invention relates to a kind of composition containing electrolytic manganese residues, and it is applied in preparation double exempt from the building materials such as brick, while specific open
The preparation method of electrolytic manganese residues double exempt from the building materials such as brick.
Background technology
Electrolytic manganese residues be by the manganese spar based on manganese carbonate ore, after levigate and sulfuric acid reaction to obtain manganese sulfate molten
Liquid, by oxidation, neutralize, purification and electrolysis after extract manganese metal after faintly acid industrial residue, with grain graininess it is tiny, contain
Water rate is up to 16%~40%, it is sticky and easily blocking the features such as.Manganese metal is one of important strategic resource in national economy,
China is also the electrolytic manganese big producer of the production history for having had nearly more than 50 years, but simultaneously as the electricity of typical hydrometallurgy
Solution manganese industry, belong to three industries high of typical highly energy-consuming, high pollution and maximum discharge, promote economic development and meanwhile also bring as
The serious environmental problem that electrolytic manganese residues are stacked and polluted.It is general to use electroextraction manganese metal method, often extract 1t electrolytic metals
The acid-soaked waste residue amount that manganese is discharged is about 8~9t.2008,2009,2010,2011 and 2012 electrolytic manganeses of China
Actual production is respectively 1,140,000 tons, 1,310,000 tons, 1,380,000 tons, 1,480,000 tons and 1,160,000 tons, and 5 years accumulative 6,470,000 tons, produces extremely
Few fifty-five million ton electrolytic manganese residues, this is also without the manganese quantity of slag being deposited in Tailings Dam over the years before 2008.Electrolytic manganese residues contain manganese,
The mineralogical compositions such as Sulfates, ammonia nitrogen, arsenic, selenium, according to national regulation, still fall within general industry waste, but wherein sulfate, ammonia
Nitrogen, selenium and manganese ion concentration are high, and its leachate still may make a big impact to environment.Due to current electrolysis manganese slag money
Source producing level is extremely low, and substantial amounts of electrolytic manganese residues are still emitted into tailings reservoir for piling using wet method, and so big waste residue amount was both
Take a large amount of soils and pollute environment again, tremendous economic and environmental protection pressure are brought to electrolytic manganese manufacturing enterprise and manganese ore surrounding enviroment.
Harm and the volume of cargo in storage of electrolytic manganese residues are reduced to greatest extent, carry out electrolytic manganese residues recycling, it is extremely urgent.
The current many scholars of China also carry out the research and application of electrolytic manganese residues recycling.Have focused largely on valuable unit
Element reclaims, as retarder in manufacture of cement, high-temperature firing sulphate aluminium cement and prepare inferior grade Binder Materials aspect, in electricity
The brickmaking research of solution manganese slag is less, and is generally addition cement and other materials, the research of steam-pressing brisk is prepared using steam-cured mode, existing
Only Wang Zhi, Zhao Minglun et al. has carried out electrolytic manganese residues and has prepared non-burning brick research in document, but Wang Zhi et al. 30% powder of use
Binder Materials prepared by coal ash, 10% quick lime, 10% cement and 50% original state electrolytic manganese residues, according to Binder Materials：River sand=
1:0.9, water-solid ratio is 0.10~0.20, and actual non-burning brick proportioning is original state electrolytic manganese residues：Flyash：Quick lime：Cement：River sand
=26.3%：15.8%：5.3%：5.3%：47.3%, electrolytic manganese residues utilization rate is less than 30%, and non-burning brick for preparing
MU10 strength grades can be reached；Zhao Minglun etc. uses 60%~70% electrolytic manganese residues, 10%~20% cement, 5%~10% life
Lime and a small amount of surfactant are constituted, and the light-weight brick of MU10 grades is prepared in stirring vibration moulding, and electrolytic manganese residues utilization rate is most
It is high by 70%, with Wang Zhi prepare it is non-burning brick the same, it is still desirable to the cement and more than 5% quick lime of use more than 10%, brick
Strength grade only has MU10, fails to play electrolytic manganese residues potential hydraulicity activity, also greatly limit its application field and big
Measure dissolving for electrolytic manganese residues.
Certain electrolytic manganese residues is taken from, levigate, specific surface area 570.3m is dried2/ kg, its chemical composition and mineral composition are as follows.
Electrolytic manganese residues amplify 5000 times SEM such as Fig. 1.Electrolytic manganese residues XRD such as Fig. 2.
The electrolytic manganese residues chemical composition of table 1
| CaO | MgO | MnO | Loss on ignition | |||||||||
| Content | 10.21 | 31.49 | 5.25 | 1.19 | 22.00 | 15.55 | 1.25 | 11.02 | 0.01 | 0.57 | 0.28 | 1.18 |
The content of the invention
It is an object of the invention to make full use of electrolytic manganese residues lateral reactivity, using activity excitant neutral and alkali material or contain
Aluminum improves electrolytic manganese residues reactivity, and electrolytic manganese residues physical reactions are improved by surface active ingredient in activity excitant
Can, strengthening brick body density, part aggregate chips improves brick intensity as brick body aggregate, so as to electrolytic manganese residues of significantly dissolving can be reached
With its environmental pollution of reduction, the free of calcining and steam curing foster double exempt from the building materials such as brick of more than the MU15 of better performances can be prepared again.
The present invention is realized in above-mentioned purpose：
A kind of composition containing electrolytic manganese residues, said composition includes that the raw material of following weight portion is constituted：Levigate electrolytic manganese residues
70%-80%, aggregate chips 15%-25%, activity excitant 5%-10%, account for the water of the 10%-15% of raw material total amount.
More preferably levigate electrolytic manganese residues 75%, aggregate chips 25%, activity excitant 5% accounts for raw material total amount
13.5% water.
Described electrolytic manganese residues are neutralized to pH for 7.5-8 for the doped quick lime of original state electrolytic manganese residues, 60 after standing 24h
DEG C drying, and specific surface area is milled to more than 500m2Electrolytic manganese residues obtained by/kg.
Described aggregate chips is made up of the aggregate chips of variable grain particle diameter, and the largest particles particle diameter is 10mm, and wherein 10mm~5mm is accounted for
0~10%, below 5mm account for more than 40%, and below 1.25mm accounts for more than 20%.
Described activity excitant includes accounting for the alkaline excitation material and account for gross mass 30-40% that gross mass is 60-70%
Surfactant, wherein, alkaline excitation material include clinker, sodium metaaluminate, metakaolin, red mud, quick lime in one kind
Or it is various be composited, surfactant include naphthalenesulfonate formaldehyde condensation compound, sulfonated melamine compound condensation polymer, wooden sulphur
It is composited for one or more in sour sodium.
More preferably activity excitant includes accounting for the alkaline excitation material and account for gross mass 35% that gross mass is 65%
Surfactant, wherein, alkaline excitation material be clinker, metakaolin, quick lime in be composited, surfactant is naphthalene
Sulfonate and formaldehyde condensation product, sulfonated melamine compound condensation polymer, wooden sodium sulfonate are composited.
Composition containing electrolytic manganese residues described in will be above-mentioned is applied to prepare in electrolytic manganese residues double exempt from the building materials such as brick.
The method that composition containing electrolytic manganese residues described in will be above-mentioned prepares electrolytic manganese residues double exempt from the building materials such as brick, comprises the following steps：
By levigate electrolytic manganese residues, aggregate chips, activity excitant is mixed into mixer, dry to stir 2-4min, adds moisture, high-speed stirred 5-10min,
Half siccative is formed, by automatic distributing machine, is dispensed to brick compacting mold, compressing under 18-25MPa, the brick that will be suppressed exists
Conserved to 25-30 days under natural conditions, obtain final product electrolytic manganese residues double exempt from the building materials such as brick.
Electrolytic manganese residues are chemically seen based on silicon, calcium, sulphur, iron, manganese, aluminium etc. on composition, main component dihydrate gypsum, quartz
With mullite mineral, also containing ferrous sulfate, manganese dioxide and some unformed phase mineral, wherein dihydrate gypsum accounts for total amount
20% or so, SiO2More than 30% is accounted for, contains Al2O3And Fe2O3Also more than 20%.According to Binder Materials theory, it is rich in
Aluminium (iron) lower in strong alkaline condition or the induction of already present silicon-aluminum containing solion can occur Al with lateral reactivity mineral
(Fe) chemical bond rupture such as-O, forms Al3+(Fe3+) hydration solution, these hydrated ions can be with two water stones of pass into solution
, there is complicated chemical reaction in cream, generate one of main hydration products that general hydrated cementitious hardening is obtained ----entringite；Stone
English and mullite mineral can also issue the fracture of first portion key key and structural rearrangement in strong alkali solution, generate general hydrated cementitious
One of main hydration products that hardening is obtained ----hydrated calcium silicate gel；Residue does not participate in the inert mineral of chemical reaction, then
Construction inner is filled in, structure packing is increased, so that a compaction strength structure higher is formed, as long as therefore
Excited by suitable exciting agent, can be prepared the non-burning brick of function admirable using its lateral reactivity completely.
Two kinds of main hydrated product water with gelling property of double exempt from the building materials such as brick are prepared from elemental composition and as electrolytic manganese residues
Change gel of calcium silicate and entringite analysis, it is desirable to provide its original chemical reacts strong alkaline condition, improve electrolytic manganese residues containing CaO and
Al2O3Isoreactivity mineral content.In the present invention in activity excitant sodium metaaluminate, metakaolin, red mud etc. be mainly to provide it is more
Al2O3Isoreactivity mineral content, quick lime can significantly improve reaction solution alkalescence, while also can be the shape of hydrated calcium silicate
Into calcium source is provided, clinker is can to increase Al2O3Isoreactivity mineral content, can improve original chemical reaction strong basicity again, increase energy
Enough generate the active mineral content of hydrated calcium silicate.Electrolytic manganese residues grain graininess is superfine, adds water sticky, cause water consumption larger and
The water of actual participation chemical reaction is simultaneously few, and substantial amounts of moisture is dispersed in microstructure body, easily causes brick laying structure not close
Real intensity is not high, and the performance such as freeze proof is bad, the one kind such as naphthalenesulfonate formaldehyde condensation compound of the present invention, triethanolamine, wooden sodium sulfonate
Improve electrolytic manganese residues surface lubrication activity with various materials being composited, improve pressing process efficiency and use is greatly reduced simultaneously
Water, is conducive to non-burning brick compacting, the raising of intensity and the improvement of non-burning brick combination property；The addition of aggregate chips, in non-burning brick knot
Serve as filler aggregate and skeleton function in structure body, be conducive to the raising of the stabilization and combination property of non-burning brick structure.
A kind of electrolytic manganese residues double exempt from the building materials such as brick preparation method of the present invention, will levigate electrolytic manganese residues, aggregate chips and activity excitant press
Enter forced action type twin-shaft mixer after being weighed according to certain proportion, the 3~5min of stirring that adds water forms half siccative, by automatic distributing machine
Dispense to brick compacting mold, compressing under 20MPa pressure, normal temperature is conserved to the 240mm × 115mm of regulation age × 53mm
Size finished product electrolytic manganese residues double exempt from the building materials such as brick.
Advantages of the present invention：(1) electrolytic manganese residues double exempt from the building materials such as brick preparation process is simple is feasible, energy-conserving and environment-protective, market prospects are wide, easily
In popularization；(3) electrolytic manganese slag brick better performances；(4) electrolytic manganese residues double exempt from the building materials such as brick electrolytic manganese residues utilization rate is high.
Brief description of the drawings
Fig. 1 is electrolytic manganese residues SEM (× 5000).
Fig. 2 is electrolytic manganese residues XRD.
Specific embodiment：
Embodiment 1：
Take levigate electrolytic manganese residues 75kg, aggregate chips 20kg, activity excitant 5kg (5-10mm particles 1.5kg wherein in aggregate chips,
2-5mm particles 12.5kg, 0.5-1.25mm particle 6.0kg；By clinker 1.0kg in activity excitant, sodium metaaluminate 1.0kg, partially
Kaolin 0.75kg, quick lime 0.5kg, naphthalenesulfonate formaldehyde condensation compound 1.0kg, sulfonated melamine compound condensation polymer 0.5kg,
Wooden sodium sulfonate 0.25kg constitute) mixing after, add 13.5kg water, by all material add forced stirrer stir 3~5min
Half siccative is formed, is dispensed to brick compacting mold by automatic distributing machine, compressing under 20MPa pressure, the brick that will be suppressed exists
Conserved 25 days under natural conditions, that is, obtain 240mm × 115mm × 53mm size finished product electrolytic manganese residues double exempt from the building materials such as brick.
According to JC/T 422-2007 non-sintered rubbish tailing-bricks standard testings, its mean compressive strength is 22.2MPa, soft
Change coefficient 0.83, mean water absorption rate 15.1%, dimensional discrepancy and presentation quality etc. meet the requirements.Mn2+Leaching concentration 1.2mg/L
Less than GB8978-1996《Integrated wastewater discharge standard》Middle 2mg/L requirements.
Embodiment 2：
Levigate electrolytic manganese residues 75kg is taken, (wherein 5-10mm particles are accounted in aggregate chips for aggregate chips 15kg, activity excitant 10kg
1.2kg, 2-5mm particle account for 9.2kg, and 0.5-1.25mm accounts for 4.6kg；By quick lime 2.8kg, sodium metaaluminate in activity excitant
1.2kg, red mud 2.0kg, clinker 0.5kg, naphthalenesulfonate formaldehyde condensation compound 0.75kg, wooden sodium sulfonate 2.75kg compositions) mixing
Afterwards, add water 12kg, adds forced stirrer to stir 3~5min all material and forms half siccative, dispensed by automatic distributing machine
Compressing under 20MPa pressure to brick compacting mold, the brick that will be suppressed is conserved 28 days under field conditions (factors), that is, obtain 240mm
× 115mm × 53mm size finished product electrolytic manganese residues double exempt from the building materials such as brick.
According to JC/T 422-2007 non-sintered rubbish tailing-bricks standard testings, its mean compressive strength is 28.4MPa, soft
Change coefficient 0.90, mean water absorption rate 13.3%, dimensional discrepancy and presentation quality etc. meet the requirements.Mn2+Leaching concentration 0.9mg/L
Less than GB8978-1996《Integrated wastewater discharge standard》Middle 2mg/L requirements.
Embodiment 3：
Take levigate electrolytic manganese residues 70kg, aggregate chips 20kg, activity excitant 10kg (5-10mm particles 1kg, 2- wherein in aggregate chips
5mm particles 10kg, 0.5-1.25mm particle 9kg；By clinker 2.0kg in activity excitant, quick lime 1.5kg, red mud 3.0kg,
Wooden sodium sulfonate 3.5kg constitute) mixing after, add water 10kg, by all material add forced stirrer stir 3~5min formed
Half siccative, is dispensed to brick compacting mold by automatic distributing machine, compressing under 20MPa pressure, and the brick that will be suppressed is in nature
Under the conditions of conserve 30 days, that is, obtain 240mm × 115mm × 53mm size finished product electrolytic manganese residues double exempt from the building materials such as brick.
According to JC/T 422-2007 non-sintered rubbish tailing-bricks standard testings, its mean compressive strength is 30.2MPa, soft
Change coefficient 0.94, mean water absorption rate 9.1%, dimensional discrepancy and presentation quality etc. meet the requirements.Mn2+Leaching concentration 0.8mg/L
Less than GB8978-1996《Integrated wastewater discharge standard》Middle 2mg/L requirements.
Embodiment 4：
Take levigate electrolytic manganese residues 73kg, aggregate chips 20kg, activity excitant 7kg (5-10mm particles 1.2kg wherein in aggregate chips,
2-5mm particles 10.4kg, 0.5-1.25mm particle 8.4kg；By clinker 2.2kg in activity excitant, metakaolin 2.0kg is red
Mud 0.35kg, sulfonated melamine compound condensation polymer 1.35kg, wooden sodium sulfonate 1.1kg composition) after mixing, water 15kg is added,
Add forced stirrer to stir 3~5min all material to form half siccative, dispensed to brick compacting mold by automatic distributing machine,
Compressing under 20MPa pressure, the brick that will be suppressed is conserved 26 days under field conditions (factors), that is, obtain 240mm × 115mm × 53mm
Size finished product electrolytic manganese residues double exempt from the building materials such as brick.
According to JC/T 422-2007 non-sintered rubbish tailing-bricks standard testings, its mean compressive strength is 28.7MPa, soft
Change coefficient 0.92, mean water absorption rate 10.8%, dimensional discrepancy and presentation quality etc. meet the requirements.Mn2+Leaching concentration 1.1mg/L
Less than GB8978-1996《Integrated wastewater discharge standard》Middle 2mg/L requirements.
Embodiment 5：
Take levigate electrolytic manganese residues 70kg, aggregate chips 25kg, activity excitant 5kg (5-10mm particles 1.5kg wherein in aggregate chips,
2-5mm particles 13kg, 0.5-1.25mm particle 10.5；By clinker 3.25kg, naphthalenesulfonate formaldehyde condensation compound in activity excitant
1.75kg constitute) mixing after, add water 12kg, by all material add forced stirrer stir 3~5min formed half siccative, lead to
Cross automatic distributing machine to dispense to brick compacting mold, compressing under 20MPa pressure, the brick that will be suppressed is conserved under field conditions (factors)
27 days, that is, obtain 240mm × 115mm × 53mm size finished product electrolytic manganese residues double exempt from the building materials such as brick.
According to JC/T 422-2007 non-sintered rubbish tailing-bricks standard testings, its mean compressive strength is 25.2MPa, soft
Change coefficient 0.88, mean water absorption rate 12.1%, dimensional discrepancy and presentation quality etc. meet the requirements.Mn2+Leaching concentration 1.0mg/L
Less than GB8978-1996《Integrated wastewater discharge standard》Middle 2mg/L requirements.
Claims (1)
1. a kind of method that composition containing electrolytic manganese residues prepares electrolytic manganese residues double exempt from the building materials such as brick, it is characterised in that comprise the following steps：Will
Levigate electrolytic manganese residues, aggregate chips, activity excitant is mixed into mixer, dry to stir 2-4min, adds moisture, high-speed stirred 5-10min, shape
Into half siccative, by automatic distributing machine, dispense to brick compacting mold, compressing under 18-25MPa, the brick that will be suppressed is certainly
Conserved to 25-30 days under the conditions of so, obtain final product electrolytic manganese residues double exempt from the building materials such as brick；Described levigate electrolytic manganese residues are original state electrolytic manganese residues through mixing
Miscellaneous quick lime is neutralized to pH for 7.5-8, is dried at 60 DEG C after standing 24h, and is milled to specific surface area more than 500m2Obtained by/kg
Electrolytic manganese residues；Aggregate chips is made up of the aggregate chips of variable grain particle diameter, and the largest particles particle diameter is 10mm, and wherein 5mm ~ 10mm accounts for 5-
7.5%, 2-5mm account for 50-62.5%, and 0.5-1.25mm accounts for 30-45%；Described activity excitant includes accounting for the alkali that gross mass is 65%
Property excitation material and account for the surfactant of gross mass 35%, wherein, during alkaline excitation material is clinker, metakaolin, quick lime
Be composited, surfactant be naphthalenesulfonate formaldehyde condensation compound, sulfonated melamine compound condensation polymer, wooden sodium sulfonate be combined
Form；The raw material composition of percetage by weight：Levigate electrolytic manganese residues 70%-80%, aggregate chips 15%-25%, activity excitant 5%-10%, account for
The water of the 10%-15% of raw material total amount.
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| CN106082914A (en) * | 2016-06-20 | 2016-11-09 | 安徽金丰新型建材有限公司 | The gangue of a kind of light weight high intensity is non-burning brick |
| CN106082821A (en) * | 2016-06-20 | 2016-11-09 | 安徽金丰新型建材有限公司 | A kind of gangue with antimildew and antibacterial effect is non-burning brick |
| CN109127650B (en) * | 2018-07-26 | 2021-11-02 | 四川海沛环保科技有限公司 | Method for harmlessly treating electrolytic manganese slag by using cement kiln intermediate product |
| CN109721299B (en) * | 2019-01-31 | 2021-11-23 | 贵州大学 | Method for preparing baking-free ceramsite by electrolytic manganese slag |
| CN110002829B (en) * | 2019-04-30 | 2021-08-06 | 广东泉兴生态科技有限公司 | Electrolytic manganese slag baking-free brick and preparation method thereof |
| CN110423085B (en) * | 2019-09-11 | 2020-08-04 | 北京科技大学 | Anti-cracking water-stabilizing layer material for electrolytic manganese slag-containing road and preparation method thereof |
| CN114394814B (en) * | 2021-12-29 | 2023-04-07 | 武汉大学(肇庆)资源与环境技术研究院 | Method for recovering ammonia nitrogen in electrolytic manganese slag and preparing baking-free brick and baking-free brick |
| CN114213068B (en) * | 2022-01-17 | 2022-10-18 | 陕西理工大学 | Preparation method of heat-insulating compression-resistant energy-saving environment-friendly baking-free brick |
| CN114671640A (en) * | 2022-02-22 | 2022-06-28 | 中国科学院武汉岩土力学研究所 | Electrolytic manganese slag low-carbon roadbed material and preparation method thereof |
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| CN101570037B (en) * | 2009-06-01 | 2013-06-05 | 中国环境科学研究院 | Method for preparing construction material by utilizing electrolytic manganese slag |
| CN101644089B (en) * | 2009-07-22 | 2014-03-19 | 贵州省建筑材料科学研究设计院 | Electrolytic manganese slag brick and preparation method thereof |
| CN102503205A (en) * | 2011-11-04 | 2012-06-20 | 卿富安 | New formula and process method for preparing electrolytic manganese slag brick |
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