CN104725001A - Composition containing electrolytic manganese residues and application in preparation of electrolytic manganese residue non-fired and non-steam brick - Google Patents
Composition containing electrolytic manganese residues and application in preparation of electrolytic manganese residue non-fired and non-steam brick Download PDFInfo
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- CN104725001A CN104725001A CN201510108364.6A CN201510108364A CN104725001A CN 104725001 A CN104725001 A CN 104725001A CN 201510108364 A CN201510108364 A CN 201510108364A CN 104725001 A CN104725001 A CN 104725001A
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Abstract
The invention discloses a composition containing electrolytic manganese residues. The composition comprises levigated electrolytic manganese residues, stone chips and a reactive activator, wherein the levigated electrolytic manganese residues are prepared by doping undisturbed electrolytic manganese residues with quicklime, neutralizing, standing, baking and grinding until the specific surface area is greater than 500m<2>/kg; the stone chips are mixtures of which the maximal particle diameters are 10mm, 10-5mm, 5mm and 1.25mm; the reactive activator comprises an alkali-active material and a surfactant; the alkali-active material comprises one or more of clinker, sodium metaaluminate, metakaolin, red mud and quicklime; and the surfactant comprises one or more of naphthyl sulfonate formaldehyde condensate, sulfonated melamine formaldehyde polycondensate and sodium lignosulphonate. The composition containing the electrolytic manganese residues is applied to preparation of the electrolytic manganese residue non-fired and non-steam brick; the prepared non-fired and non-steam brick is above the grade MU15; the composition has the advantages of simple process, energy-saving, environmentally friendly and wide in market prospect; and the electrolytic manganese residue brick is relatively good in property.
Description
Technical field
The present invention relates to a kind of containing electrolytic manganese residues composition, and be applied to that preparation is two exempts from brick, specifically disclose the two preparation method exempting from brick of electrolytic manganese residues simultaneously.
Background technology
Electrolytic manganese residues is by the rhodochrosite based on manganese carbonate ore, manganese sulfate solution is obtained with sulfuric acid reaction after levigate, by oxidation, in and, extract manganese metal after purification and electrolysis after slightly acidic industrial residue, have that grain graininess is tiny, water ratio up to 16% ~ 40%, thickness very easily become the features such as block.Manganese metal is one of strategic resource important in national economy, China is also the electrolytic manganese production big country of the production history having had nearly more than 50 years, but simultaneously as the electrolytic manganese industry of typical hydrometallurgy, belong to three high industries of typical highly energy-consuming, high pollution and maximum discharge, in the serious environmental problem also brought and stack and pollute as electrolytic manganese residues of promoting economic development simultaneously.General employing electrowinning manganese metal method, the acid-soaked waste residue amount that often extraction 1t electrolytic metal Mn discharges is about 8 ~ 9t.The electrolytic manganese actual output of 2008,2009,2010,2011 and China in 2012 is respectively 1,140,000 tons, 1,310,000 tons, 1,380,000 tons, 1,480,000 tons and 1,160,000 tons, within 5 years, add up 6,470,000 tons, produce at least fifty-five million ton electrolytic manganese residues, this is not also containing the manganese quantity of slag be deposited in over the years before 2008 in Tailings Dam.Electrolytic manganese residues contains the mineralogical compositions such as manganese, Sulfates, ammonia nitrogen, arsenic, selenium, and according to national regulation, still belong to general industry refuse, but wherein vitriol, ammonia nitrogen, selenium and manganese ion concentration are high, its leach liquor still may make a big impact to environment.Because current electrolysis manganese slag resource utilization degree is extremely low, a large amount of electrolytic manganese residues still adopts wet method to be disposed to tailings reservoir for piling, so large waste residue amount had not only taken a large amount of soil but also contaminate environment, brought tremendous economic and environmental protection pressure to electrolytic manganese production enterprise and manganese ore surrounding enviroment.Reduce harm and the volume of cargo in storage of electrolytic manganese residues to greatest extent, carry out electrolytic manganese residues recycling, extremely urgent.
The many scholars of current China also carry out the investigation and application of electrolytic manganese residues recycling.Mostly concentrate on valuable element to reclaim, as retardant in manufacture of cement, high-temperature firing aluminosulfate cement and preparation inferior grade gelling material aspect, less in electrolytic manganese residues brickmaking research, and mostly be interpolation cement and other materials, steam-cured mode is adopted to prepare the research of autoclaved brick, only Wang Zhi is had in existing document, the people such as Zhao Minglun have carried out electrolytic manganese residues and have prepared non-burning brick research, but the people such as Wang Zhi adopt 30% flyash, 10% unslaked lime, gelling material prepared by 10% cement and 50% original state electrolytic manganese residues, according to gelling material: river sand=1:0.9, water-solid ratio is 0.10 ~ 0.20, actual non-burning brick proportioning is original state electrolytic manganese residues: flyash: unslaked lime: cement: river sand=26.3%:15.8%:5.3%:5.3%:47.3%, electrolytic manganese residues utilization ratio is less than 30%, and the non-burning brick of preparation can only reach MU10 strength grade, Zhao Minglun etc. adopt 60% ~ 70% electrolytic manganese residues, 10% ~ 20% cement, 5% ~ 10% unslaked lime and a small amount of tensio-active agent composition, stir the light cinder brick that MU10 grade is prepared in vibratory compaction, electrolytic manganese residues utilization ratio is the highest by 70%, with Wang Zhi prepare non-burning brick the same, still cement and more than 5% unslaked lime of use more than 10% is needed, the strength grade of brick only has MU10, fail to play the potential hydraulicity of electrolytic manganese residues active, also greatly limit dissolving of its Application Areas and a large amount of electrolytic manganese residues.
Take from certain electrolytic manganese residues, dry levigate, specific surface area 570.3m
2/ kg, its chemical composition and mineral composition as follows.Electrolytic manganese residues amplifies the SEM of 5000 times as Fig. 1.Electrolytic manganese residues XRD is as Fig. 2.
Table 1 electrolytic manganese residues chemical constitution
| CaO | SiO 2 | Al 2O 3 | MgO | SO 3 | Fe 2O 3 | K 2O | MnO | Na 2O | P 2O 5 | TiO 2 | 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 |
Summary of the invention
The object of the invention is to make full use of electrolytic manganese residues lateral reactivity, activity excitant neutral and alkali material or alumina-bearing material is utilized to improve electrolytic manganese residues reactive behavior, electrolytic manganese residues physical reaction performance is improved by surface active ingredient in activity excitant, strengthen brick body density, part aggregate chips improves brick intensity as brick body aggregate, thus can reach and significantly dissolve electrolytic manganese residues and reduce its environmental pollution, what the free of calcining and steam curing preparing again more than the MU15 of better performances was supported two exempts from brick.
The present invention realizes above-mentioned purpose like this:
A kind of containing electrolytic manganese residues composition, said composition comprises the raw material composition of following weight part: 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 the water of 13.5% of raw material total amount.
Described electrolytic manganese residues is original state electrolytic manganese residues through doping neutralization with lime to pH is 7.5-8, leaves standstill 60 DEG C of oven dry after 24h, and is milled to specific surface area and is greater than 500m
2the electrolytic manganese residues of/kg gained.
Described aggregate chips is made up of the aggregate chips of variable grain particle diameter, and largest particle particle diameter is 10mm, and wherein 10mm ~ 5mm accounts for 0 ~ 10%, below 5mm and accounts for more than 40%, below 1.25mm and account for more than 20%.
Described activity excitant comprises and accounts for alkaline excitation material that total mass is 60-70% and account for the tensio-active agent of total mass 30-40%, wherein, alkaline excitation material comprise in grog, sodium metaaluminate, metakaolin, red mud, unslaked lime one or more be composited, tensio-active agent comprise in naphthalenesulfonate formaldehyde condensation compound, sulfonated melamine compound polycondensate, wooden sodium sulfonate one or more be composited.
More preferably activity excitant comprises that to account for total mass be the alkaline excitation material of 65% and account for the tensio-active agent of total mass 35%, wherein, alkaline excitation material is be composited in grog, metakaolin, unslaked lime, and tensio-active agent is naphthalenesulfonate formaldehyde condensation compound, sulfonated melamine compound polycondensate, wooden sodium sulfonate are composited.
Being applied to containing electrolytic manganese residues composition described in above-mentioned is prepared that electrolytic manganese residues is two exempts from brick.
The electrolytic manganese residues composition that contains described in above-mentioned is prepared the two method exempting from brick of electrolytic manganese residues, comprises the steps: levigate electrolytic manganese residues, aggregate chips, activity excitant is mixed into stirrer, dryly stir 2-4min, add moisture, high-speed stirring 5-10min, form half siccative, by automatic distributing machine, spreading to brick compacting mold, compression moulding under 18-25MPa, by the brick that suppresses under field conditions (factors) maintenance to 25-30 days, obtain that electrolytic manganese residues is two exempts from brick.
Electrolytic manganese residues chemically composition is seen based on silicon, calcium, sulphur, iron, manganese, aluminium etc., main component dihydrate gypsum, quartz and mullite mineral, also containing ferrous sulfate, Manganse Dioxide and some unformed phase mineral, wherein dihydrate gypsum accounts for total amount about 20%, SiO
2account for more than 30%, containing Al
2o
3and Fe
2o
3also more than 20%.According to gelling material theory, be rich in aluminium (iron) have lateral reactivity mineral can strong alkaline condition or already present silicon-aluminum containing solion induction under there is the chemical bond ruptures such as Al (Fe)-O, formed Al
3+(Fe
3+) hydration solution, these hydrated ions can with the dihydrate gypsum of pass into solution, there is complicated chemical reaction, generate general hydrated cementitious and to harden one of main hydration products of obtaining----ettringite; Quartz and mullite mineral also can in the bond rupture of generating portion key and structural rearrangements under strong alkali solution, generate general hydrated cementitious and to harden one of main hydration products of obtaining----hydrated calcium silicate gel; Residue does not participate in the inert mineral of chemical reaction, then be filled in construction inner, add structure degree of compactness, thus form the higher structure of a compaction strength, as long as therefore excited by suitable exciting agent, its lateral reactivity can be utilized completely to prepare the non-burning brick of excellent property.
Exempt from from elemental composition with as electrolytic manganese residues preparation is two hydrated product hydrated calcium silicate gel and the ettringite analysis that main two kinds of brick have gelling property, need to provide its original chemical to react strong alkaline condition, improve electrolytic manganese residues containing CaO and Al
2o
3isoreactivity mineral content.In the present invention, in activity excitant, sodium metaaluminate, metakaolin, red mud etc. mainly provide more Al
2o
3isoreactivity mineral content, unslaked lime can significantly improve reaction soln alkalescence, and also can provide calcium source for the formation of hydrated calcium silicate, grog to increase Al simultaneously
2o
3isoreactivity mineral content, can improve again original chemical reaction strong basicity, increase the active mineral content that can generate hydrated calcium silicate.Electrolytic manganese residues grain graininess is superfine, add water thickness, cause water consumption comparatively greatly and the water yield of actual participation chemical reaction is also few, a large amount of moisture is dispersed in microtexture body, easily cause brick laying structure eakiness intensity not high, the performance such as freeze proof is bad, it is active that a kind of and multiple material be composited such as naphthalenesulfonate formaldehyde condensation compound of the present invention, trolamine, wooden sodium sulfonate improves electrolytic manganese residues surface lubrication, improve pressing process efficiency and significantly reduce water consumption simultaneously, be conducive to non-burning brick compacting, the raising of intensity and the improvement of non-burning brick over-all properties; Adding of aggregate chips, in non-burning brick structure, serve as filler aggregate and skeleton function, be conducive to the raising of the stable of non-burning brick structure and over-all properties.
A kind of electrolytic manganese residues of the present invention is two exempts from brick preparation method, forced action type twin-shaft mixer is entered after weighing according to a certain percentage by levigate electrolytic manganese residues, aggregate chips and activity excitant, stirring 3 ~ the 5min that adds water forms half siccative, by automatic distributing machine spreading to brick compacting mold, make type at 20MPa pressure, normal temperature maintenance exempts from brick to the 240mm × 115mm × 53mm size finished product electrolytic manganese residues pair in the regulation length of time.
Advantage of the present invention: (1) electrolytic manganese residues is two exempt from process for producing bricks simple possible, energy-conserving and environment-protective, market outlook wide, be easy to promote; (3) electrolytic manganese slag brick better performances; (4) two to exempt from brick electrolytic manganese residues utilization ratio high for electrolytic manganese residues.
Accompanying drawing explanation
Fig. 1 is electrolytic manganese residues SEM (× 5000).
Fig. 2 is electrolytic manganese residues XRD.
Embodiment:
Embodiment 1:
Get levigate electrolytic manganese residues 75kg, aggregate chips 20kg, activity excitant 5kg (wherein 5-10mm particle 1.5kg in aggregate chips, 2-5mm particle 12.5kg, 0.5-1.25mm particle 6.0kg, by grog 1.0kg in activity excitant, sodium metaaluminate 1.0kg, metakaolin 0.75kg, unslaked lime 0.5kg, naphthalenesulfonate formaldehyde condensation compound 1.0kg, sulfonated melamine compound polycondensate 0.5kg, wooden sodium sulfonate 0.25kg forms) mixing after, add 13.5kg water, all material is added forced stirrer stirring 3 ~ 5min and form half siccative, by automatic distributing machine spreading to brick compacting mold, type is made at 20MPa pressure, by the maintenance 25 days under field conditions (factors) of the brick that suppresses, namely obtain 240mm × 115mm × 53mm size finished product electrolytic manganese residues pair and exempt from brick.
According to the standard testing of JC/T 422-2007 non-sintered rubbish tailing-bricks, its mean compressive strength is 22.2MPa, coefficient of softening 0.83, and mean water absorption rate 15.1%, size deviation and visual appearance etc. all meet the requirements.Mn
2+leaching concentration 1.2mg/L is lower than 2mg/L requirement in GB8978-1996 " integrated wastewater discharge standard ".
Embodiment 2:
Get levigate electrolytic manganese residues 75kg, aggregate chips 15kg, (wherein in aggregate chips, 5-10mm particle accounts for 1.2kg to activity excitant 10kg, and 2-5mm particle accounts for 9.2kg, and 0.5-1.25mm accounts for 4.6kg; By unslaked lime 2.8kg in activity excitant, sodium metaaluminate 1.2kg, red mud 2.0kg, grog 0.5kg, naphthalenesulfonate formaldehyde condensation compound 0.75kg, wooden sodium sulfonate 2.75kg form) mixing after, add water 12kg, all material is added forced stirrer stirring 3 ~ 5min and form half siccative, by automatic distributing machine spreading to brick compacting mold, type is made at 20MPa pressure, by the maintenance 28 days under field conditions (factors) of the brick that suppresses, namely obtain that 240mm × 115mm × 53mm size finished product electrolytic manganese residues is two exempts from brick.
According to the standard testing of JC/T 422-2007 non-sintered rubbish tailing-bricks, its mean compressive strength is 28.4MPa, coefficient of softening 0.90, and mean water absorption rate 13.3%, size deviation and visual appearance etc. all meet the requirements.Mn
2+leaching concentration 0.9mg/L is lower than 2mg/L requirement in GB8978-1996 " integrated wastewater discharge standard ".
Embodiment 3:
Get levigate electrolytic manganese residues 70kg, aggregate chips 20kg, activity excitant 10kg (wherein 5-10mm particle 1kg in aggregate chips, 2-5mm particle 10kg, 0.5-1.25mm particle 9kg; By grog 2.0kg in activity excitant, unslaked lime 1.5kg, red mud 3.0kg, wooden sodium sulfonate 3.5kg forms) after mixing, add water 10kg, all material is added forced stirrer and stir 3 ~ 5min and form half siccative, by automatic distributing machine spreading to brick compacting mold, make type at 20MPa pressure, by the maintenance 30 days under field conditions (factors) of the brick that suppresses, namely obtain that 240mm × 115mm × 53mm size finished product electrolytic manganese residues is two exempts from brick.
According to the standard testing of JC/T 422-2007 non-sintered rubbish tailing-bricks, its mean compressive strength is 30.2MPa, coefficient of softening 0.94, and mean water absorption rate 9.1%, size deviation and visual appearance etc. all meet the requirements.Mn
2+leaching concentration 0.8mg/L is lower than 2mg/L requirement in GB8978-1996 " integrated wastewater discharge standard ".
Embodiment 4:
Get levigate electrolytic manganese residues 73kg, aggregate chips 20kg, activity excitant 7kg (wherein 5-10mm particle 1.2kg in aggregate chips, 2-5mm particle 10.4kg, 0.5-1.25mm particle 8.4kg; By grog 2.2kg in activity excitant, metakaolin 2.0kg, red mud 0.35kg, sulfonated melamine compound polycondensate 1.35kg, wooden sodium sulfonate 1.1kg form) after mixing, add water 15kg, all material is added forced stirrer stirring 3 ~ 5min and form half siccative, by automatic distributing machine spreading to brick compacting mold, make type at 20MPa pressure, by the maintenance 26 days under field conditions (factors) of the brick that suppresses, namely obtain that 240mm × 115mm × 53mm size finished product electrolytic manganese residues is two exempts from brick.
According to the standard testing of JC/T 422-2007 non-sintered rubbish tailing-bricks, its mean compressive strength is 28.7MPa, coefficient of softening 0.92, and mean water absorption rate 10.8%, size deviation and visual appearance etc. all meet the requirements.Mn
2+leaching concentration 1.1mg/L is lower than 2mg/L requirement in GB8978-1996 " integrated wastewater discharge standard ".
Embodiment 5:
Get levigate electrolytic manganese residues 70kg, aggregate chips 25kg, activity excitant 5kg (wherein 5-10mm particle 1.5kg in aggregate chips, 2-5mm particle 13kg, 0.5-1.25mm particle 10.5; By grog 3.25kg in activity excitant, naphthalenesulfonate formaldehyde condensation compound 1.75kg forms) mixing after, add water 12kg, all material is added forced stirrer stirring 3 ~ 5min and form half siccative, by automatic distributing machine spreading to brick compacting mold, make type at 20MPa pressure, by the maintenance 27 days under field conditions (factors) of the brick that suppresses, namely obtain that 240mm × 115mm × 53mm size finished product electrolytic manganese residues is two exempts from brick.
According to the standard testing of JC/T 422-2007 non-sintered rubbish tailing-bricks, its mean compressive strength is 25.2MPa, coefficient of softening 0.88, and mean water absorption rate 12.1%, size deviation and visual appearance etc. all meet the requirements.Mn
2+leaching concentration 1.0mg/L is lower than 2mg/L requirement in GB8978-1996 " integrated wastewater discharge standard ".
Claims (8)
1. containing an electrolytic manganese residues composition, it is characterized in that, said composition comprises the raw material composition of following weight percentage: 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.
2. containing an electrolytic manganese residues composition, it is characterized in that, said composition comprises the raw material composition of following weight percentage: levigate electrolytic manganese residues 75%, aggregate chips 25%, activity excitant 5%, accounts for the water of 13.5% of raw material total amount.
3. according to claim 1 and 2 containing electrolytic manganese residues composition, it is characterized in that, described levigate electrolytic manganese residues is original state electrolytic manganese residues is 7.5-8 through doping neutralization with lime to pH, leaves standstill 60 DEG C of oven dry after 24h, and is milled to specific surface area and is greater than 500m
2the electrolytic manganese residues of/kg gained.
4. according to claim 1 and 2 containing electrolytic manganese residues composition, it is characterized in that, aggregate chips is made up of the aggregate chips of variable grain particle diameter, and largest particle particle diameter is 10mm, and wherein 10mm ~ 5mm accounts for 0 ~ 10%, below 5mm and accounts for more than 40%, below 1.25mm and account for more than 20%.
5. according to claim 1 and 2 containing electrolytic manganese residues composition, it is characterized in that, described activity excitant comprises and accounts for alkaline excitation material that total mass is 60-70% and account for the tensio-active agent of total mass 30-40%, wherein, alkaline excitation material comprise in grog, sodium metaaluminate, metakaolin, red mud, unslaked lime one or more be composited, tensio-active agent comprise in naphthalenesulfonate formaldehyde condensation compound, sulfonated melamine compound polycondensate, wooden sodium sulfonate one or more be composited.
6. according to claim 1 and 2 containing electrolytic manganese residues composition, it is characterized in that, described activity excitant comprises that to account for total mass be the alkaline excitation material of 65% and account for the tensio-active agent of total mass 35%, wherein, alkaline excitation material is be composited in grog, metakaolin, unslaked lime, and tensio-active agent is naphthalenesulfonate formaldehyde condensation compound, sulfonated melamine compound polycondensate, wooden sodium sulfonate are composited.
7. the electrolytic manganese residues composition that contains according to any one of claim 1 ~ 6 is preparing the two application of exempting from brick of electrolytic manganese residues.
8. the electrolytic manganese residues composition that contains according to any one of claim 1 ~ 7 prepares the two method exempting from brick of electrolytic manganese residues, it is characterized in that, comprises the steps: levigate electrolytic manganese residues, aggregate chips, activity excitant is mixed into stirrer, dryly stirs 2-4min, add moisture, high-speed stirring 5-10min, forms half siccative, passes through automatic distributing machine, spreading is to brick compacting mold, compression moulding under 18-25MPa, by the brick that suppresses under field conditions (factors) maintenance to 25-30 days, obtain that electrolytic manganese residues is two exempts from brick.
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| CN110423085A (en) * | 2019-09-11 | 2019-11-08 | 北京科技大学 | One kind cracking resistance steady layer of water material of road containing electrolytic manganese residues and preparation method thereof |
| CN114213068A (en) * | 2022-01-17 | 2022-03-22 | 陕西理工大学 | Preparation method of heat-insulating compression-resistant energy-saving environment-friendly baking-free brick |
| CN114394814A (en) * | 2021-12-29 | 2022-04-26 | 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 |
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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 |
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| CN109127650A (en) * | 2018-07-26 | 2019-01-04 | 四川海沛环保科技有限公司 | A method of utilizing cement kiln intermediate product harmless treatment electrolytic manganese residues |
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| CN109721299A (en) * | 2019-01-31 | 2019-05-07 | 贵州大学 | A kind of method that electrolytic manganese residues prepare baking-free ceramicite |
| CN110002829A (en) * | 2019-04-30 | 2019-07-12 | 肇庆泉兴生态科技有限公司 | A kind of electrolytic manganese residues are non-burning brick and preparation method thereof |
| 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 |
| CN110423085A (en) * | 2019-09-11 | 2019-11-08 | 北京科技大学 | One kind cracking resistance steady layer of water material of road containing electrolytic manganese residues 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 |
| CN114394814A (en) * | 2021-12-29 | 2022-04-26 | 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 |
| CN114213068A (en) * | 2022-01-17 | 2022-03-22 | 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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