The Influence of CO_(2) Cured Manganese Slag on the Performance and Mechanical Properties of Ultra-High Performance Concrete

The presence of toxic elements in manganese slag(MSG)poses a threat to the environment due to potential pollution.Utilizing CO_(2) curing on MS offers a promising approach to immobilize toxic substances within this material,thereby mitigating their release into the natural surroundings.This study investigates the impact of CO_(2) cured MS on various rheological parameters,including slump flow,plastic viscosity(η),and yield shear stress(τ).Additionally,it assesses flexural and compressive strengths(f_(t) and f_(cu)),drying shrinkage rates(DSR),durability indicators(chloride ion migration coefficient(CMC),carbonization depth(CD)),and the leaching behavior of heavy metal elements.Microscopic examination via scanning electron microscopy(SEM)is employed to elucidate the underlying mechanisms.The results indicate that CO_(2) curing significantly enhances the slump flow of ultra-high performance concrete(UHPC)by up to 51.2%.Moreover,it reduces UHPC’sηandτby rates ranging from 0%to 52.7%and 0%to 40.2%,respectively.The DSR exhibits a linear increase corresponding to the mass ratio of CO_(2) cured MS.Furthermore,CO_(2) curing enhances both f_(t) and f_(cu) of UHPC by up to 28.7%and 17.6%,respectively.The electrical resistance is also improved,showing an increase of up to 53.7%.The relationship between mechanical strengths and electrical resistance follows a cubic relationship.The CO_(2) cured MS demonstrates a notable decrease in the CMC and CD by rates ranging from 0%to 52.6%and 0%to 26.1%,respectively.The reductions of leached chromium(Cr)and manganese(Mn)are up to 576.3%and 1312.7%,respectively.Overall,CO_(2) curing also enhances the compactness of UHPC,thereby demonstrating its potential to improve both mechanical and durability properties.

Preparation of electronic grade manganese sulfate from leaching solution of ferromanganese slag

Preparation of electronic grade manganese sulfate from ferromanganese slag, including grinding, leaching and purification, was studied. The impurities, such as Fe3+, Al3+, Ca2+, Mg2+, heavy metal ions and Na+, K+, were removed from leaching solution by neutralized-hydrolysis, fluorination precipitation, sulfuration precipitation and re-crystallization. Effects of pH of reaction, temperature and dosage of the different additives on removal rates of the metallic ions in leaching solution were investigated, and the suitable temperature, pH and the added amount of precipitating agent were obtained. The prepared manganese sulfate product, of which the mass fractions of Ca2+, Mg2+, Na+, K+ are all smaller than 0.005%, the mass fractions of Fe3+, Al3+ and heavy metal ions are smaller than 0.001%, and the mass fraction of Mn2+ is greater than 32%, can meet the demand of anode materials of lithium-ion batteries.

Mechanism of Boron Oxide as a Phase Regulator for Modification of Manganese Slag

The current research focused on adjusting the low hydration activity of the metallurgical slag by phase reconstruction technique. Boron oxide was used as a phase regulator to improve the amorphous phase composition of the manganese slag, consequently enhancing its hydraulic activity. The effects of boron oxide dosage and calcination temperature on the manganese slag amorphous phase content were investigated. XRD and DTG were performed to analyze the hydration mechanism of the manganese slag powder and cement. Results show that, when boron oxide dosage is 15%, calcination temperature is 1 300℃, and holding time for 1 hour, the amorphous content of the modified manganese slag reaches 95% and its 28-day activity index reaches 8 1.7%. The manganese slag powder can then be used as cement or concrete admixtures for the building materials industry.

Lithium and manganese extraction from manganese-rich slag originated from pyrometallurgy of spent lithium-ion battery

Mn and Li were selectively extracted from the manganese-rich slag by sulfation roasting−water leaching.The extraction mechanisms of Mn and Li were investigated by means of XRD,TG−DSC,and SEM−EDS.73.71%Mn and 73.28%Li were leached under optimal experimental conditions:acid concentration of 82 wt.%,acid-to-slag mass ratio of 1.5:1,roasting temperature of 800°C,and roasting time of 2 h.During the roasting process,the manganese-rich slag first reacted with concentrated sulfuric acid,producing MnSO_(4),MnSO_(4)·H_(2)O,Li_(2)Mg(SO_(4))_(2),Al_(2)(SO_(4))_(3),and H_(4)SiO_(4).With the roasting temperature increasing,H_(4)SiO_(4) and Al_(2)(SO_(4))_(3) decomposed successively,resulting in generation of mullite and spinel.The mullite formation aided in decreasing the leaching efficiencies of Al and Si,while increasing the Li leaching efficiency.The formation of spinel,however,decreased the leaching efficiencies of Mn and Li.

Thermodynamic Behavior of Manganese and Phosphorus between Liquid Iron and CaO-MgO-SiO_2-Al_2O_3-Fe_tO-MnO-P_2O_5 Slags

The thermodynamic behavior of manganese and phosphorus between liquid iron and CaO-MgO-SiO2-Al2O3-FetO-MnO-P2O5 ladle slag system was addressed by investigating the thermodynamic equilibria between liquid iron containing Mn and P and the ladle slag at 1873 K. The Mn distribution ratio L-Mn increases with increasing FetO content and decreasing the basicity ((%CaO + %MgO)/(%SiO2 + %Al2O3 + %P2O5)) in slag, while the P distribution ratio Lp seems to be increased as FetO content and the basicity increases. The values of L-Mn and L-p decrease by the addition of Al2O3 into slag. The expression of the dependence of L-Mn and L-p on the basicity and FetO content in slag was obtained.

Applicability of law of mass action to distribution of manganese between slag melts and liquid iron

According to the law of mass action and the coexistence theory of slag structure, the distribution of manganese between MnO FeO SiO 2 and MgO MnO FeO SiO 2 slag melts as well as liquid iron was analyzed. It is shown that K ′ Mn and K MnO are only dependent on temperature and don’t change with basicities and compositions of slag melts. So the distribution of manganese between the above mentioned slag melts and molten iron obeys the law of mass action. But analysis of experimental results from other sources shows that K ′ Mn and K MnO really change with basicities of slag, which is probably arisen from not approaching equilibrium under low basicity slag melts.

锰渣-沼渣复合材料对Sb^(3+)的吸附特性及吸附机理

以沼气渣和锰渣为原料,采用混合-共热解法制备了负载锰渣的生物炭复合吸附材料(MBC)。通过静态吸附试验探究了热解温度、锰渣与沼渣的质量比、溶液初始pH和材料投加量对吸附Sb^(3+)效果的影响,结合XRF、XRD、FTIR、SEM-EDS和XPS等表征方法探究其吸附机理。结果表明,MBC表面孔隙结构较为丰富,且负载着许多铁、锰、钙化合物,SiO_(2)、CaCO_(3)和CaS是MBC的主要晶相。在热解温度为600℃、质量配比m(锰渣)∶m(沼渣)为6∶4、初始pH为3、投加量为20 mg的条件下,MBC对Sb^(3+)的最大吸附量为28.71 mg/g,比改性前提高了60.82%。MBC对Sb^(3+)的吸附机理主要包括共沉淀、氧化还原反应、络合作用和离子交换。

Mn evaporation and denitrification behaviors of molten Mn steel in the vacuum refining with slag process

Considering the precise composition control on the vacuum refining of high-Mn steel, the behaviors of both Mn evaporation and nitrogen removal from molten Mn steel were investigated via vacuum slag refining in a vacuum induction furnace. It was found that the reaction interfaces of denitrification and Mn evaporation tend to migrate from the surface of slag layer to the surface of molten steel with the gradual exposure of molten steel during the vacuum slag refining process. Significantly, compared with the experimental group without slag addition, the addition of slag into steel can result in a lower Mn evaporation rate constant of 0.0192 cm·min~(-1) at 370 Pa, while the denitrification rate is almost not affected. Besides, the slag has a stronger inhibitory effect on Mn evaporation than the reduced vacuum pressure. Moreover, the inhibitory effect of the slag layer on Mn evaporation can be weakened with the increase of the initial Mn content in molten steel. The slag layer can work as an inhibitory layer to reduce the Mn evaporation from molten steel, the evaporation reaction of Mn mainly proceeds on the surface of the molten steel. This may be attributed to the Mn mass transfer coefficient for one of reaction at steel/slag interface, mass transfer in molten slag, and evaporation reaction at slag/gas interface is lower than that of evaporation reaction at steel/gas interface. The introduction of slag is proposed for both denitrification and manganese control during the vacuum refining process of Mn steels.

Effect of Al content on the reaction between Fe-10Mn-xAl(x=0.035wt%,0.5wt%,1wt%,and 2wt%)steel and CaO-SiO_(2)-Al_(2)O_(3)-MgO slag

The effect of Al content(0.035 wt%,0.5 wt%,1 wt%,and 2 wt%)on the composition change of steel and slag as well as inclusion transformation of high manganese steel after it has equilibrated with Ca O-Si O_(2)-Al_(2)O_(3)-Mg O slag was studied using the method of slag/steel reaction.The experimental results showed that as the initial content of Al increased from 0.035 wt%to 2 wt%,Al gradually replaced Mn to react with Si O_(2)in slag to avoid the loss of Mn due to the reaction;this process caused both Al_(2)O_(3)in slag and Si in steel to increase while Si O_(2)and Mn O in slag to reduce.In addition,the type of inclusions also evolved as the initial Al content increased.The evolution route of inclusions was Mn O→Mn O-Al_(2)O_(3)-Mg O→Mg O→Mn O-Ca O-Al_(2)O_(3)-Mg O and Mn O-Ca O-Mg O.The shape of inclusions evolved from spherical to irregular,became faceted,and finally transformed to spherical.The average size of inclusions presented a trend that was increasing first and then decreasing.The transformation mechanism of inclusions was explored.As the initial content of Al increased,Mg and Ca were reduced from top slag into molten steel in sequence,which consequently caused the transformation of inclusions.

中国西南地区电解锰渣特性分析及影响因素研究

电解锰行业发展面临的困境之一是锰渣的处理处置方法。为探索绿色低碳的锰渣无害化处理技术,选取中国5家典型电解锰企业新、旧电解锰渣,通过其理化特性及浸出毒性分析,研究堆存条件、时间及工艺参数等因素对不同企业锰渣特性的影响。结果显示:不同企业的新、旧锰渣平均质量含水率相差最大时均达19%以上,浸出液pH值最高分别相差0.95、1.45,不同企业新鲜锰渣的SiO_(2)和Al_(2)O_(3)平均质量分数最大相差分别为43.18%、146.25%,且可溶性盐质量分数均超过10%,未达到填埋入场标准。锰渣中石膏和石英的质量分数随堆存条件和时间发生不同的变化。企业C在堆存过程中石膏和石英的质量分数在增加,而企业E锰渣中烧石膏质量分数在增加,石英质量分数在减少。历史锰渣浸出液中Mn^(2+)和氨氮(NH_(4)^(+)N)的质量浓度较高,分别超过GB/T 8978—1996一级排放标准限值的65.92~935.00倍和2.56~63.80倍,表明长期堆存的锰渣仍存在较大的环境污染风险。不同地区企业的锰渣应通过无害化处理与资源化利用来降低其环境污染风险,须根据化学成分、理化性质不同选择合适的资源化方式。

铁尾矿—硅锰渣—赤泥协同制备超高性能混凝土力学性能研究

选用铁尾矿粉、硅锰渣粉和赤泥作为矿物掺合料代替部分普通硅酸盐水泥,协同制备了2种不同水胶比的超高性能混凝土,研究了掺入铁尾矿—硅锰渣—赤泥的超高性能混凝土(Ultra-high Performance Concrete,UHPC)的力学性能,探究了铁尾矿粉掺量对UHPC的抗弯强度、劈裂抗拉强度和抗压强度的影响。结果表明:①水胶比较低的超高性能混凝土中,铁尾矿粉对混凝土抗弯强度影响较大,对劈裂抗拉强度影响较小;②水胶比较高的超高性能混凝土中,铁尾矿粉对混凝土抗弯强度的影响与对劈裂抗拉强度的影响基本一致;③随着铁尾矿粉掺量增加,水胶比为0.20和0.25的超高性能混凝土抗压强度降低,硅锰渣—赤泥组超高性能混凝土28 d抗压强度最大降低幅度分别为19.2%和22.9%。上述分析进一步反映出:①铁尾矿粉在超高性能混凝土中的掺量不宜超过矿物掺合料总量的40%;②铁尾矿粉的掺加不利于超高性能混凝土的早期抗压强度提升,但适量掺加铁尾矿粉(20%)有利于超高性能混凝土后期抗压强度增长;③三参数模型系数相对于铁尾矿—硅锰渣—赤泥超高性能混凝土的抗压强度和养护龄期关系相对集中,拟合相关系数较高。

生物炭辅助湿法球磨锰渣增效吸附Sb(V)

为提高废弃物锰渣Sb(Ⅴ)吸附效能,推动锰渣资源化利用,将生物炭和锰渣1:1混合辅助湿法球磨技术制备了球磨炭基锰渣复合材料(QBM),并结合材料理化性质、浸出毒性和Sb(Ⅴ)吸附性能进行探讨.结果表明,在固液比(材料:去离子水)1:6,转速150r/min室温持续8h湿法球磨下,复合材料pH值、电导率、阳离子交换容量和粒径各降低了9.7%、64%、15%、71%,同时Zeta电位更负,由-15mV降至-21mV(P<0.05).同时,湿法球磨将锰渣中锰离子和氨氮的浸出分别由415mg/L和82mg/L降至《污水综合排放标准》(GB 8978-1996)一级标准2mg/L和15mg/L以下,提高了复合材料安全性.此外,球磨将复合材料Sb(V)去除率从32%提升至81%(P<0.05),增强了复合材料吸附性能.最后,本研究揭示了湿法球磨通过改善材料理化性质提高Sb(Ⅴ)吸附性能和安全性的影响规律,显示出生物炭辅助湿法球磨锰渣增效吸附Sb(V)在治理环境锑污染领域的应用潜力,为资源化利用锰渣和缓解锰渣堆存带来的环境污染问题提供了理论支撑.

电解锰渣资源化回收利用技术研究进展及“双碳”影响评估

我国电解锰产业每年产生大量含有锰、氨氮等毒害组分的电解锰渣,传统的堆存处置方式存在较大环境风险,其资源化利用对电解锰产业环境污染治理具有重要意义。系统梳理了电解锰渣干法、火法及湿法三类资源化利用技术最新研究进展,全面解析了技术开发中的环境风险点,深入讨论了相关技术资源化过程中的碳排放情况。最后,结合行业发展需求与“双碳”目标,提出了电解锰渣资源化利用的优先发展技术方向、过程碳排放核算、加速资源化产品市场应用等建议,旨在为推动电解锰产业绿色、低碳转型升级提供技术支撑。

铁锰固废促进污泥堆肥进程及其腐殖化特性

利用铁锰类工业固废提升污泥堆肥腐殖化程度,可实现污泥与工业固废的协同处理与资源化利用。文章以污水厂脱水污泥为对象,添加铁锰冶炼渣或铁锰尾矿开展15 d堆肥试验,探究了污泥堆肥的腐殖化进程及特性。将铁锰固废添加至污泥类有机质固体废物中,堆体升温速率更快,50℃以上高温期可达96 h;堆肥处理15 d后,HA/FA均不低于1.0,种子发芽指数GI达到100%以上。堆肥产物除As外,其他重金属含量均低于《农用污泥污染物控制标准》(GB 4284-2018)A级标准限值,堆肥产物适于园地、牧草地、不种植食用农作物耕地使用。添加铁锰冶炼渣的堆肥产物多酚氧化酶、脱氢酶活性最高分别达到2.2μmol/(h·g)、13.5 mg/(d·g),水溶性有机碳含量明显上升,铁锰冶炼渣有利于有机质中间组分向胡敏酸类大分子物质转化,在保留碳素、氮素的同时,提高堆肥稳定性和腐熟度。

水淬锰渣-炉渣-石灰石复合微粉的活性试验

研究了经过物理激发的水淬锰渣微粉和炉渣微粉活性指数,进而确定水淬锰渣、炉渣适宜的比表面积;采用石膏、生石灰、水玻璃3种激发剂对水淬锰渣、炉渣、石灰石复合微粉进行了化学激发试验;探讨单一激发和复合激发对复合微粉的影响。结果表明:物理激发微粉时,水淬锰渣的适宜比表面积为470 m^(2)/kg,炉渣的适宜比表面积为410 m^(2)/kg;化学激发复合微粉时,使用4%的石膏和1%生石灰作为复合激发剂对复合微粉激发效果最佳,7、28 d活性指数达到最高,此时复合微粉7 d活性指数为55.7%,28 d活性指数为78.3%,均满足《用于水泥、砂浆和混凝土中的粒化高炉矿渣粉》(GB/T 18046—2017)中S75等级标准。

水淬硅锰渣的机械粉磨特性

这是一篇矿物加工工程领域的论文。根据机械力化学原理,采用振动磨的方式对水淬硅锰渣进行粉磨,通过研究粉磨时间对水淬硅锰渣粉比表面积、粒度分布、活性评价等影响,并使用比表面积和激光粒度分析仪、XRD和SEM等表征方法对水淬硅锰渣粉的比表面积、粒径分布、难磨物相和颗粒形貌进行了探讨,同时也研究了不同粉磨时间的水淬硅锰渣粉作掺合料对地聚物抗压强度的影响。结果表明,随着粉磨时间延长,硅锰渣粒度分布逐渐左移,颗粒粒径逐步细化,石英相逐渐向无定形结构转变。从成本角度考虑,当粉磨时间为25 min、比表面积为1.8281 m^(2)/g时作粉煤灰地聚物掺合料时,28 d抗压强度可达26.79 MPa。并确定出难磨物相为直锰辉石晶体结构,以及不同的含锰物相。

KH560对电解锰渣场原位修复防渗固结体性能的影响

固废填埋场渗漏原位修复过程中常见胶凝材料遇水膨胀,影响强度情况,为了解决该问题,采用两步水溶液聚合法将具有两性基团的KH560加入聚丙烯酸钠与电解锰渣中,制备电解锰渣基复合胶凝材料,通过抗压试验、渗水试验及腐蚀试验分析了固结体的抗压抗渗及耐腐蚀性能,利用红外光谱(FTIR)对固结体的分子结构进行了表征,通过SEM-EDS分析了固结体的表面形貌及元素含量变化,揭示了KH560对电解锰渣胶凝材料的力学增强机制和防渗作用机理。结果表明:①适量添加KH560可显著提升复合胶凝材料的抗压、抗渗及耐腐蚀性能,在KH560添加量为3%时,固结体的无侧限抗压强度是未添加KH560的固结体的2.25倍,渗透系数比未添加KH560的固结体降低了61.3%,抗蚀系数达0.85。②KH560分子结构中的硅氧基团Si—OCH_(3)与电解锰渣中的自由水发生了水解缩合反应,形成了Si—O—Si连接结构,减少了水隙通道,使固结体表面平整光滑,抗渗效果和耐腐蚀性能得到显著提升。

260 t转炉终点余锰含量控制实践

针对转炉冶炼终点余锰含量不合理影响产品质量和生产成本的问题,分析了铁水中锰含量、转炉终点温度、底吹状态、炉渣碱度及渣量等因素对终点余锰含量的影响,结果表明,转炉底吹状态、炉渣碱度及渣量是影响终点余锰含量的主要原因。采取优化转炉底吹制度和转炉吹炼工艺制度后,转炉终点余锰含量可以稳定控制在0.10%~0.12%。

不同晶化温度对硅锰渣铸石的内部温差、析晶和物理性能的影响规律

以硅锰渣为主要原料,采用熔渣冷却析晶一步法(铸石浇铸法),在800、900、1000和1050℃四个不同晶化温度,分别制备了规格为ϕ100 mm×20 mm的铸石样品CT-800、CT-900、CT-1000和CT-1050,通过构建实验装置,测试了熔渣在成型和热处理全过程中心与边缘温度变化规律,并结合X射线衍射(XRD)、差示扫描量热分析(DSC)、扫描电子显微镜和能谱(SEM–EDS)等手段,分析了不同晶化温度对铸石中心和边缘的温差、析晶与物理性能的影响规律.研究表明:以硅锰渣为主要原料在900~1050℃保温析晶可以制备出满足天然花岗岩建筑板材标准(GB/T18601—2009)的铸石,晶相为辉石、黄长石以及硫化锰.CT-1000和CT-1050铸石析出更多和更大尺寸的晶相,存在微观孔隙和宏观缩孔,降低了其力学性能.CT-900具有最佳性能,而CT-800以玻璃相为主,热处理后发生断裂.在本实验条件下,最大温差(32℃)发生在把熔渣倒入模具的凝固成型阶段,且晶化温度越低,温差越大.CT-1000和CT-1050析晶阶段存在的大量析晶放热导致温差二次增大,延长了中心和边缘温度一致的时间.硫化锰是高温熔融态下析出晶相,易于氧化分解,快速冷却的边缘存在更多硫化锰相.黄长石较辉石在更高的温度下析出,较高的晶化温度处理样品和相同晶化温度下样品的中心部分均存在相对更多的黄长石相.

利用电解锰渣制备陶瓷骨料及在混凝土中的应用

电解锰渣的堆放威胁着人们健康和生态环境,因此电解锰渣的无害化处理成为亟需解决的难题。利用1 100℃高温烧结使电解锰渣中可溶的Mn和Cr固化在晶粒内,同时热分解含氨复盐。高温烧结后的电解锰渣已经瓷化且拥有较高的抗压强度,经过破碎分级后可替代混凝土中的骨料。研究结果表明,电解锰渣陶瓷粗骨料和细骨料能基本满足GB/T 25177—2010《混凝土用再生粗骨料》,由XRD和EDS分析可知,烧结后的电解锰渣含有一定量的CaSO_(4),CaSO_(4)的存在促进了水泥水化产物钙钒石的合成,使陶瓷骨料与水泥结合更加紧密,混凝土试块在断裂时陶瓷骨料不以拔出的形式失效,增加了混凝土试块力学的强度。利用陶瓷粗骨料和天然砂细骨料制备的混凝土试块14 d抗折强度为7.54 MPa,优于粗骨料和细骨料均为天然砂石的样品(5.36 MPa),且陶瓷粗骨料在混凝土中所含质量分数较大(48.55%),对于电解锰渣再利用具有重要意义。