Preparation of manganese sulfate from low-grade manganese carbonate ores by sulfuric acid leaching

In this study, a method for preparing pure manganese sulfate from low-grade ores with a granule mean size of 0.47 mm by direct acid leaching was developed. The effects of the types of leaching agents, sulfitric acid concentration, reaction temperature, and agitation rate on the leaching efficiency of manganese were investigated. We observed that sulfuric acid used as a leaching agent provides a similar leach- ing efficiency of manganese and superior selectivity against calcium compared to hydrochloric acid. The optimal leaching conditions in sul- furic acid media were determined; under the optimal conditions, the leaching efficiencies of Mn and Ca were 92.42% and 9.61%, respec- tively. Moreover, the kinetics of manganese leaching indicated that the leaching follows the diffusion-controlled model with an apparent ac- tivation energy of 12.28 kJ·mol-l. The purification conditions of the leaching solution were also discussed. The results show that manganese dioxide is a suitable oxidant of ferrous ions and sodium dimethyldithiocarbamate is an effective precipitant of heavy metals. Finally, through chemical analysis and X-ray diffraction analysis, the obtained product was determined to contain 98% of MnSOa4·H20.

Pitfalls of acid leaching method for determining organic and inorganic carbon contents in marine sediments

Organic and inorganic carbon contents of marine sediments are important to reconstruct marine productivity,global carbon cycle, and climate change. A proper method to separate and determine organic and inorganic carbons is thus of great necessity. Although the best method is still disputable, the acid leaching method is widely used in many laboratories because of its ease-of-use and high accuracy. The results of the elemental analysis of sediment trap samples reveal that organic and inorganic carbon contents cannot be obtained using the acid leaching method, causing an infinitely amplified error when the carbon content of the decarbonated sample is 12%±1% according to a mathematical derivation. Acid fumigation and gasometric methods are used for comparison, which indicates that other methods can avoid this problem in organic carbon analysis. For the first time, this study uncovers the pitfalls of the acid leaching method, which limits the implication in practical laboratory measurement, and recommends alternative solutions of organic/inorganic carbon determination in marine sediments.

Dynamics of Humic Substance-Complexed Copper and Copper Leaching During Composting of Chicken Manure

Chicken manure was composted for 110 d to evaluate changes in organic carbon (C) and humic substance-complexed copper (HS-Cu) extracted with water,sodium hydroxide (NaOH),and sodium pyrophosphate and sodium hydroxide mixture (Na 4 P 2 O 7-NaOH).The average HS-Cu content from the Na 4 P 2 O 7-NaOH extraction accounted for 46.8% of the total Cu in the compost,followed by those from the NaOH and water extractions,which accounted for 34.5% and 6% of the total Cu in the compost,respectively.NaOH-Na 4 P 2 O 7-extractable HS-Cu increased throughout the composting process.NaOH-extractable HS-Cu increased during the first 50 d of composting and then leveled off.Water-extractable HS-Cu enhanced during the first 21 d and then decreased.Water-extractable HS-Cu was not correlated to NaOH-or NaOH-Na 4 P 2 O 7-extractable organic C.The average amount of Cu leached from the compost was about 20% of the total Cu in the chicken manure and Cu leaching increased during the first 35 d of composting and then decreased.Leaching of Cu was significantly correlated to the concentrations of HS-Cu extracted with NaOH and water,but was not correlated to the concentration of HS-Cu extracted with NaOH-Na 4 P 2 O 7.Thus,NaOH-and water-extractable HS-Cu were relatively labile and NaOH-Na 4 P 2 O 7-extractable HS-Cu was relatively immobile.Composting process after rapid decomposition could result in low potential of Cu leaching because of formation of more NaOH-Na 4 P 2 O 7-extractable HS-Cu.

Leaching of Silver from Boorchi Ag-Pb Ore in Mongolia with Acidic Thiourea Solution

A hydrometallurgical process to extract silver from the silver-lead ore in Boorchi,Mongolia by using thiourea leaching solution is studied in this work.Through the observation of optical and scanning electron microscopes,and energy spectral analysis,it is determined that 5 kinds of silver minerals exist in the ore,including argentite,Ag-tetrahedrite,Ag-Zn-Sb-tetrahedrite,freibergite and acanthite.The experimental results of direct thiourea leaching of the ore show that 56%～60% of silver is leached.The main reason for the low leaching rate is due to silver minerals enveloped in galena and other minerals,even though the ore is ground to the particle size of 75μm.When the ore is pretreated with ammonium carbonate solution under oxidation,the experimental results of thiourea leaching show that the leaching rate of silver increases to near 75% with the pretreatment.Based on the leaching experiments,a principle hydrometallurgical technological route to extract silver from the Ag-Pb ore is proposed.

废旧特斯拉电池LiNi_(0.815)Co_(0.15)Al_(0.035)O_(2)正极物料选择性焙烧转型提锂

在“碳达峰碳中和”战略目标下,新能源产业受到国家政策的大力扶持,我国锂电新能源产业迅猛发展,作为新能源汽车核心部件的锂离子电池的产量及报废量持续增加。废旧三元锂电池含大量的有价金属和危险废物,对其综合回收利用兼具经济和环境效益。传统火法工艺存在能耗高、锂损失率大、污染重等缺点,而常规湿法工艺亦存在流程长、净化工序复杂、锂综合回收率低、废水量大等问题。现阶段研究多以LiNi_(0.5)Co_(0.2)Al_(0.3)O_(2)(NCM)三元正极材料为研究对象,而针对新型含铝特斯拉电池物料的回收鲜有报道,因此以典型的特斯拉三元正极材料LiNi_(0.815)Co_(0.15)Al_(0.035)O_(2)(NCA)为原料,以碳和氢气为还原剂,采用“还原焙烧转型-选择性提锂”工艺对废旧锂电池中的锂进行选择性提取回收,并从还原焙烧及浸出方式、能耗和环保等方面进行对比。结果表明:采用碳还原焙烧选择性提锂工艺,在碳含量为15.0%、温度为700℃、焙烧时间为90 min的条件下,Li、Ni、Co、Al的提取率分别为97.84%、0.45%、0.36%、0.75%;采用氢还原焙烧选择性提锂工艺处理NCA物料,转型温度较低,在相同焙烧时间下,在焙烧温度500℃、氢气流速300 mL/min的条件下,Li提取率为95.97%,Al的提取率为8.65%,Ni、Co提取率均小于0.5%,同时产物中无CO、CO_(2)等污染气体产生。因此,氢还原焙烧具有较大的工业应用潜力。

Studies on Environmentally Friendly Leaching Processes in China

The newly developed green leaching processes for chromium, lead and gold extraction from ores or concentrates are described. The chromium is extracted from the iron chromite ore with fused sodium hydroxide at 500－550°C as sodium chromate. The galena in lead sulfide concentrate is converted into lead carbonate in ammonium or sodium carbonate solution at 50－80°C followed by the separation of lead carbonate formed from the unconverted sulfide ores by flotation. Gold associated with sulfide ore (such as pyrite and chalcopyrite) can be extracted into sodium thiosulfate solution without any pretreatment such as roasting, high pressure aqueous oxidation or bacteria pre-leaching.

配施紫云英对不同类型水稻土溶解性有机碳氮淋溶及损失的影响

为探讨配施紫云英对不同类型稻田土壤溶解性有机碳(Dissolved organic carbon,DOC)和溶解性有机氮(Dissolved organic nitrogen,DON)含量的影响程度,阐明稻田土壤DOC和DON的淋溶特性,本研究以亚热带3种典型水稻土(黄泥田、灰黄泥田和灰泥田)为研究对象,通过田间试验,探讨等氮磷钾条件下单施化肥(CK)和紫云英配施化肥(cmv)处理对不同水稻土DOC和DON的动态变化、淋溶特性及损失的影响。结果表明,不同土壤类型水稻土DOC和DON的淋溶特性有所不同。3种供试水稻土中,灰泥田水稻土DOC淋溶损失量最大,其CK处理DOC淋溶损失量较灰黄泥田和黄泥田分别显著提高24.09%和72.15%,cmv处理淋溶损失量较灰黄泥田和黄泥田分别显著提高16.53%和40.55%;而黄泥田水稻土DON淋溶损失量最大,其CK处理淋溶损失量较灰黄泥田和灰泥田分别显著提高18.93%和37.01%,cmv处理3种不同类型水稻土DON淋溶损失量无显著差异。配施紫云英可显著降低水稻土DON的淋溶损失量,每季水稻中cmv处理黄泥田、灰黄泥田和灰泥田DON淋溶损失量较CK处理分别降低了24.67%、14.88%和13.54%;黄泥田cmv处理DOC较CK处理提高了19.19%,而灰黄泥田和灰泥田2种施肥处理无显著差异。供试稻田中DOC和DON在土层间的淋溶具有一定的延迟性,且DOC的延迟时间大于DON。灰色关联分析表明,在土壤性质中有机质是影响水稻土DOC淋溶损失的重要因素,孔隙度是DON淋溶损失的重要影响因素。不同类型水稻土DON的淋失早于DOC,且DON在黄泥田中淋溶损失较高,而DOC在灰泥田中淋溶损失较高;在等氮磷钾的条件下,配施紫云英可减少水稻土DON的淋溶损失,而低肥力水稻土DOC的淋溶损失量有所增加。

煤气化细渣高炭组分超声强化酸浸法制备多孔材料

煤气化细渣是煤炭清洁高效利用的副产物之一,其资源化应用迫在眉睫。通过简单筛分得到固定碳含量高于60%的高炭组分,并以此为原料,采用超声酸浸法制备多孔材料。以核废水中放射性碘的吸附处理为应用背景,用碘吸附值表征多孔材料的吸附性能。结合SEM、BET、XRD和FT-IR等性质和结构分析方法,系统研究了超声时间、超声功率、酸浓度和温度对多孔材料碘吸附性能和组成结构的影响规律;并探讨了超声强化酸浸对残炭的组成结构的影响机制和灰成分的迁移转化规律,总结出超声强化酸浸作用机理。结果表明,煤气化细渣高炭组分在酸浓度为4 mol/L、酸浸温度为50℃、超声功率为210 W,超声时间1.5 h的条件下,所制备多孔材料的碘吸附性能最佳,为468.53 mg/g,比表面积达到474.97 m^(2)/g,且具有以介孔为主的丰富孔隙结构。各因素对多孔材料碘吸附性能影响的顺序为:超声时间>酸浓度>超声功率>酸浸温度。超声强化酸浸作用机理是超声空化和机械波作用一方面强化炭灰黏附颗粒的解离,使堵塞在气化细渣孔道内的灰颗粒脱附,增加孔隙结构的连通性;其次,会导致炭灰颗粒表面裂纹的产生,增强碳颗粒内部无机组分的可及性;第三,能够提高酸浸过程的传质速率,强化气化细渣中的无机组分的浸出效果。

工业含钙固废矿化CO_(2)的实验

双碳背景下,CO_(2)矿化作为一种有效固碳技术受到更多关注。本文针对6种工业含钙固废,分别采用氯化铵溶液浸出并制备矿化母液,然后在常温常压下开展直接和间接矿化模拟燃煤烟气中CO_(2)的实验,并对6种固废的矿化效率和矿化产物进行详细分析,同时测试了浸出剂浸出含钙固废的循环能力。结果表明,由于含钙矿物相种类与含量的不同,6种固废的Ca^(2+)浸出率介于18.88%~95.15%之间,浸出液Ca^(2+)浓度大小为:净化灰>烧结法赤泥>燃煤飞灰2>燃煤飞灰1>烘干灰>拜耳法赤泥。氯化铵溶液循环浸出净化灰、燃煤飞灰2和烧结法赤泥后,随着循环次数的增加,燃煤飞灰2和净化灰中的间接矿化效率仅降低了1.44%和1.34%,烧结法赤泥的间接矿化效率降低了6.21%。6种固废中电石净化灰拥有最高间接矿化效率达57.60%,烧结法赤泥拥有最高直接湿法矿化效率为67.25%。CO_(2)间接矿化的产物为粒径介于2~5μm的菱面体方解石。

煤气化渣制备碳硅介孔材料及甲基橙吸附性能研究

开发了一种煤气化渣低成本制备碳硅介孔材料的方法,探究了影响孔结构的因素和在甲基橙中的吸附性能。采用酸浸法制备碳硅介孔材料,通过材料的孔隙结构和金属氧化物浸出率对制备工艺进行优化。结果表明,温度和时间影响较小,原料粒径和酸浓度影响较大。粒径较小的原料酸浸之后比表面积更大,酸浓度对于碳硅介孔材料的影响比较明显,最佳的酸浓度为16%(质量分数),金属氧化物浸出率和残余碳含量综合影响着比表面积和孔容的大小。煤气化渣基碳硅介孔材料的吸附过程与伪二阶吸附模型最为接近,吸附平衡符合Langmuir模型,对甲基橙最大的吸附量为89.13 mg/g。

Rare earth recovery from fluoride molten-salt electrolytic slag by sodium carbonate roasting-hydrochloric acid leaching

Fluorinated rare earth molten-salt electrolytic slag contains a considerable amount of rare earth elements,as well as a variety of heavy metals and fluorides that cause environmental pollution.Therefore,it is of great importance to fully utilise this resource.In this study,the transformation mechanism of fluorinated rare earth molten-salt electrolytic slag roasted with sodium carbonate,and the regulation mechanism of rare earth leaching under different roasting conditions were investigated with the help of thermodynamic calculation of the reactions and kinetic analysis.The thermodynamic and differential thermal thermogravimetric(DTA-TG)analysis shows that the transformation of rare earth fluoride to rare earth oxide is promoted at elevated temperature.Furthermore,the leaching experimental results show that increasing the temperature,time,hydrochloric acid concentration,and liquid-solid ratio can effectively promote the recovery of rare earths.The optimum experimental conditions are a roasting temperature of 700℃,roasting time of 2 h,and sodium carbonate to molten salt electrolytic slag mass ratio of 0.6,followed by leaching at 80℃with a liquid-solid ratio of 10:1 by adding 3 moI/L hydrochlo ric acid with stirring for 2 h.Under these conditions,the rare earths in the molten salt electrolytic slag are biologically transformed at a lower temperature and the leaching efficiency of rare earths exceeds 98%.

从红土镍矿湿法废水中回收镁和锰

红土镍矿湿法冶炼工艺被广泛应用于工业生产,伴随产生大量含Mn^(^(2+))、Ca^(2+)、Mg^(2+)等有价金属的废液,选择性回收不仅能提高经济效益,还能降低废液处理的难度。以CO_(2)为碳源,NaOH作pH值调节剂,在NaOH浓度10%、反应时间15min、液相pH=6.6的条件下能选择性回收废液中的锰,制备含Mn41%、Ca2.5%、Mg0.8%的粗级碳酸锰。回收锰后的废液进一步用0.5mol/L碳酸钠溶液调节pH值至10,回收液相中的Mg^(2+)。此回收工艺能提高经济效益,减少湿法冶炼工艺的碳排放量,具有较高的绿色、经济应用前景。

滤材沉积法回收贫液中载金粉炭试验研究

内蒙古某金矿每年随贫液上浸堆的固体量约73 t,其中粉炭量约40 t,吨炭载金量约373 g,金随粉炭流失的同时,堆上浸出的金还被粉炭截留,采用管道中布置滤袋效果不理想。试验采用滤材沉积方式捕收贫液中粉炭,即将滤材折叠形成一定构型,放入贫液池使粉炭自然沉积。针对粉炭和贫液性质选择3种滤材,并进行表面粗糙度测试,通过试验对比粉炭在不同滤材的沉积效果,发现沉积能力与滤材表面粗糙度呈正相关;通过沉积动力学试验,探明沉积率随时间先增后降,且沉积能力受滤材孔径影响,孔径为粉炭粒径D80的1.5倍时最佳;采用高压气水联合脱附沉积粉炭。结果表明:20μm聚丙烯无纺滤材沉积16 h效果最佳,单位面积沉积量为79.31 g/m2,贫液流经沉积单元所含粉炭量40%可被捕收,脱附率达88.7%,综合回收率达35.5%,且脱附后滤材有较好的二次使用性。研究结果对采用活性炭作为吸附剂的堆浸工艺均有一定的借鉴意义。

基于生物刺激的中性地浸采铀地下水修复试验研究

以某中性地浸铀矿山采区内地下水为研究对象,基于生物刺激修复方式,加入碳源,开展了地下水+砂岩混合体系的污染修复室内试验,筛选得到了优势碳源,确定了优势碳源的最佳投加水平,并验证了优势碳源对U的修复效果。结果表明,乙醇对中性地浸地下水中U的修复效率最高,可达97.48%,修复效果与pH和Eh显著相关(Pearson’s r>0.7,P<0.01)。乙醇的生物代谢过程对水-岩体系的扰动较少,能保证HCO_(3)^(-)和SO_(4)^(2-)等离子环境的相对稳定,更易实现地下水中U的长期稳定。

铅冶炼次氧化锌烟灰浸出脱氯试验研究

次氧化锌烟灰主要成分为氧化锌,具有易于浸出且锌回收率高的特点,但随着氟、氯等元素增多,对后期的锌浸出及电积工艺控制造成很大的影响。高效去除次氧化锌烟灰中的氟氯成为锌冶炼行业研究的重点内容。通过单因素试验,以水和碳酸钠溶液作为浸出剂,分别考察液固比、浸出温度、浸出时间、pH等因素对铅冶炼生产过程产生的次氧化锌烟灰中氯离子脱除率及锌离子损失率的影响,并确定最佳工艺参数。结果表明,采用碳酸钠碱性浸出,液固比8∶1,浸出温度45℃,浸出时间100 min,pH=11.0,在此优化参数下,氯离子脱除率可达到87.43%,锌损失率为0.5%。

锶同位素地层学新方法探究

锶同位素地层学(Strontium Isotope Stratigraphy,简称SIS)是建立海相沉积岩层年代模型的一种重要方法。该方法在油气勘探、古气候重建等领域有着广泛的应用。应用SIS的前提是:(1)全球海水锶同位素成分相对均一且随时间推移逐渐变化;(2)样品的锶同位素代表样品形成时原始海水的成分。但是,后期成岩蚀变以及样品表面吸附的杂质会改变样品的锶同位素组成,从而造成无意义的SIS年龄。因此,样品选择与前处理至关重要。文章全面总结了已有的海相碳酸盐岩锶同位素地层学的测试方法,包括样品前处理和锶同位素测试。近年来,为了精准地提取古海洋成分信息,多项应用碳酸盐钕、铅和锂同位素的研究对样品前处理流程进行了深入的探讨。结合这些领域的新发展,作者全面地研究了一个具有独立年龄限制的采集于埃及苏黎世海湾浅海中新世沉积地层中的牡蛎化石样品,根据淋洗溶液中的元素含量变化,推荐一套新的碳酸盐样品前处理流程。文章同时也总结和比较了使用热电离质谱仪(TIMS)和多接收电感耦合等离子质谱(MC-ICPMS)测试的锶同位素的准确度和精度。尽管对于锶含量较高的样品,新一代MC-ICP-MS能够达到与老一代TIMS相似的精度,但是对于含量较低或者对精度要求较高的样品,TIMS仍然是SIS研究的首选。最后,作者对使用MC-ICP-MS开展锶同位素地层学提出一些建议。

Application of Rice Husk Biochar for Achieving Sustainable Agriculture and Environment

This paper critically reviewed the current knowledge and challenges of rice husk biochar(RHB)production and its effects on soil properties,plant growth,immobilization of heavy metals,reduction of nutrient leaching and mitigation of greenhouse gas emissions.The characteristics of RHBs produced at various pyrolysis temperatures were discussed and compared to biochars derived from other agro-industrial wastes.RHBs produced at higher pyrolysis temperatures show lower hydrogen/carbon ratio,which suggests the presence of higher aromatic carbon compounds.The increase of pyrolysis temperature also results in production of RHBs with higher ash content,lower yield and higher surface area.RHB usually has higher silicon and ash contents and lower carbon content compared to biochars derived from other feedstocks at the same pyrolysis conditions.Although it depends on soil type,RHB application can improve soil organic carbon content,cation exchange capacity,available K concentration,bulk density and microbial activity.The effect of RHB on soil aggregation mainly depends on soil texture.The growth of different crops is also enhanced by application of RHB.RHB addition to soil can immobilize heavy metals and herbicides and reduce their bioavailability.RHB application shows a significant capacity in reduction of nitrate leaching,although its magnitude depends on the biochar application rate and soil biogeochemical characteristics.Use of RHB,especially in paddy fields,shows a promising mitigation effect on greenhouse gas(CH4,CO2 and N2O)emissions.Although RHB characteristics are also related to other factors such as pyrolysis heating rate and residence time,its performance for specific applications(e.g.carbon sequestration,pH amendment)can be manipulated by adjusting the pyrolysis temperature.More research is needed on long-term field applications of RHB to fully understand the advantages and disadvantages of RHB as a soil amendment.

Calcareous Sodic Soil Reclamation as Affected by Corn Stalk Application and Incubation: A Laboratory Study

A laboratory lysimeter experiment was conducted to investigate the effects of forage corn (Zea mays L.) stalk application on the CO2 concentration in soil air and calcareous sodic soil reclamation. The experimental treatments tested were soil exchangeable sodium percentage (ESP) levels of 1, 11, and 19, added corn stalk contents of 0 to 36 g kg-1, and incubation durations of 30 and 60 days. The experimental results indicated that corn stalk application and incubation significantly increased CO2 partial pressure in soil profile and lowered pH value in soil solution, subsequently increased native CaCO3 mineral dissolution and electrolyte concentration of soil solution, and finally significantly contributed to reduction on soil sodicity level. The reclamation effciency of calcareous sodic soils increased with the added corn stalk. When corn stalks were added at the rates of 22 and 34 g kg-1 into the soil with initial ESP of 19, its ESP value was decreased by 56% and 78%, respectively, after incubation of 60 days and the leaching of 6.5 pore volumes (about 48 L of percolation water) with distilled water. Therefore, crop stalk application and incubation could be used as a choice to reclaim moderate calcareous sodic soils or as a supplement of phytoremediation to improve reclamation effciency.

白云石炼镁收尘灰制备碳酸钙工艺研究

以白云石炼镁收尘灰为原料,利用铵浸-碳化法制备碳酸钙。采用XRD、SEM和EDS对制备的样品进行表征。研究了制备碳酸钙的3个过程中消化水量、消化时间、消化温度、氯化铵浓度、铵浸温度、碳化时间、碳化温度及二氧化碳流速对样品产率影响。得到了制备碳酸钙的最佳工艺:水和炼镁收尘灰的质量比为7∶1、消化温度30℃、消化时间80 min,氯化铵浓度2 mol·L^(-1)、铵浸温度55℃、铵浸时间15 min、二氧化碳流速250mL·min^(-1)、碳化温度30℃、碳化时间9min。最佳工艺下制备的碳酸钙由物质的量比为1∶1的方解石和球霰石两相组成,产率86.62%,纯度97.5%。

煅烧-铵盐两步浸出法对磷矿浮选尾矿钙镁回收研究

采用煅烧-铵盐两步浸出法对磷矿浮选尾矿中的钙和镁进行回收,考查了铵盐种类及用量、固液比、反应温度、反应时间等对氧化钙和氧化镁浸出率的影响。磷矿浮选尾矿的最佳煅烧温度为1000℃、煅烧时间为60 min。在氧化钙与氯化铵摩尔比为1∶2.2、固液比为1∶7、反应温度为35℃、反应时间为20 min的条件下,氧化钙的浸出率为56.69%,氧化镁的浸出率为4.29%,较好地实现了钙镁分离。在氧化镁与硫酸铵摩尔比为1∶1.4、固液比为1∶10、反应温度为90℃、反应时间为60 min的条件下,氧化镁的浸出率达83.43%。煅烧-铵盐两步浸出法能有效实现对磷矿浮选尾矿的二次利用。