电炉不锈钢渣硅热法在线还原解毒的工业试验

由于电炉不锈钢的冶炼工序特点,渣中铬含量较高,存在Cr6+浸出风险。在电炉不锈钢冶炼末期,利用硅热法对渣液层进行在线还原解毒,可有效降低渣中重金属氧化物含量,渣中w(Cr2O3)从6.10%降至0.79%,还原解毒率最大可达到87.1%。解毒后电炉渣中作为Cr6+主要赋存相的钙铬石(Ca Cr O4)消失。经毒性浸出检测,其总铬浸出量降至0.08 mg/L,Cr6+浸出量降至0.01 mg/L以下,均明显低于国家堆存限值和利用限值,可实现不锈钢EAF渣的安全排放及后续资源化利用。     

高冰镍浸出渣还原浸出工艺研究

以湿法冶炼高冰镍过程中产生的高冰镍浸出渣为研究对象,采用二氧化硫对高冰镍渣加压还原浸出,考察了初始硫酸浓度、液固比、通气方式、浸出温度和浸出时间对高冰镍渣还原浸出过程铜、铁行为的影响;对还原浸出液采用置换沉淀和冷冻结晶的方法,对还原浸出中铜和铁进行分离回收。结果表明：在初始硫酸浓度100 g/L、液固比6 mL/g、反应时间3 h、反应温度90℃、二氧化硫分压0.15 MPa的条件下,铁和铜的浸出率分别为99.35%、77.46%,浸出液中铁几乎全部为亚铁离子;在硫酸含量20～30 g/L、温度70℃、铁粉加入量5.7 g/L、反应时间40 min的条件下,对还原浸出液进行置换沉铜,沉铜率达到了99.70%,渣含铜为67.91%。在温度—10℃、保温时间20～30 min、初始硫酸浓度100 g/L的条件下,对沉铜后液进行冷冻结晶制备硫酸亚铁,铁沉淀率达到了72.6%,七水硫酸亚铁纯度达到了92.93%。     

氯化浸出-还原法处理铜阳极泥分铜渣

采用氯化法浸出铜阳极泥分铜渣中的金、硒、碲,并采用硫酸亚铁选择性还原浸出液中的金。结果表明:在最佳浸出条件即浸出时间150min、浸出温度60℃、氯酸钠浓度65g/L、液固比4∶1、氯化钠浓度50g/L、硫酸浓度300g/L下,金浸出率为93.7%,硒浸出率为96.5%,碲浸出率为76.4%;用硫酸亚铁还原氯化浸出液中的氯金酸是完全可行的,金还原率可达99.7%,还原产物中金以单质形式存在,基本不含单质硒、碲及其他杂质。     

镁盐共沉淀法深度除铬及WO_3的回收研究

研究了还原水解-镁盐共沉淀法对Na_2WO_4溶液深度除铬的工艺,并用碱浸法一次实现了铬镁渣中的钨铬分离。结果表明:在70℃下加入3倍理论量的Na_2S,控制pH值为8～9,反应0.5 h,加入1%的MgSO_4溶液继续反应0.5 h后过滤,滤液m(Cr)/m(WO_3)1.6×10~(-4);铬镁渣浸出终点碱度控制在30～40 g/L,最终可实现WO_3回收率96%,浸出液m(Cr)/m(WO_3)1.6×10~(-4)。     

从电解锰阳极泥中两段浸出锰富集硒试验研究

研究了以蔗髓和铁粉为还原剂,在酸性条件下从电解锰阳极泥中两段浸出锰并富集硒,考察了浸出温度、浸出时间、硫酸浓度、蔗髓用量、铁粉加入量对锰、硒浸出率和浸出液中残余有机物浓度的影响。结果表明:第1浸出阶段,在蔗髓/阳极泥质量比0.075 g/g、硫酸浓度4.4 mol/L、浸出温度90℃、浸出时间3 h条件下,锰、硒浸出率分别为74.31%和43.56%,浸出液中COD质量浓度0.337 g/L;在第2浸出阶段,阳极泥中未被浸出的锰,按铁粉/阳极泥质量比0.09 g/g添加铁粉,继续还原浸出,铁粉在还原浸出锰的同时,将溶液中的硒还原为单质硒沉淀,锰浸出率达99.31%,而硒的最终浸出率仅为0.50%,富集在浸出渣中。     

石油焦钒浸出液的黏度研究

研究了温度、氢氧化钠浓度、碳酸钠浓度和次氯酸钠用量对石油焦中钒的浸出率和浸出液的黏度变化的影响。结果表明,增加温度可以提高浸出率、降低溶液的黏度。氢氧化钠、碳酸钠、次氯酸钠浓度的增加在提高钒浸出率的同时,也增加了浸出液的黏度。适宜的工艺条件为:温度90℃、次氯酸钠用量0.249%、氢氧化钠浓度150g/L、碳酸钠浓度90g/L。钒浸出率~61%,黏度5.4mPa·s。     

铬渣中六价铬的浸出及还原试验研究

提出了硫酸浸出—浸出渣水合肼还原的铬渣解毒工艺,考察了相关因素对铬渣中六价铬去除率的影响,确定了铬渣解毒优化条件。试验结果表明:在80℃下用硫酸浸出铬渣,控制液固体积质量比8∶1,浸出终点pH为8.0左右,浸出时间120min,铬渣中的六价铬浸出率为76%;然后用水合肼还原浸出渣中剩余的六价铬,水合肼加入量为浸出渣质量的0.06%,最终渣中水溶性六价铬质量分数降至5mg/kg以下,达到排放要求。     

从高氟氯次氧化锌中回收锌铅

采用氢氧化钠和碳酸钠混合碱液洗涤脱除次氧化锌中的氟氯。在碱液中氢氧化钠和碳酸钠摩尔比为1∶1,控制液固比、洗涤温度时,氟、氯脱除率分别为92.31%和96.57%。碱洗液经沉锌、沉氟、沉氯处理,溶液中锌、氟、氯浓度分别为0.37、0.048、0.083g/L。采用锌电解废液浸出经碱洗脱除氟氯后的次氧化锌,控制电解废液硫酸浓度、液固比、浸出温度,浸出液中锌、铅、氟、氯浓度分别为86.27g/L、0.027g/L、0.042mg/L、0.078mg/L,浸出渣中锌和铅含量分别为9.13%和50.84%,锌和铅回收率分别为95.36%和96.57%。     

酸性铵盐沉钒在钒铬溶液中的应用研究

以钒渣钠化焙烧工艺得到的碱性钒浸出液为原料,在除去主要杂质硅和磷后,通过添加硫酸钠和三氧化铬,配制成一定组分的钒铬溶液,采用典型的酸性铵盐沉钒工艺,考察了溶液中钠、铬、钒含量以及加铵系数对沉钒率及最终V_2O_5中Na_2O含量的影响。结果表明:钒铬溶液在一定的浓度范围内可以采用酸性铵盐沉钒工艺,并取得较好效果。在满足高沉钒率及V_2O_5产品质量合格的前提下,溶液中钠的最大允许浓度为c(Na)/c(V)=2.4;在c(Na)/c(V)=1.8时,随着溶液钒浓度的增加,铬的最大允许浓度发生变化,表现为c(Cr)/c(V)逐步减小;对c(V)=25 g/L、c(Na)=45 g/L、c(Cr)=24 g/L的溶液浓缩后进行沉钒,通过降低浸出液固比提高钒浓度,钒的最大允许浓度为26 g/L;当加铵系数在1.5以上时,获得的V_2O_5产品满足相关质量要求;溶液离子浓度及加铵系数对沉钒率的影响很小。     

铬渣的微生物治理新技术研究

本研究采用课题组发现的还原Cr（VI）的专属无色杆菌属Ch-1菌株,对铬渣进行微生物治理。结果表明：铬渣渗滤液经该菌处理后,其中的Cr（VI）可达排放标准,沉淀物中Cr（OH）3含量达32.8％,具有实际回收价值。将铬渣进行微生物柱浸,7d后溶液中检测不出cr（VI）;解毒后铬渣中Cr（VI）达到国家危险废物毒性鉴别标准（GB5085-1996）。     

Treatment of Cr(VI) in COPR Using Ferrous Sulfate–Sulfuric Acid or Cationic Polysulfides

Column tests were conducted to evaluate two treatment strategies for reducing and stabilizing hexavalent chromium, Cr(VI), in chromium ore processing residue (COPR): permeation with a FeSO4–H2SO4 solution and blending with a cationic polysulfide reagent (CaSX). Cr(VI) leached at concentrations exceeding 50?mg/L from untreated COPR permeated with synthetic groundwater for >20 pore volumes of flow (PVF), and concentrations of Cr(VI) in the solid phase remained high (6,600?mg/kg). Permeation with solutions containing FeSO4–H2SO4 eliminated Cr(VI) from the effluent after initial, elevated leaching of Cr(VI) (100–1,500?mg/kg); however, high solid-phase concentrations of Cr(VI) remained in the column residuals (>1,300?mg/kg). COPR treated with CaSX leached Cr at <0.33?mg/L for 23.5 PVF and had solid-phase concentrations of Cr(VI) <10?mg/kg, although mineralogical analyses of treated solids showed potential chromate-containing mineral phases. Mineralogical analyses showed that precipitation and cementation occurred in the pore space of the COPR permeated with FeSO4–H2SO4, initially lowering the hydraulic conductivity > two orders of magnitude. However, acid dissolution channels eventually formed, resulting in preferential flow. COPR permeated with FeSO4–H2SO4 contained less brownmillerite and Cr(VI)-bearing hydrocalumite and hydrogarnet relative to untreated COPR. For COPR treated with CaSx, S encapsulated the subparticles of COPR with some micropore penetration, suggesting permanence of excess reductant after leaching with 23.5 PVF of synthetic rainwater.     

In situ reduction of hexavalent chromium in alkaline soils enriched with chromite ore processing residue

In investigating chromium sites in New Jersey, it has been observed that an organic-rich 0.5- to 4-foot-thick layer of decayed vegetation (locally known as "meadowmat") underlying the chromium-containing material acts as a natural barrier to the migration of Cr(VI). The groundwater in a sand layer directly beneath the meadowmat has been shown to contain low or nondetectable levels of chromium. The meadowmat is under highly reduced conditions due to bacterial activity associated with the organic material. Based on the observed ability of the meadowmat to reduce Cr(VI) to Cr(III), the feasibility of in situ reduction of Cr(VI) to Cr(III) at chromite ore processing residue (COPR) sites was investigated in biologically-active, laboratory-scale test columns. COPR typically has a high pH (in excess of 12) and may contain total chromium concentrations as high as 70,000 mg/kg. Experimental results demonstrated that the addition of a mineral acid (to lower the pH to between 7.0 and 9.5) and a bacteria-rich organic substrate (fresh manure) resulted in the reduction of Cr(VI) to the less toxic and less mobile trivalent form. Pore water Cr(VI) was reduced from approximately 800 mg/L to less than 0.05 mg/L over a period of eight months. This is less than the U.S. Environmental Protection Agency's (EPA) Maximum Contaminant Level (MCL) for chromium in drinking water of 0.1 mg/L. Solid phase Cr(VI) concentrations decreased from approximately 2,000 mg/kg to less than 10 mg/kg in the columns over a period of 11 months while the total chromium concentrations remained unchanged. Toxicity Characteristic Leaching Procedure (TCLP) extract from the treated columns met the regulatory limit of 5 mg/L of Cr, whereas the untreated samples had TCLP extract concentrations greater than 40 mg/L. This study demonstrated the potential applicability of in situ reduction to soils contaminated with Cr(VI) by adjusting the pH to between 7.0 and 9.5 and mixing in a bacteria-rich organic substrate.     

Importance of Mineralogy in the Geoenvironmental Characterization and Treatment of Chromite Ore Processing Residue

The geoenvironmental characterization of COPR at two deposition sites (New Jersey and Maryland) included geotechnical, chemical, mineralogical, and leaching analyses of three main chromite ore processing residue (COPR) types [gray-black (GB), hard brown (HB), clayey (C)]. Quantitative mineralogical analyses were instrumental in the delineation of the geochemical differences between the three COPR types, which enabled a framework to predict COPR response to potential remediation schemes. Overall, COPR mineralogy resembled cement, with hydration and pozzolanic reactions dominating its geochemistry. GB COPR was largely unreacted despite its prolonged exposure to humid conditions, while HB COPR was completely hydrated and contained high Cr(VI) concentrations. The two materials were chemically similar, with dilution accounting for the chemical and density differences. While the total acid neutralization capacity (ANC) of GB and HB was the same, the ANC at high pH (8–12) was higher in HB due to the dominance of hydrating materials, leading to more buffering capacity and lower Cr(VI) leaching levels. It is concluded that GB and HB were derived from the same ore and process and that postdepositional transformations account for the emergence of HB layers in COPR sites. The physicochemical properties of HB [hardness, high and inaccessible Cr(VI), high ANC] are complicating factors for in situ COPR reductive treatment in the presence of HB.     

砂岩铀矿围岩中性条件下对铀的吸附试验

砂岩型铀矿地浸采铀体系中,溶解铀在水岩界面发生的吸附作用对铀的浸出造成一定影响。为研究CO_2+O_2中性地浸条件下含矿层砂岩介质对溶解铀的吸附特征,采用取自新疆蒙其古尔铀矿床围岩和含铀浸出液,在实验室开展了不同粒径介质和不同固液比的吸附试验。结果表明,不同粒径介质对铀的平衡吸附量介于11.62～20.28mg/g,铀的平衡吸附量以及吸附率与粒径负相关;不同液固比试验条件的平衡吸附量介于10.07～18.23mg/g,铀的平衡吸附量与液固比正相关,铀的吸附率则与液固比负相关。围岩对铀的吸附动力学特征符合粒内扩散模型。试验结果可以为地浸采铀溶质运移模拟过程中吸附模型及其参数的确定提供依据。     

碱性溶液低浓度镓的回收

某氧化铝厂赤泥除含大量的Fe_2O_3、Al_2O_3和Na_2O外,其Ga_2O_3含量高达96.25mg/kg。采用电解废旧阴极高温还原赤泥分离铁、铝、钠的过程中,除获得铝和钠的高效回收外,Ga_2O_3浸出率高达90.41%,浸出液中Ga_2O_3的浓度为7.19mg/L,具有回收价值。采用树脂离子交换工艺对还原性烧结熟料浸出液中的镓进行富集回收,结果表明,最适宜镓吸附条件为:LSC-700树脂用量0.6g/L、温度(50±0.5)℃、接触时间24h、振荡速率120r/min,镓吸附效率为52.13%;对镓负载树脂采用酸法解吸,镓的平均解吸率为92.29%,解吸溶液含镓平均86.43mg/L,比初次浸出溶液(7.19mg/L)和二次循环浸出溶液(21.62mg/L)分别富集了12倍和4倍。     

电解锰废水中Cr~(6+)、Mn~(2+)的去除方法研究

通过实验研究了还原沉淀-晶种曝气组合工艺去除电解锰废水中Cr6+和Mn2+,并探索了最佳工艺条件.首先以Na2SO3做还原剂将Cr6+转化为Cr3+后再通过化学沉淀法除去,然后采用加入MnO2做晶种曝气氧化去除废水中的Mn2+.结果表明:当Na2SO3投加量为0.5 g/L,还原反应pH值为4,还原反应时间6 min,Cr6+可完全转化为Cr3+.Cr3+在pH值为8时沉淀最完全,出水总铬浓度可从100 mg/L降到0.5 mg/L以下.除铬后,当MnO2投加量为25 g/L,废水pH值为9,曝气10 min,出水Mn2+浓度可从1 000 mg/L降到0.4 mg/L以下.通过以上处理出水总铬和总锰均达到我国《污水综合排放标准(GB8978-1996)》一级要求.     

从贫化电炉渣浮选尾砂中氨浸铜的动力学研究

研究了采用(NH4)2CO3-NH3·H2O体系从湖北大冶某冶炼厂电炉渣浮选尾砂中浸出铜,考察了炉渣粒度、浸出温度、氨水浓度、固液质量体积比、碳酸铵用量、搅拌速度等因素对铜浸出率的影响。试验获得从电炉渣浮选尾砂中浸出铜的最佳条件为:炉渣粒度0～0.045mm,浸出温度80℃,氨水质量浓度70g/L,固液质量体积比1∶10,碳酸铵用量1.5g,搅拌速度500r/min。浸出过程前、后期受固膜扩散控制,浸出中期受扩散与化学反应共同控制。     

CO2+O2地浸采铀强化浸出试验研究

新疆蒙其古尔铀矿床CO2+O2地浸采铀工艺中,铀浓度与HCO3-呈显著的正相关关系,但经过浸出初期后,提高CO2加入量不能有效提升体系HCO3-浓度,而对多数地浸单元的矿化条件而言,HCO3-浓度也尚未达最佳浸出需求。为此在该矿床某采区,采用补加碳酸氢铵和提高CO2加入量相配合的工艺,开展了强化浸出试验。结果表明,强化浸出效果显著,该采区浸出液中HCO3-从850 mg/L提升至1 200 mg/L,单孔铀浓度提升1.73~44.33 mg/L,集合样铀浓度提升8 mg/L。将pH调控在6.2~6.3和降低O2加入量稳定SO42-浓度,能避免强化浸出过程中发生碳酸钙和硫酸钙的沉淀,抽、注流量也并未受到影响。该强化浸出技术在多采区应用取得了良好的浸出效果和经济效益,是对该矿床CO2+O2浸出工艺的进一步优化。     

硫对含草酸钠铝酸钠溶液蒸发排盐的影响

通过添加不同量的硫酸钠和硫化钠,研究硫对含一定浓度草酸钠(Ns)的铝酸钠溶液蒸发排盐的影响。结果表明,当Ns=6g/L时,硫酸钠对铝酸钠溶液中Na_2CO_3、硫盐、Na_2C_2O_4和NaAlO_2的结晶析出均有影响,随着添加量的增加,盐析出率均增大,排盐率也增大,当Ns=6g/L时,排盐率达到92.02%,排盐渣中存在Na_2CO_3、Na_2C_2 O4、NaAlO_2·1.25H_2O、Na_2SO_4以及Na_6CO_3(SO_4)_2、Na_4(SO_4)1.39(CO_3)0.61等结晶复盐;添加硫化钠也可以增加盐析出率与排盐率,但是效果不明显,在当Ns=6g/L时,排盐率仅为71.71%,结晶物相有Na_2CO_3、Na_2C_2O_4、NaAlO_2·1.25H_2O以及Na_2S,Na_2S2O_3,Na_2SO_3等,并不存在结晶复盐;随着硫化钠添加量的增加,抽滤时间增长,增加了排盐的难度,硫化钠滞留在溶液中,继续对生产产生危害,需要引入氧化剂将硫化钠充分氧化为硫酸钠,才能达到良好的强化排盐效果。