P204-TBP协萃体系从高浓度硫酸钴溶液中萃取分离Mn和Ca

针对从高浓度硫酸钴料液中分离钴锰相关研究较少的问题,采用P204与TBP形成的混合萃取体系从工业高浓度硫酸钴溶液中萃取分离Ca~(2+)、Co~(2+)、Mn~(2+),考察了萃取平衡pH、TBP体积分数、萃取相比、有机相皂化度对Ca~(2+)、Co~(2+)、Mn~(2+)萃取率的影响,并通过对有机相的洗涤来分离Ca~(2+)、Co~(2+)、Mn~(2+)。结果表明,以25%P204+10%TBP为萃取剂,65%煤油为稀释剂,在水相平衡pH为3.7,皂化率为45%和相比O/A为1∶2的条件下,Ca~(2+)、Co~(2+)及Mn~(2+)的萃取率分别为88.1%、69.8%和19.3%;再以30g/L硫酸锰溶液为洗涤液,在水相平衡pH为3.5、相比O/A为20∶1、洗涤级数为4的洗涤条件下,负载有机相中Mn~(2+)浓度为7.14g/L,Ca~2和Co~(2+)浓度分别仅为0.05g/L和0.14g/L。该工艺有效实现了高浓度硫酸钴溶液中钴、锰、钙的分离。     

含Ni~(2+),Fe~(3+),Mg~(2+)的硫酸盐溶液萃取分离Cu~(2+)

采用Lix984作萃取剂,煤油作稀释剂混合而成溶液萃取的有机相,从含Ni~(2+),Fe~(3+),Mg~(2+)离子的硫酸盐溶液中萃取分离Cu~(2+).实验结果表明,在一定范围内,铜萃取率随萃取剂浓度的升高、相比的增加、萃取时间的延长、初始水相pH值的增加、萃取温度的升高以及搅拌时间的延长而增加.本实验的优化条件为萃取剂体积分数达60%,相比为O∶A=2∶1,萃取时间为16 min,萃取初始水相pH值为2.5,萃取温度在25~45℃之间,搅拌速度为240 r/min.在最佳条件下,铜萃取率高达95.55%.Fe~(3+)萃取率为8.82%,Ni~(2+)的萃取率为5.47%,Mg~(2+)的萃取率为2.36%.从而达到Cu~(2+)与其它金属离子有效分离的效果.     

料液中添加NH_4Cl对Sm~(3+)和Zn~(2+)萃取性能的影响

采用1.5 mol/L P507-煤油为有机相,以SmCl_3和ZnCl_2的混合溶液作为料液,改变料液中添加NH4Cl浓度、料液酸度、Zn~(2+)浓度、有机皂化度、相比、混合时间,进行了Sm~(3+)和Zn~(2+)的萃取分离研究。结果表明,萃取分离Sm~(3+)和Zn~(2+)最佳的工艺参数为,有机皂化度为0.54 mol/L、料液中添加3 mol/L的NH_4Cl、料液酸度为0.15 mol/L、萃取相比O/A为2.5∶1以上,混合时间为4 min,Sm~(3+)和Zn~(2+)的最大分离因素βSm/Zn达到39.31。     

用P204从不锈钢酸洗污泥浸出液中萃取重金属试验研究

研究了用P204作萃取剂从不锈钢酸洗污泥浸出液中萃取分离重金属,考察了萃取剂皂化率、振荡时间、稀释剂、相比、料液初始pH、温度等对重金属萃取效果的影响。结果表明:在有机相皂化率75%、相比1/1、料液初始pH=3.0、以260#溶剂油为稀释剂、萃取5 min条件下,铬、镍、铁萃取率分别达87.93%、14.19%和59.83%,分离系数β(Cr/Ni)=44.12,β(Cr/Fe)=4.90,铬与镍、铁得到分离;用稀硫酸反萃取铬,效果较好。     

用N235从热镀锌酸洗废液中萃取分离锌铁

研究了用N235从热镀锌盐酸酸洗废液中萃取Zn~(2+)、Fe~(3+)和Fe~(2+),考察了废液中Zn~(2+)质量浓度、萃取时间、萃取剂体积分数、相比(V_o/V_a)、温度及助萃剂Cl~-浓度对金属离子萃取率及分离系数的影响。结果表明:在有机相组成为50%N235+50%260~#溶剂油、V_o/V_a=1/1、室温(24℃±1℃)条件下,废液中加入适量Cl~-,萃取5 min, Zn~(2+)单级萃取率为83.06%,Zn/∑Fe分离系数达41.90;经过3级逆流萃取,Zn~(2+)萃取率达94.8%,总铁萃取率为16.52%,锌/铁分离效果较好。通过萃取前后对有机相的红外光谱分析,确定N235萃取金属离子的机制为金属配阴离子与胺盐中的氯离子发生交换形成疏水性离子缔合体而进入有机相。     

萃取法回收黄钠铁矾渣浸出液中的铜镍

黄钠铁矾渣用浓氨水分解,浸出液经盐酸处理后,用LIX984萃取剂和磷酸二异辛酯(P204)分别萃取铜和镍。探讨了原料液中pH值、有机相中萃取剂体积分数、相比(O/A)、铜、镍离子浓度、反萃取相比(O/A)等萃取条件对铜镍萃取率的影响。结果表明:LIX984萃取剂体积分数为20%、pH值为2.5、相比(O/A)为1∶1、Cu~(2+)和Ni~(2+)浓度均约为5 g/L,Cu~(2+)的萃取率约为92%,反萃取相比(O/A)为1∶1,铜的反萃取率高达99%,调节萃余液中pH值约为5.5时,P204对镍的萃取率超过98%,镍的反萃取率约为91%。LIX984和P204萃取剂对铜和镍的萃取效果显著,能够选择性地萃取回收黄钠铁矾渣浸出液中的铜和镍。     

用微乳液从废催化剂浸出液中分离铝

研究了用皂化P507从废催化剂浸出液中萃取铝,再经硫酸反萃取、蒸发结晶制备水合硫酸铝,考察了萃取、反萃取过程中几种主要因素对Al~(3+)回收的影响。结果表明:以皂化率45%的25%P507+10%正戊醇+65%260~#溶剂油为萃取剂,在料液中Al~(3+)、Mg~(2+)、Ni~(2+)质量浓度分别为2 g/L、50 mg/L和10 mg/L,料液pH=1.5,萃取相比(V_o/V_a)=1/1,萃取时间3 min条件下,Al~(3+)、Mg~(2+)、Ni~(2+)萃取率分别为99.35%、2.83%、0.56%;负载铝的有机相用硫酸反萃取,在硫酸溶液浓度3 mol/L、反萃取相比(V_a/V_o)=1/1条件下,Al~(3+)反萃取率为95.13%;该反萃取液以蒸发结晶法制备水合硫酸铝,其质量符合HG/T 2225—2010标准Ⅰ类产品要求。     

锌与钐的萃取分离工艺研究

采用1.5 mol/L P507-煤油为有机相,以氯化钐和氯化锌的混合溶液作为料液,研究了料液酸度、Zn2+浓度、有机皂化度、相比、混合时间等对Sm3+和Zn2+萃取分离的影响,得到了萃取分离Sm3+和Zn2+的最佳工艺参数:有机皂化度为0.54 mol/L,料液酸度为0.15 mol/L,萃取相比(O/A)为3:1,混合时间为4 min以上。Sm3+和Zn2+的分离因素βSm/Zn达到12。     

用P507-Cyanex272协萃体系从电解锰合格液中萃取分离锰镁钙

研究了采用P507-Cyanex272协萃体系从电解锰合格液中萃取分离锰镁钙，考察了水相pH、有机相皂化率、萃取相比、萃取剂体积分数、萃取温度、混合时间及Cyanex272添加量对锰、镁、钙离子萃取率的影响，并对负载有机相进行洗涤、反萃取分离去除钙镁杂质。结果表明：在水相pH=4.5、有机相皂化率50%、萃取相比V_o/V_a=2.5/1、萃取剂体积分数30%、萃取温度35℃、混合时间5 min、Cyanex272占比60%条件下，锰、镁、钙萃取率分别为64.28%、15.77%和16.24%;负载有机相分别用0.03 mol/L稀硫酸溶液和30 g/L硫酸锰溶液进行两段洗涤，再以1 mol/L硫酸反萃取，反萃取液中锰、镁离子质量浓度分别为52.57 g/L和0.27 g/L,反萃取液再经高纯碳酸锰中和—协同萃取—反萃取，可满足电池级硫酸锰生产要求。     

P204+P507对钴浸出液协同萃取除钙锰铜锌

针对分步萃取法萃取钴工艺流程繁杂、萃取级数较多的问题,采用P204+P507为复配萃取剂从工业硫酸钴浸出液中一次分离出Zn2+、Ca2+、Mn2+、Cu2+等。探究了平衡pH、复配萃取剂配比、萃取相比O/A、有机相皂化率等对元素萃取率的影响。结果表明：以28%P204+7%P507为复配萃取剂,65%溶剂油为稀释剂,在有机相皂化率为50%、萃取平衡pH=3.57、相比O/A=2的条件下,Zn2+、Ca2+、Mn2+、Cu2+的单级萃取率分别达到99.97%、94.65%、88.42%、87.18%,Co2+萃取率仅有17.42%。后续使用1.5 mol/L硫酸在反萃相比O/A=20、两次洗涤条件下可以将99%的钴洗涤下来。     

Coordination geometries of selected transition metal ions (Co2+, Ni2+, Cu2+, Zn2+, Cd2+, and Hg2+) in metalloproteins

In order to determine preferred coordination geometries of six divalent cations (Co2+, Ni2+, Cu2+, Zn2+, Cd2+, and Hg2+), two sources of experimental data were exploited: Protein Data Bank and Cambridge Structural Database. Metal-binding sites of approximately 100 metalloproteins and 3000 smaller transition metal complexes were analyzed and classified. The correlation between the geometries of small-molecule crystal structures and the metal-binding sites in metalloproteins was investigated. The abundance of amino acid residues participating in coordination metal-protein bonds of metalloproteins was evaluated. From the performed analysis it follows that the octahedral arrangement is preferred by Co2+ and Ni2+, tetrahedral by Zn2+, square planar by Cu2+, and linear by Hg2+. Cadmium (II) cation tends to bind in both tetrahedral and octahedral arrangements and single coordination geometry cannot be unambiguously ascribed to it.     

Mg~（2＋）,Ca~（2＋）,Ba~（2＋）离子部分取代对SrAl_2O_4：Eu~（2＋）,Dy~（3＋）晶体结构和发光性能的影响

采用高温固相反应法制备了Sr0.9M0.1Al2O4：Eu2＋,Dy3＋（M=Mg,Ca,Ba）长余辉发光材料,并对其晶体结构、光谱性质、余辉特性进行了分析.X射线衍射测试结果表明,Mg2＋,Ca2＋,Ba2＋离子部分取代SrAl2O4基质中的Sr后,基质晶体结构并没有发生改变.光谱测试结果表明,Mg2＋,Ca2＋,Ba2＋取代后发光材料的激发光谱都是一个从250~450 nm范围内的宽激发带,在266nm,320nm,360nm,416 nm处各有一个激发峰.发射光谱中Mg2＋和Ba2＋的取代使波长出现蓝移,而Ca2＋的取代使波长出现红移.余辉测试结果表明,Ca2＋取代后的余辉时间长于Mg2＋和Ba2＋的取代.     

The effects of Mg2+, Mn2+, Zn2+, and Al3+ on the nickel deposit during electrowinning from sulfate bath

The presence of impurities like Mg²⁺, Mn²⁺, Zn²⁺, and Al³⁺ during electrowinning of nickel shows several effects. The effects include current efficiency, deposit quality, purity, crystallographic orientation, surface morphology, and polarization behavior. Addition of the impurities did not change the current efficiency significantly but did change the quality and purity of the electrodeposited nickel. Based on the quality of the deposits obtained, the tolerance limits of these impurities in nickel bath were obtained. Although no deviation of nickel structure from fee was observed, the peak height values for different orientations changed with all of the impurities and the values varied with impurity concentration. The surface morphologies of electrodeposited nickel in the presence of impurities also showed changes. The potentiodynamic scan curves for nickel deposition showed deviations in the presence of all the impurities studied. Based on the results, an attempt was made to correlate the various effects.     

Ni2+、Cu2+、Zn2+对氧化亚铁硫杆菌氧化 活性影响

为研究金属离子对氧化亚铁硫杆菌（Acidithiobacillus ferrooxidans,At.f）氧化活性的影响,通过测定经初步驯化的At.f菌在不同初始pH下的生长活性,开展不同浓度梯度的Ni2+、Cu2+、Zn2+及三种金属离子共存时对At.f菌的氧化活性影响的试验。结果表明,当初始pH为1.8时,At.f菌生长活性最好,且低浓度的Ni2+、Zn2+对At.f菌氧化活性影响较小,对两种金属离子的耐受浓度均在20 g/L以上;而该细菌对Cu2+比较敏感,当Cu2+浓度为2.5 g/L时,菌株的生长活性明显下降,特别是10 g/L时,对At.f菌的氧化能力有显著的抑制作用。三种金属离子同时存在时对At.f菌氧化活性的影响大于单一金属离子,当三种金属离子的浓度均为2.5 g/L时,在48小时内对At.f菌的氧化能力有显著的抑制作用,当三种金属离子的浓度均为5 g/L时,80小时时菌株对Fe2+的氧化率极低,说明At.f菌需要经过多种金属离子共存驯化培养后才能更好地运用于多金属复杂矿物的处理。     

Preparation and Long Persistence Red Luminescence of M0.2Ca0.8TiO3∶Pr3+(M=Mg2+,Sr2+,Ba2+,Zn2+)

M0.2Ca0.8TiO3∶Pr3 (M=Mg2 , Sr2 , Ba2 , Zn2 ) long persistence red phosphors were prepared by solid state reaction. The influence of the partially replacing Ca2 in CaTiO3 with Mg2 , Sr2 , Ba2 , Zn2 on the excitation spectra, the emission spectra and the long persistence properties were studied. The results suggest that certain quantity of Mg2 , Sr2 , Ba2 , Zn2 which partially replace Ca2 can enhance the luminescent intensity and prolong the afterglow persistence of the samples. The intensity of Mg0.2Ca0.8TiO3∶Pr3 is above all of the samples. Take Mg0.2Ca0.8TiO3∶Pr3 as the basic sample, the influence of Pr3 concentrations(C(Pr3 )) on the long afterglow properties were also studied. The results suggest that when the C(Pr3 ) is 0.10%(mol fraction) the intensity of the sample is the highest. The excitation spectra of all these samples show broad band spectra ranging from 300～500 nm peaking at about 342 nm. The emission spectra also exhibit a broad band peaking at 613 nm(CaTiO3∶Pr3 is 612 nm). XRD research indicates that the crystalline phases change due to the replacement of divalent metal ions.The research on the thermoluminescence spectra of Mg0.2Ca0.8TiO3∶Pr3 indicates that the peak is at 107.35 ℃ and the depth of the trap energy is about 0.852 eV.