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1.
采用二(2-乙基己基)磷酸酯(P204)-磺化煤油萃取体系从高硫酸氰化尾渣矿浆电解液中富集铁离子,重点研究了P204浓度、相比(O/A)、振荡时间、振荡频率及温度等对Fe3+萃取率的影响及其萃取过程。研究表明,在P204体积分数为25%、电解液pH为1.5、温度25℃、O/A=1∶1、振荡时间10 min、振荡频率180r/min的条件下,电解液中Fe3+的单级萃取率可达97.73%以上,饱和萃取容量可达到21.57g/L。Fe3+在有机相中的萃取富集主要归因于其与P204分子结构中羟基的阳离子交换反应以及磷酰基的配位反应,形成的配合物为FeSO4A(HA)3与FeA3(HA)3。在草酸1mol/L、O/A=1∶1、振荡时间10min、振荡频率190r/min的条件下,负载有机相中Fe3+的单级反萃率可达82.64%以上,反萃液中铁主要以[Fe(C2O4)3<...  相似文献   

2.
The adsorption of N2 on a copper ion-exchanged ZSM-5 sample (CuZSM-5) prepared by ion exchange using an aqueous solution of copper propionate, Cu(C2H5COO)2, was examined at room temperature by measuring the FT-IR spectra, adsorption isotherms and heat of adsorption. This sample was found to be extremely efficient in terms of N2 adsorption with regard to both the amount and the energy (i.e., heat) of adsorption, compared with samples prepared by a conventional ion-exchange method using an aqueous solution involving Cu2+ and simple counter ions, Cl or NO3. To clarify the specificity of the newly-prepared sample, the ion-exchange of ZSM-5 with Cu2+ was carried out by employing aqueous solutions involving Cu2+ and various types of counter ions [propionate (C2H5COO), acetate (CH3COO), formate (HCOO), chloride (Cl) and nitrate (NO3) ions]. When the ion exchange was performed by using a Cu(C2H5COO)2 or Cu(CH3COO)2 solution, the Cu2+ species with propionate or acetate ligand (in the monomer state) were ion-exchanged in ZSM-5, as confirmed by the DR, EPR and FT-IR spectra for CuZSM-5. In contrast, Cu2+ species were present in the form of aquo-complexes in samples prepared with other solutions. This distinct difference can be ascribed to the difference in the pKa values of the counter ions; carboxylate ions, with a high pKa value, are inclined to form a complex with Cu2+. Using this newly applied Cu(C2H5COO)2 solution, the present ion-exchange method has the potential to develop new effective materials that possess the specific adsorption and catalytic properties of CuZSM-5.  相似文献   

3.
Complete Ni2+ exchange of a single crystal of zeolite X of composition Na92Si100Al92O384 per unit cell was attempted at 73°C with flowing aqueous 0.05 M NiCl2 (pH=4.3 at 23°C). After partial dehydration at 23°C and ≈10−3 Torr for two days, its structure, now of composition Ni2(NiOH)35(Ni4AlO4)2(H3O)46Si101Al91O384 per unit cell, was determined by X-ray diffraction techniques at 23°C (space group Fd , a0=24.788(5) Å). It was refined using all intensities; R1=0.080 for the 236 reflections for which Fo>4σ(Fo), and wR2=0.187 using all 1138 unique reflections measured. At four crystallographic sites, 45 Ni2+ ions were found per unit cell. Thirty of these are at two different site III′ positions. Twenty of those are close to the sides of 12-rings near O–Si–O sequences, where each coordinates octahedrally to two framework oxygens, to three water molecules which hydrogen bond to the zeolite framework, and to an OH ion. The remaining 10 are near O–Al–O sequences; only three members of a likely octahedral coordination sphere could be found. In addition, two Ni2+ ions are at site I, eight are at site I′, and five are at site II. Forty six H3O+ ions per unit cell, 24 at site II′ and 22 at site II, each hydrogen bond triply to six rings of the zeolite framework. Each of the 22 H3O+ ions also hydrogen bonds to a H2O molecule that coordinates to a site III′ Ni2+ ion. Six of the eight sodalite cages each contain four H3O+ ions at site II′; the remaining two each contains a tetrahedral orthoaluminate anion at its center. Each tetrahedral face of each orthoaluminate ion is centered by a site I′ Ni2+ ion to give two Ni4AlO4 clusters. The five site II Ni2+ ions each coordinate to a OH ion. With 46 H3O+ ions per unit cell, the great tendency of hydrated Ni2+ to hydrolyze within zeolite X is demonstrated. With a relatively weak single-crystal diffraction pattern, with dealumination of the zeolite framework, and with an apparent decrease in long-range Si/Al ordering likely due to the formation of antidomains, this crystal like others treated with hydrolyzing cations appears to have been damaged by Ni2+ exchange and partial dehydration.  相似文献   

4.
王俊  贾庆源  郭瑞丽  张建树 《化工学报》2016,67(10):4282-4289
采用亲水的PAN为成膜材料,制备了掺杂H1.6Mn1.6O4的PAN-H1.6Mn1.6O4锂离子筛膜。通过SEM、Li+静态吸附实验、(NH42S2O8对锂的洗脱实验和卤水中吸附实验,研究了锂离子筛的添加量对PAN-H1.6Mn1.6O4锂离子筛膜结构、Li+吸附-洗脱性能的影响。结果表明,PAN浓度为10%(质量),H1.6Mn1.6O4的添加量为50%(质量)时,PAN-H1.6Mn1.6O4离子筛膜的吸附量为17.45 mg·g-1,达到粉末状吸附量的88.0%。以(NH42S2O8为洗脱剂,当浓度为0.3 mol·L-1、液固比为600:1、时间为12 h时,锂洗脱量为17.23 mg·g-1,锰溶损率仅为1.14%。在含有Na+、K+、Mg2+和Ca2+的罗布泊老卤卤水中,锂离子筛膜对Li+有很高的选择性。在卤水中进行10次吸附与解吸循环,吸附量从11.64 mg·g-1下降到10.94 mg·g-1,吸附容量仅损失6.0%。总体结果表明亲水性载体对H1.6Mn1.6O4吸附容量影响较小,温和的洗脱剂对锂离子筛膜的化学稳定性有利。  相似文献   

5.
钛系锂离子筛具有较高的锂吸附容量和稳定性,对其制备工艺及性能进行改进研究具有重要意义。使用硝酸锂和碳酸锂混合物作为锂源,与二氧化钛在500℃下进行固相反应,生成层状钛酸锂;使用0.2 mol·L -1盐酸对其酸洗24 h,得到了锂离子筛吸附剂;采用X射线衍射、扫描电镜、粒度分析、N 2吸附-脱附方法等,对其性能进行了表征;通过锂离子的吸附实验,确定了吸附和再生性能;探究了该新型吸附剂的锂离子吸附机理。结果表明:吸附过程是单分子层化学吸附;经过改性,离子筛颗粒更加细小,孔体积和比表面积更大,结构完整;在70 mg·L -1的Li +溶液中,吸附量为25.01 mg·g -1,准二级吸附速率常数为0.2762 g·(mg·h) -1,吸附速率较之未改性提高了54.56%;该离子筛对浓度为11.6 mg·L -1的Li +溶液,其锂去除率可以达到99.77%。  相似文献   

6.
The precursor of zirconium oxide is synthesized by the sol-gel method by reacting zirconyi chloride octahydrate (ZrOCl2 8H2O) and citric acid in ammonia solution. The ionized complex compounds (R(COO-+NH4)3) were first formed from the reaction of complex agent (citric acid) and ammonium hydroxide. Zirconyi chloride octahydrate first hydrolyzed to produce zirconium tetranuclear complex molecule [Zr4(OH)8(OH2)l6(—OOC)3R]8+ which subsequently produced a large complex molecule ([Zr4(OH)5(OH2)|6(—OOC)3R)5+ or [Zr4(OH)8(OH2)13(—OOC)3R]5+) through the polymerization of zirconium tetramer with the ionized complex agent. The effect of the reaction conditions on the precursor solution's viscosity and average particle size were investigated in order to understand the kinetics of the reaction. A rational reaction mechanism is proposed satisfactorily to explain the formation and growth of the particles and viscosity of the sol.  相似文献   

7.
Catalytic oxidation of sulfide ions over nickel hydroxides   总被引:2,自引:0,他引:2  
The catalytic sulfide ion oxidation by oxygen to elemental sulfur over β-Ni(OH)2 and LiNiO2 has been studied. As a result of experimental investigation performed, a reaction mechanism is suggested which involves heterogeneous and homogeneous processes. Dioxygen activation in the heterogeneous process proceeds via a redox Ni2+ ↔ Ni3+ transition and participation of OH groups. The active HO2 species thus formed carries on the reaction in homogeneous phase. Nickel hydroxides are promising catalysts for practical application.  相似文献   

8.
Conductivity of molten Mg(NO3)2. 6H2O + NH4NO3 system containing up to 80 mole percent of the latter was measured in the temperature range 320–400 K. Temperature dependence of conductivity exhibited Arrhenian behaviour. Conductivity—composition isotherms were non-linear indicating weak ordering tendencies. Equivalent conductivity data did not obey Markov equation; deviations have been interpreted in terms of the Tobolsky parameter (θ). Constancy of θ indicate that the water of hydration in the system remains with Mg2+ ions and is unaffected by the addition of NH+4 ions.  相似文献   

9.
Layered double hydroxide pillared by Paratungstate A ion, Mg12Al6(OH)36(W7O24)·4H2O, was prepared via anion exchange reaction of the synthetic precursor, Mg4Al2(OH)12TA·xH2O (TA2−=terephthalate), and [W7O24]6− ion. Some physico-chemical properties were measured and the preparation conditions were studied. Trace aqueous organocholorine pesticide, hexachlorocyclohexane (HCH), was totally degraded and mineralized into CO2 and HCl by irradiating a Mg12Al6(OH)36(W7O24)·4H2O suspension in the near UV area. Disappearance of trace HCH follows Langmuir–Hinshelwood first-order kinetics. The model and mechanism for the photocatalytic degradation of HCH on the Mg12Al6(OH)36(W7O24)·4H2O were proposed, indicating that the interlayer space is the reaction field, and that photogeneration of OH√ radicals are responsible for the degradation pathway.  相似文献   

10.
以自养硝化颗粒污泥作为吸附剂,研究了其对铜离子的吸附效果及最佳吸附工艺条件,并探索了其吸附等温线。通过单因素实验研究铜离子浓度、吸附时间、污泥浓度、搅拌速度和温度对吸附效果的影响,最终得出搅拌速度、吸附时间以及污泥浓度对吸附效果有明显影响。在此基础上,通过响应曲面法耦合出吸附的最佳工况点:时间(A)=2.50h,转速(B)=125r/min,污泥量(C)=5250mg/L。在此条件下研究了颗粒污泥的吸附特性及稳定性。结果表明,硝化颗粒污泥在重金属废水中表现出极强的耐受性与稳定性,不同浓度下颗粒化率均维持在93%以上。Langmuir与Freundlich方程动力学拟合结果显示:Langmuir等温方程的拟合度R2Cu=0.999,表明硝化颗粒污泥对于Cu2+属于典型的单分子层吸附,且能描述最大吸附量为Qmax=15.02mg/g。Freundlich等温方程的拟合过程中,相关系数R2Cu=0.969,1/n=0.1305,表明硝化颗粒污泥对Cu2+吸附能力较强;较高的拟合度也在一定程度上表明硝化颗粒污泥对Cu2+的吸附是一个复杂的物理化学过程。  相似文献   

11.
The effect of HClO4 concentration on the rate of electrode processes on a stationary indium amalgam electrode in stirred In(ClO4)3 solutions at constant ionic strength (3 M NaClO4) has been investigated. Alongside with the measurement of polarization curves, the exchange current and the true rate of the anodic process of amalgam dissolution (ia at different potentials (φ) were determined by a radiochemical method. With an increase in the HClO4 concentration, a sharp decrease in the exchange current is observed; at HClO4 concentrations below 0.2 M at constant φ, the ia values are inversely proportional to the HClO4 concentration. The experimental results are expressed by the equation p] ia = k[In][H+]−1 exp (βφF|RT),

where [In] is the concentration of the indium amalgam. The rate of the cathodic process at constant φ also decreases with a decrease in pH. A hypothesis is advanced according to which partially hydrolysed In(H2O)5OH2+ ions, rather than In(H2O)63+ which are predominant in the solution, participate in the electrode process. The OH ions, like some other anions, appear to be capable of facilitating the transfer of electrons between the electrode surface and the reacting particle. An analysis of the results obtained (and of data in the literature) shows that partially hydrolysed metal ions play an essential role in electrode processes.  相似文献   


12.
采用实验方法研究了低成本环境友好型添加剂抗坏血酸(AA)对Fe2+/H2O2体系氧化NO气体及其对体系内H2O2分解的影响,分析了AA对体系氧化NO能力及H2O2分解的影响机制。研究结果表明:AA通过加速Fe3+向Fe2+的转化而促进Fe2+/H2O2体系对NO的氧化。[AA]0:[Fe2+]0对体系氧化NO的能力及H2O2的分解具有重要影响。综合考虑NO氧化脱除量及H2O2消耗量,合理的[AA]0:[Fe2+]0为1/3~1/2。AA的分次添加方式可大幅度提升体系氧化NO气体的能力。研究结果可望为发展基于H2O2为氧化剂的烟气NO绿色氧化技术提供理论基础。  相似文献   

13.
The effect of oxygen concentration on the pulse and steady-state selective catalytic reduction (SCR) of NO with C3H6 over CuO/γ-Al2O3 has been studied by infrared spectroscopy (IR) coupled with mass spectroscopy studies. IR studies revealed that the pulse SCR occurred via (i) the oxidation of Cu0/Cu+ to Cu2+ by NO and O2, (ii) the co-adsorption of NO/NO2/O2 to produce Cu2+(NO3)2, and (iii) the reaction of Cu2+(NO3)2 with C3H6 to produce N2, CO2, and H2O. Increasing the O2/NO ratio from 25.0 to 83.4 promotes the formation of NO2 from gas phase oxidation of NO, resulting in a reactant mixture of NO/NO2/O2. This reactant mixture allows the formation of Cu2+(NO3)2 and its reaction with the C3H6 to occur at a higher rate with a higher selectivity toward N2 than the low O2/NO flow. Both the high and low O2/NO steady-state SCR reactions follow the same pathway, proceeding via adsorbed C3H7---NO2, C3H7---ONO, CH3COO, Cu0---CN, and Cu+---NCO intermediates toward N2, CO2, and H2O products. High O2 concentration in the high O2/NO SCR accelerates both the formation and destruction of adsorbates, resulting in their intensities similar to the low O2/NO SCR at 523–698 K. High O2 concentration in the reactant mixture resulted in a higher rate of destruction of the intermediates than low O2 concentration at temperatures above 723 K.  相似文献   

14.
In metal-free ZSM-5, the decrease in the concentration of Bronsted and Lewis acid sites parallels the increase in the SiO2/Al2O3 ratio. In the presence of residual moisture, the adsorption of small alkanes does not markedly depend on the SiO2/Al2O3 ratio in the range from 30 to 150. The acidity is more important for the adsorption of alkenes (propene) which oligomerize following adsorption. The addition of 5 wt.% of La does not significantly affect the strength of the surface acid sites but does decrease their concentration. It causes a transformation, in a part, of the Bronsted acid sites. These new centers could perhaps be assigned to LaO(OH) or La(OH)2+ species which may be formed on the surface in La-containing ZSM-5. La could exchange only the strongest acidic sites without inducing large changes in their total concentration. La addition has a very small effect on the adsorption of small hydrocarbons. The exchange of the protons by Cu2+ decreases the concentration of Bronsted acid sites. At a sufficient loading of the ZSM-5 by Cu2+, i.e. at an atomic ratio Cu/Al > 1.0, the exchange can almost totally suppress the Bronsted acidity. Another effect of the ion exchange is the suppression of the adsorption capacity of small hydrocarbons due to lowered surface area and internal pore volume. The lowered available internal pore volume also limits the extent of the oligomerization of propene.  相似文献   

15.
研究了氯化铬(CrCl3·6H2O)和氯化镍(NiCl2·6H2O)浓度和存在形式对氯化胆碱-乙二醇(ChCl-EG)低共熔溶剂的黏度和电导率的影响。电喷雾质谱(ESI-MS)分析结果表明,在溶解有CrCl3?6H2O和NiCl2?6H2O 的ChCl-EG(ChCl-EG-NiCl2·6H2O-CrCl3·6H2O)溶液中出现了配阴离子[Cr(H2O)2Cl4]和[Ni(H2O)2Cl4]2-。由此可以推断,Cr3+(或Ni2+)的两个d轨道、4s 和4p轨道发生d2sp3杂化,形成6个等同的杂化轨道,接受6个配体(Cl-和H2O)形成阴离子配合物。该溶液的电导率随温度的升高而增大,随总金属离子浓度的增大而减小。此外,溶液黏度随温度和总金属离子浓度的变化趋势与电导率相反。这主要是由于镍和铬配离子的形成改变了溶液中的离子组成。  相似文献   

16.
Periodic current/potential curves were taken potentiostatically at 30 mV/sec on smooth platinum in 1 N HClO4 with different additions of HCl, HBr, and HI, in the potential range between hydrogen evolution and deposition of oxygen or of the respective halide ion. The effect of increasing halide ion concentration, starting at 10−6 M, on hydrogen adsorption and oxygen adsorption was studied systematically. Impedance measurements were made at 1000 c/s under the same conditions as the measurements of the current/potential curves. It is concluded from the dependence of the double layer capacitance upon the bulk concentration of halide ions in the double layer region that nearly a monolayer of adsorbed ions is present there for 0cCl ≈ 10−2 M, 0cBr ≈ 10−4 M, and 0cHI ≈ 10−5 M. The measurements at larger concentrations, especially for I, show additional effects which are due to the deposition of halides and to the reverse reaction.  相似文献   

17.
以盐湖高锂卤水为原料,采用化学沉淀法,以无水氯化钙作为沉淀剂,脱除卤水中的硫酸根。详细考察了原料配比(钙离子与硫酸根物质量的比)、加料方式、加料时间、反应时间、搅拌转速和反应温度等条件对除硫率的影响,同时重点研究了反应过程中锂的夹带损失率和生成锂的复盐形式。得到除硫的适宜条件:原料配比为1.2,加料方式为正向加料即氯化钙溶液加入卤水中,反应温度为25 ℃,加料时间为24 min,搅拌转速为150 r/min,反应时间为60 min。在该实验条件下卤水中硫酸根的脱除率达到99.02%,锂的夹带损失率达到27.71%;通过扫描电镜可以得到沉淀产物的形貌,通过XRD表征结果可以说明在分离硫酸根的过程中锂离子主要是以Li2SO4·H2O和LiAl2(OH)7(H2O)2的形式夹带损失。  相似文献   

18.
以采用共沉淀法制备的磁性Fe3O4为核,通过硅烷化及酰胺化反应,制备了羧基化磁性Fe3O4复合材料(Fe3O4?SiO2?NH?COOH),通过红外光谱仪(FTIR)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、磁强度计(VSM)和X射线衍射仪(XRD)等对复合材料的结构进行了表征,并对不同作用条件下Fe3O4?SiO2?NH?COOH吸附Pb2+的效果及Fe3O4?SiO2?NH?COOH的重复使用效能进行了研究。结果表明,具有Fe3O4?SiO2?NH?COOH结构的复合材料已被成功被制备,且该材料仍然能够实现快速磁性分离;Fe3O4?SiO2?NH?COOH对Pb2+的静态吸附动力学数据更符合准二阶动力学,吸附时间为100 min、pH=4.5、Fe3O4?SiO2?NH?COOH用量为1.0 g/L时,Fe3O4?SiO2?NH?COOH对Pb2+的最大吸附容量为208.7 mg/g,且Langmuir方程更能描述该吸附等温过程;Fe3O4?SiO2?NH?COOH对Pb2+的吸附是吸热过程;Fe3O4?SiO2?NH?COOH对Pb2+的吸附量随时间延长先增加后趋于稳定,随pH值的增加先增加后减小;相比于一价阳离子,溶液中二价Ca2+、Mg2+的存在对吸附反应具有一定抑制作用;Fe3O4?SiO2?NH?COOH吸附Pb2+后可洗脱再生,连续重复使用6次后对Pb2+的去除率仍大于50 %。  相似文献   

19.
针对锰基锂离子筛容量发挥不充分、使用寿命短的问题,以电解二氧化锰、氯化锂及无水氯化铝为原料,采用水热法合成了铝原子掺杂锰基离子筛前驱体,经酸洗脱附锂离子后得到锰基锂离子筛H1.6(Mn1-x Al x1.6O4。扫描电镜结果表明,铝原子掺杂后,样品呈均匀光滑的纳米片多面体形貌,进一步的吸脱附等温线分析显示,样品的比表面积显著提高。锂离子吸脱附特性研究结果表明,Li1.6(Mn0.7Al0.31.6O4具有最佳的吸附提锂性能,锂离子溶液初始质量浓度为80 mg/L时,吸附容量为32.32 mg/L,5次循环提锂后,锂离子吸附容量可保持为初始吸附容量的95%。这些结果表明,结晶性好、比表面积大的纳米多面体锰基锂离子筛,吸附容量大、结构稳定性好,可为当前盐湖卤水中锂资源的开发和工艺优化提供技术参考。  相似文献   

20.
江洪波  毋少庚 《化工进展》2015,34(4):1088-1092,1121
采用桥联茂金属催化体系rac-Et(1-Ind)2ZrCl2/Al(iBu)3/[Me2NHPh]+[B(C6F5)4]-催化1-癸烯聚合,考察了茂金属浓度、Al/Zr摩尔比、B/Zr摩尔比、温度、反应时间对反应转化率、黏度和摩尔质量的影响.当反应条件为1-癸烯20mL、甲苯20mL、Zr/烯摩尔比8×10-5、Al/Zr摩尔比80、B/Zr摩尔比1.5、温度80℃、反应时间1h时,转化率达到96.2%.采用13C NMR和1H NMR表征了产物的结构,优化条件下所得的聚合产物具有高黏度指数(259)和低分子量分布(2.088),可作为理想的润滑油基础油的原料.  相似文献   

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