用海藻类生物吸附剂去除废水中的重金属离子——一种经济型新技术

Heavy metal pollution from industrial wastewater is a worldwide environmental issue. Biosorption of heavy metals by using biosorbents derived from various types of biomass has been shown to be effective for the uptake of heavy metal ions. In this study, biosorbents derived from the biomass of a group of marine macroalgae were used for the removal and recovery of heavy metal ions from aqueous solutions. Results indicated that the biosorbents have high uptake capacities and affinities for a number of heavy metal ions. The uptake capacities of the biosorbents were in the range of 1.0 to 1.5mmol·g-1 for divalent heavy metal ions. The kinetics of the uptake process was fast and the process can be used in both batch and fixed-bed operations. It appears that the biosorption process by using biosorbents from marine macroalgae can be an efficient and cost effective technology for the treatment of heavy metal containing wastewater.     

铟、镓、铊金属离子通过色谱纤维支撑固态膜的传递行为(英文)

The transport of metal ions of indium, gallium and thallium from source solution to receiving phase through the chromatographic fiber supported solid membrane in the acetylacetone (HAA) containing mixed solvent system has been explored. The fibers supported solid membranes were prepared with chemical synthesis from cellulose fibers and citric acid with the carboxylic acid ion exchange groups introduced. The experimental variables, such as concentration of metal ions (10-2 to 10-4 mol·L-1) in the source solu...     

基于硫酸钙固体燃料化学链气化过程制备合成气的研究(英文)

Chemical-looping gasification (CLG) is a novel process for syngas generation from solid fuels,sharing the same basic principles as chemical-looping combustion (CLC).It also uses oxygen carriers (mainly metal oxide and calcium sulfate) to transfer heat and oxygen to the fuel.In this paper,the primary investigation into the CLG process with CaSO4 as oxygen carrier was carried out by thermodynamic analysis and experiments in the tube reactor.Sulfur-contained gas emission was mainly H2S rather than SO2 in the CLG process,showing some different features from the CLC.The mass and heat balance of CLG processes were calculated thermodynamically to determinate the auto-thermal operating conditions with different CaSO4/C and steam/C molar ratios.It was found that the CaSO4/C molar ratio should be higher than 0.2 to reach auto-thermal balance.The effect of temperature on the reactions between oxygen carrier and coal was investigated based on Gibbs free energy minimum method and experimental results.It indicated that high temperature favored the CLG process in the fuel reactor and part of syngas was consumed to compensate for auto-thermal system.     

分子动力学模拟研究盐离子对十二烷基硫酸钠胶束溶液中亲水亲油协调机制的影响

The presence of salt has a profound effect on the size, shape and structure of sodium dodecyl sulfate (SDS) micelles. There have been a great number of experiments on SDS micelles in the presence and absence of salt to study this complex problem. Unfortunately, it is not clear yet how electrolyte ions influence the structure of micelles. By describing the compromise between dominant mechanisms, a simplified atomic model of SDS in presence of salt has been developed and the molecular dynamics (MD) simulations of two series of systems with different concentrations of salt and charges of ion have been performed. Polydispersity of micelle size is founded at relatively high concentration of SDS and low charge of cation. Although the counter-ion pairs with head groups are formed, the transition of micelle shape is not observed because the charge of cation is not enough to neutralize the polar of micelle surface.     

菌丝体-甲壳素水处理剂对重金属离子吸附性能的研究

The adsorption properties of chitin adsorbent from mycelium of fermentation industries for the removal of heavy metal ions were studied.The result shows that the chitin adsorbent has high adsorption capacity for many heavy metal ions and Ni^2 in citric acid.The influence of pH was significant:When pH is higher than 4.0,the high adsorption capacity is obtained.otherwise H^ ion inhibits the adsorption of heavy metal ions.The comparison of the chitin adsorbent with some other commercial adsorbents was made,in which that the adsorption behavior of chitin adsorbent is close to that of commercial cation exchange adsorbents,and its cost is much lower than those commercial adsorbents.     

L-瓜氨酸酶法制备中精氨酸脱亚氨酸酶的活性与稳定性研究

A novel Enterococcus faecalis strain designated N J402 was found with high activity of arginine deiminase （ADI）. The optimum condition for catalytic activity was determined in terms of temperature （about 40℃）, thermostability （available 37℃） and pH （6-7）. The effects of substrate and product concentration were studied. The effects of various metal ions added in reaction mixtures on the biocatalyst were investigated and ADI of N J402 was found to exhibit Co^2＋ dependence, different from previous reports. Surfactant, cetyl trimethyl ammonium bromide, was one of the most important keys for producing L-citrulline. The enzyme in resting cells possessed the quality of high stability for reuse.     

Development of barium@alginate adsorbents for sulfate removal in lithium refining

The demand for lithium has been steadily growing in recent years due to the boom of electric cars.High purity lithium is commonly used in the manufacture of battery grade lithium electrolyte.Sulfate residuals originating from acid leaching of lithium ores must be limited to below 20 mg·L^?1 during refining.There are methods to remove sulfate such as membrane processing and chemical precipitation using barium salts.However,membrane separation is unable to achieve the required purity while chemical precipitation often causes secondary contamination with barium and requires extra filtration processes that lead to increased processing costs.In this study,we developed a polymeric matrix entrapped with barium ions as a novel adsorbent to selectively adsorb sulfate in aqueous solutions.The adsorbent was prepared by dropwise injection method where alginate droplets were crosslinked with barium to form hydrogel microcapsules.In a typical scenario,the microcapsules had a diameter of 3 mm and contained 5 wt-%alginate.The microcapsules could successfully reduce sulfate concentration in a solution from 100 to 16 mg·L^?1,exceeding the removal target.However,the microcapsules were mechanically unstable in the presence of an excess amount of sulfate.Hence,calcium ions were added as a secondary crosslinking agent to improve the integrity of the microcapsules.The two-step Ca/Ba@alginate microcapsules showed an exceptional adsorption performance,reducing the sulfate concentration to as low as 0.02 mg·L^?1.Since the sulfate selective microcapsules can be easily removed from the aqueous system and do not result in secondary barium contamination,these Ca/Ba@alginate adsorbents will find applications in ultra-refining of lithium in industry.     

Ghezeljeh nanoclay as a new natural adsorbent for the removal of copper and mercury ions:Equilibrium,kinetics and thermodynamics studies

Heavy metal determination was carried out by applying the solid phase extraction (SPE) method in batch mode followed by atomic absorption spectroscopy (AAS) and inductively coupled plasma atomic emission spectrosco-py (ICP-AES) from aqueous solutions using Ghezeljeh montmoril onite nanoclay as a new natural adsorbent. The Ghezeljeh clay is characterized by using Fourier Transform Infrared (FT-IR) Spectroscopy, Scanning Electron Mi-croscopy–Energy Dispersive Spectrometry (SEM–EDS) and X-ray Diffractometry (XRD) and X-ray Fluorescence (XRF). The results of XRD and FT-IR of nanoclay confirm that montmoril onite is the dominant mineral phase. Based on SEM images of Ghezeljeh clay, it can be seen that the distance between the plates is Nano. The effects of varying parameters such as initial concentration of metal ions, pH and type of buffer solutions, amount of ad-sorbent, contact time, and temperature on the adsorption process were examined. The effect of various interfer-ing ions was studied. The adsorption data correlated with Freundlich, Langmuir, Dubinin–Radushkevich (D–R), and Temkin isotherms. The Langmuir and Freundlich isotherms showed the best fit to the equilibrium data for Hg(I ), but the equilibrium nature of Cu(II) adsorption has been described by the Langmuir isotherm. The kinetic data were described with pseudo-first-order, pseudo-second-order and double-exponential models. The adsorp-tion process follows a pseudo-second-order reaction scheme. Calculation ofΔG0,ΔH0 andΔS0 showed that the nature of Hg(II) ion sorption onto the Ghezeljeh nanoclay was endothermic and was favored at higher temper-ature, and the nature of Cu(II) ion sorption was exothermic and was favored at lower temperature.     

Studies on batch adsorptive removal of cadmium and nickel from synthetic waste water using silty clay originated from Balochistan–Pakistan

The potentials of silty clay(SC), acquired from Chaman, Balochistan, were investigated as adsorbent for Ni(Ⅱ)and Cd(Ⅱ) removal from contaminated media. The influence of different operating factors like dose, pH, temperature, and time of contact was explored, and optimum values were noted under batch adsorption method. Isothermal study was conducted with varying concentrations of solutions on optimized conditions and different adsorption models i.e., Langmuir, Freundlich, Temkin and Dubinin–Radushkevich(D–R) isotherm, which were employed to interpret the process. The isothermal data of both Ni(Ⅱ) and Cd(Ⅱ) were well fitted to Langmuir isotherm suggesting the formation of monolayer of metal ions on silty clay. The values of adsorption capacity noted for Ni(Ⅱ) and Cd(Ⅱ) were 3.603 mg·g~(-1) and 5.480 mg·g~(-)1, respectively. Kinetic studies affirmed that pseudo second order(PSO) kinetics was being obeyed by the removal of Ni(Ⅱ) and Cd(Ⅱ). Thermodynamic variables like free energy change(ΔG°), enthalpy change(ΔH°) and entropy change(ΔS°) were calculated. The negative value of ΔG° and the positive values of ΔH° and ΔS° unfolded that the removal process of both metal ions of by SC was spontaneous, endothermic and feasible.     

石灰乳中和模拟酸性废水形成的二水硫酸钙的晶粒形貌与粒度分布

实验研究了各工艺参数及废水中Mg2+与Fe3+主要杂质离子对石灰乳中和模拟酸性废水形成的二水硫酸钙晶体形貌与大小的影响. 结果表明,反应温度是主要影响因素,当其从25℃提高至70℃时,硫酸钙晶体形貌从片状和针状向棒状转变;而搅拌转速、石灰乳浓度、石灰乳加入速度对结晶过程的影响较不明显. 废水中Mg2+和Fe3+离子对硫酸钙晶体生长有抑制作用,浓度越大,抑制作用越强,Mg2+浓度达1945 mg/L时晶体由片状转变为棒状. 石灰乳二段中和模拟工业酸性重金属废水,得到团聚的针状硫酸钙晶体,废水达标排放.     

金属离子对水热法制备半水硫酸钙晶须的形貌及粒径的影响

以二水硫酸钙为原料,采用水热法制备了半水硫酸钙晶须。通过单因素实验得出制备半水硫酸钙晶须的较优工艺条件为：反应温度120℃、料浆质量分数2%、反应时间2h、搅拌速度200r/min,此时所得晶须产物平均直径2.4μm,长径比103.9,晶须呈长针状、规则统一,分散性好。探讨了K⁺、Mg²⁺、Cu²⁺、Fe³⁺、Al³⁺对较优工艺条件下制备的半水硫酸钙晶须形貌及粒径的影响,结果表明：金属离子对晶须产物形貌及粒径有显著影响。其中低浓度的Mg²⁺、Cu²⁺有助于获得小直径、高长径比的晶须产物;Al³⁺、Fe³⁺对晶须的生长有较强的抑制作用,特别是低浓度的Al³⁺、Fe³⁺使得晶须的形貌发生明显的变化,导致长径比较低;除K⁺外,金属离子浓度越高,所得晶须产物直径越大,长径比越小,并发生团聚现象,晶须由针状变为短棒状,分散性变差。同时探讨了金属离子的作用机理。     

杂质对石膏晶须制备的影响

探讨了Mg2+、Al3+和Fe3+杂质对硫酸与氯化钙反应生成的硫酸钙晶须的影响。研究表明,当温度由80 ℃升温到102 ℃时,产品由二水硫酸钙晶须转变为半水硫酸钙晶须;搅拌速度、反应物浓度、反应时间对晶须的形成影响不显著。Mg2+、Al3+和Fe3+对硫酸钙晶须的生长均有抑制作用,相同浓度下,抑制能力为Fe3+>Al3+>Mg2+;低浓度的Fe3+或高浓度的Al3+能使得晶须的形貌发生明显的变化;在全离子的作用下,晶须形貌由针状变为雪花状,并在其表面有絮状附着物。     

膜结晶处理高浓度Na+、Mg2+//Cl——H2O溶液的结晶调控

利用真空膜蒸馏-结晶耦合技术处理多元高盐废水(Na⁺、Mg²⁺//Cl^--H₂O),回收纯水和高品质NaCl晶体产品,考察不同操作温度和不同无机盐离子浓度对膜蒸馏性能和NaCl晶体产品性质调控作用。结果表明随着温度升高导致饱和蒸气压增大,增大了跨膜压差,膜的渗透通量逐渐升高;随着溶液中Mg²⁺浓度的逐渐升高,膜的渗透通量呈下降的趋势,主要是由于水的质量分数下降和溶液黏度增加;膜蒸馏过程中,通过对比实验,分析了疏水微孔膜表面在膜蒸馏操作条件下表面晶体颗粒沉积的程度,证实了使用的中空纤维膜性能稳定,重复使用20次后仍能保持稳定通量;操作温度为65℃时,不同离子浓度的饱和原料液(MgCl₂质量占NaCl和MgCl₂总质量的0%、5.0%和10.0%)得到NaCl晶体产品平均粒径分别为91.04、91.38和122.56 μm,粒度分布的变异系数C.V.值分别为28.78、30.63和36.77,粒径分布集中,表面相貌平整,呈完美的立方体形态,没有团聚现象;同时,膜蒸馏得到的水纯度较高,电导率均小于5 μS?m^-1,采用选择性溶剂乙醇洗涤后的NaCl晶体产品纯度均大于98.15%。综上,通过膜蒸馏过程中渗透通量和膜界面的有效调控,在适宜的操作温度和较低的Mg²⁺含量下,膜蒸馏结晶过程从多元高盐废水(Na⁺、Mg²⁺//Cl^--H₂O)控制分离获得纯度较高、表面形貌完好、粒度均一的NaCl晶体产品。这一研究将为综合治理多元无机高盐废水,实现废水的近零排放和无机盐资源回用开拓新的思路。     

硫酸锌溶液脱除钙镁试验及生产应用

某硫酸锌生产厂,由于原料氧化锌矿中钙镁含量较高,用硫酸浸出后的硫酸锌溶液中钙镁含量也较高,导致生产的硫酸锌产品钙镁含量偏高,主含量偏低,影响了硫酸锌产品质量。对氢氟酸沉淀法脱除硫酸锌溶液中的钙镁离子进行了试验研究及生产应用。用氢氟酸作为沉淀剂,在较低温度和较高pH条件下可有效脱除硫酸锌溶液中的钙镁离子,并能控制氟在溶液中的累积,使制得的硫酸锌产品质量得以提高。     

Investigation of solution chemistry to enable efficient lithium recovery from low-concentration lithium-containing wastewater

In the production of lithium-ion batteries (LIBs) and recycling of spent LIBs, a large amount of low-concentration lithium-containing wastewater (LCW) is generated. The recovery of Li from this medium has attracted significant global attention from both the environmental and economic perspectives. To achieve effective Li recycling, the features of impurity removal and the interactions among different ions must be understood. However, it is generally difficult to ensure highly efficient removal of impurity ions while retaining Li in the solution for further recovery. In this study, the removal of typical impurity ions from LCW and the interactions between these species were systematically investigated from the thermodynamic and kinetics aspects. It was found that the main impurities (e.g., Fe³⁺, Al³⁺, Ca²⁺, and Mg²⁺) could be efficiently removed with high Li recovery by controlling the ionic strength of the solution. The mechanisms of Fe³⁺, Al³⁺, Ca²⁺, and Mg²⁺ removal were investigated to identify the controlling steps and reaction kinetics. It was found that the precipitates are formed by a zero-order reaction, and the activation energies tend to be low with a sequence of fast chemical reactions that reach equilibrium very quickly. Moreover, this study focused on Li loss during removal of the impurities, and the corresponding removal rates of Fe³⁺, Al³⁺, Ca²⁺, and Mg²⁺ were found to be 99.8%, 99.5%, 99%, and 99.7%, respectively. Consequently, high-purity Li₃PO₄ was obtained via one-step precipitation. Thus, this research demonstrates a potential route for the effective recovery of Li from low-concentration LCW and for the appropriate treatment of acidic LCW.     

柴达木盆地南翼山背斜构造区卤水自然蒸发实验

柴达木盆地南翼山背斜构造区卤水属高钙、低镁的氯化钙型卤水,微量元素硼、锂、锶、碘等含量相对较高,具有较高的综合利用价值。选取南翼山背斜构造区约3 000 m处深层卤水在自然状态下蒸发结晶,分析各种离子在固、液相中的分布规律、盐类结晶规律、结晶形态及微量离子的富集规律。结果表明:在室外自然状态下蒸发时,析出的盐中发现了不常见的异性结构的石盐、钾石盐和疑似K（NH₄）Mg₂Cl₆·12H₂O的类光卤石;石盐阶段和钾石盐阶段析盐规律符合Na⁺,K⁺,Mg²⁺//Cl^-—H₂O 相图,钾石盐、光卤石、南极石阶段符合K⁺,Na⁺,Ca²⁺,Mg²⁺//Cl^- —H₂O体系25 ℃简干图;微量离子中,Li ⁺、Br^-、I^-一直富集,其他离子在蒸发后期有不同程度的析出,三氧化二硼可以富集至18.77 g/L,Li⁺最高可以富集至6.520 g/L。蒸发所得的钾混盐是提钾优质原料,实验结果可以为后期综合利用提供参考。     

盐酸法磷酸萃取相的洗涤和磷酸反萃取过程初探

研究了从以磷酸三丁酯（TBP）为主的萃取相中反萃取磷酸的过程,考察了一步法流程（以硫酸溶液通过沉淀反应去除磷酸萃取有机相中氯化钙的同时反萃取磷酸）以及二步法流程（先以硫酸沉淀反应去除氯化钙,后用去离子水反萃取磷酸）所得的反萃磷酸的净化效果。结果表明,采用一步法时,反萃取磷酸的品质受到硫酸钙溶解平衡的影响,钙含量较高;而采用二步法时,反萃磷酸中氯化钙的质量分数可降低至0.002 7%以下,n（磷酸）/n（钙离子）提升了65倍以上,但有机相中磷酸的洗损为20%左右;利用聚焦光反射测量技术（FBRM）对洗涤过程中硫酸钙在有机相中的结晶过程进行了在线监测,通过扫描电镜（SEM）和X射线衍射（XRD）等手段对副产硫酸钙的晶体形貌和物相组成进行了分析,结果表明实验条件下洗涤10 min时,体系中的Ca²⁺生成半水石膏（CaSO₄·0.5H₂O）。计算表明,该盐酸法磷酸工艺洗涤过程中副产石膏值（以二水硫酸钙计）仅为二水硫酸法的8.7%,显著降低了湿法磷酸过程中的石膏处理量。     

Adsorption equilibrium,kinetics, and dynamic separation of Ca2+ and Mg2+ ions from phosphoric acid-nitric acid aqueous solution by strong acid cation resin

The separation of Ca²⁺ and Mg²⁺ ions from phosphoric acid-nitric acid aqueous solution is very significant for the neutralization process of nitrophosphate fertilizer. This paper studied the adsorption equilibrium, kinetics, and dynamic separation of Ca²⁺ and Mg²⁺ ions by strong acid cation resin, and the effects of phosphoric acid and nitric acid on the adsorption process were investigated. The results reveal that the adsorption process of Ca²⁺ and Mg²⁺ ions in pure water on resin is in good agreement with the Langmuir isotherm model and their maximal adsorption capacities are 1.86 mmol·g^-1 and 1.83 mmol·g^-1, respectively. The adsorption kinetics of Ca²⁺ and Mg²⁺ ions on resin fits better with the pseudo-first-order model, and the adsorption equilibrium in pure water is reached within 10 min contact time, while at the present of phosphoric acid, the adsorption rate of Ca²⁺ and Mg²⁺ ions on resin will go down. The dynamic separation experiments demonstrate that the designed column adsorption is able to undertake the separation of metal ions from the mix acids aqueous solution, but the dynamic operation should control the flow rate of mix acid solution. Besides nitric acid solution was proved to be effective to completely regenerate the spent resin and achieve the recyclable operation of separation process.     

多组分氯盐体系镁锂分离规律初探

以Na₂CO₃为沉淀剂,初步研究了多组分氯盐混合体系（0.6 mol MgCl₂+1.1 mol LiCl+3.2 mol NaCl）中选择性沉镁的工艺规律。结果表明：在25~80 ℃,总C与总Mg物质的量比[n（C_T）/n（Mg_T）]为 0.8~1.1时,25 ℃形成针状MgCO₃·3H₂O,40 ℃以上形成Mg₅（CO₃）₄（OH）₂·4H₂O不规则片状团聚微球,其中40~50 ℃形成的片状物较为分散且粒径较小,导致固液分离困难。40 ℃时沉镁率最低。温度越高,Li₂CO₃越易形成,沉锂率越大。n（C_T）/n（Mg_T）越大沉镁率和沉锂率越高。室温（25 ℃）、n（C_T）/n（Mg_T）=1.0时,沉镁率达98%以上,且沉锂率<0.1%,镁锂分离效果最好。