应用负载型纳米铁去除饮用水中砷的研究

砷是毒性最强的元素之一，水体中砷的污染己经引起人们广泛的关注。我国的新疆、内蒙、山西和台湾等省和地区地下水砷含量严重超标。全球共有5,000多万人遭受高砷饮用水的威胁，其中中国有1,500多万，是饮用水砷污染最严重的国家之一。WHO推荐饮用水砷的最高允许浓度从原来的50 µg•L-1已降至10 µg•L-1。更为严格的砷卫生标准的颁布，对作为饮用水源的地下水中的砷去除工艺提出了更高的要求。吸附法除砷比膜法、混凝法和离子交换法更安全、简便，是砷去除工艺中最有效的方法之一。 首先，本研究通过优化制备条件（包括炭种类的选择、炭的粒径大小、还原剂的浓度及滴定速率、反应温度、铁盐的种类及浓度、分散剂的比例及浓度），制备了负载型纳米铁。考虑到砷的去除效率、工程应用的可行性以及经济性，最优的制备条件如下：选用粒径为20~40目煤质炭，在室温、一定的分散剂比例及浓度，0.2 M KBH4滴速为20 d•min-1时所制备的Fe/炭为82.0 mg•g-1；纳米铁在活性炭孔内呈针状，其直径为30~500 nm，长度为1,000~2,000 nm。绝大多数的铁都负载到活性炭内部，这在处理水时铁不流失很重要。 其次，利用制备的负载型纳米铁作吸附载体，进行了饮用水中As(Ⅴ)的吸附去除实验。研究了该吸附剂对As(Ⅴ)的吸附等温线、动力学以及影响动力学的各种因素（包括As(Ⅴ)的不同初始浓度、吸附剂用量、pH值、共存离子和不同温度）、pH值、共存离子等环境条件对As(Ⅴ)去除的影响；以及吸附剂的再生及再生后的吸附效率等。研究发现在前12 h内吸附较快，72 h时达到了平衡。用Langmuir 吸附等温式估算出As(Ⅴ)的吸附量为12.0 mg•g-1。该吸附剂在pH 6.5， (25±2)℃， As(Ⅴ)初始浓度为2 mg•L-1，吸附剂用量为1.0 g•L-1时，As(Ⅴ)的去除率为75.2%；当把吸附剂的用量增加到1.5 g•L-1时，As(Ⅴ)的去除率可达99.9%以上。吸附剂可以用0.1M的NaOH浸泡12 h后即可再生，再生效率较高。常见的阴离子中PO43-、SiO32-对As(Ⅲ)的去除抑制较大，而SO42-、CO32-、C2O42-等离子对砷的去除影响较小。Fe2+对As(Ⅲ)的吸附抑制作用较大而其它阳离子影响不大。吸附剂可用0.1 M NaOH 有效再生，并且具有良好的机械性能。实验室初步实验数据表明，该吸附剂对饮用水除砷具有较好的应用前景。 第三，利用实验室制备的负载型纳米铁对饮用水中As(Ⅲ)的吸附去除也进行了研究。考察了吸附等温线、动力学以及影响动力学的各种因素、pH值、共存离子等环境条件对As(Ⅲ)去除的影响；以及吸附剂的再生及再生后的吸附效率等。研究发现，该吸附剂在pH 6.5， (25±2)℃， As(Ⅲ)初始浓度为2 mg•L-1，吸附剂用量为1.0 g•L-1时， 对As(Ⅲ)的去除率为99.8%；其吸附容量为1.996mg•g-1。吸附过程中部分As(Ⅲ)被氧化。与As(Ⅴ)的吸附相比，该吸附剂对As(Ⅲ)的效率比较高-而常见的其它除砷吸附剂如载铁纤维棉等，对As(Ⅴ)的效率比As(Ⅲ)高，为有效去除As(Ⅲ)，常常需要专门加上氧化这一过程。 最后，利用负载型纳米铁对饮用水中As(Ⅲ) 的氧化性能进行考察，发现该吸附剂不但能够有效吸附去除饮用水中的砷，而且还能把As(Ⅲ)有效地氧化为As(Ⅴ)。经过对吸附剂的构成组分分析发现，活性炭表面因富含多种官能团而对三价砷的氧化作用最大；其次是纳米铁也能把As(Ⅲ)氧化为As(Ⅴ)。

Preparation of uniform calcium alginate gel beads by membrane emulsification coupled with internal gelation

With the objective of making calcium alginate gel beads with small and uniform size, membrane emulsification coupled with internal gelation was proposed. Spherical gel beads with mean size of about 50 mum, and even smaller ones in water, and with narrow size distribution were successfully obtained. Experimental studies focusing mainly on the effect of process parameters on bead properties were performed. The size of the beads was mainly dependent on the diameter of the membrane pores. High transmembrane pressure made for large gel beads with wide size distribution. Low sodium alginate concentration produced nonspherical beads, whereas a high concentration was unsuitable for the production of small beads with narrow distribution. Thus 1.5% w/v was enough. A high surfactant concentration favored the formation of small beads, but the adverse effect on mass transfer should be considered in this novel process. (C) 2002 Wiley Periodicals, Inc.

Capillary electrochromatographic separation of enantiomers on chemically bonded type of cellulose derivative chiral stationary phases with a positively charged spacer

Positively charged chiral stationary phases (CSPs) were prepared for capillary electrochromatography (CEC) separation of enantiomers by chemically immobilizing cellulose derivatives onto diethylenetriaminopropylated silica (DEAPS) with tolylene-2,4-diisocyanate (TDI) as a spacer reagent. Anodic electroosmotic mobility was observed in both nonaqueous and aqueous mobile phases due to the positively charged amines on the surface of the prepared CSPs. For comparison, the traditionally used 3-aminopropyl silica (APS) was also adopted as the base material instead of DEAPS to prepare CSP. It was observed that the EOF on the DEAPS-based CSP was 18%-60% higher than that on the APS-based CSP under nonaqueous mobile phase conditions. Separation of enantiomers in CEC was performed on the positively charged CSPs with the nonaqueous mobile phases of pure ethanol or mixture of hexane-alcohol and the aqueous phases of acetonitrile-water or 95% ethanol. Fast separation of enantiomers was achieved on the newly prepared CSPs.

Affinity membrane chromatography for the analysis and purification of proteins

Affinity chromatography is unique among separation methods as it is the only technique that permits the purification of proteins based on biological functions rather than individual physical or chemical properties. The high specificity of affinity chromatography is due to the strong interaction between the ligand and the proteins of interest. Membrane separation allows the processing of a large amount of sample in a relatively short time owing to its structure, which provides a system with rapid reaction kinetics. The integration of membrane and affinity chromatography provides a number of advantages over traditional affinity chromatography with porous-bead packed columns, especially with regard to time and recovery of activity. This review gives detailed descriptions of materials used as membrane substrates, preparation of basic membranes, coupling of affinity ligands to membrane supports, and categories of affinity membrane cartridges. It also summarizes the applications of cellulose/glycidyl methacrylate composite membranes for proteins separation developed in our laboratory. (C) 2001 Elsevier Science B.V. All rights reserved.

Mercury(II) ion sensing with PVC-matrix based membrane sensors

Thiosemicarbazone derivatives have been used as ion carriers for the preparation of PVC-matrix based mercury(II)-selective membrane sensors. The electrodes give near-Nernstian responses in the linear concentration range of 1.0×10-1-5.0×10-6 M with detection limits of the order of 10-6 M. The stable potentiometric signals are obtained within a short time period of 20-25s. The effect of different plasticizers has been studied and dioctylsebacate (DOS) found to give a better response in comparison to other plasticizers. Selectivity coefficient values (log KPotHg,M) have been evaluated using fixed interference method. Better selectivity for mercury(II) ions is observed over many of the monovalent (Na+, K+ and NH4+) and divalent ions (Mg2+, Ca2+, Zn2+, Pb2+, Ni2+, Co2+, etc.). The sensors have also been used as indicator electrodes in potentiometric titration of mercury(II) ions with EDTA and its determination in synthetic water samples.

An effective method for enhancing metal-ions' selectivity of ionic liquid-based extraction system: Adding water-soluble complexing agent

Selective extraction-separation of yttrium(Ill) from heavy lanthanides into 1-octyl-3-methylimidazolium hexafluorophosphate ([C(8)mim][PF6]) containing Cyanex 923 was achieved by adding a water-soluble complexing agent (EDTA) to aqueous phase. The simple and environmentally benign complexing method was proved to be an effective strategy for enhancing the selectivity of [C(n)mim] [PF6]/[Tf2N]-based extraction system without increasing the loss of [C(n)mim](+). (c) 2007 Elsevier B.V. All rights reserved.

Fabrication of Superhydrophobic Cellulose-Based Materials through a Solution-Immersion Process

An industrial waterproof reagent [(potassium methyl siliconate) (PMS)] was used for fabricating a superhydrophobic surface on a cellulose-based material (cotton fabric or paper) through a solution-immersion method. This method involves a hydrogen bond assembly and a polycondensation process. The silanol, which was formed by a reaction of PMS aqueous solution with CO2, Was assembled on the cellulose molecule surface via hydrogen bond interactions. The polymethylsilsesquioxane coatings were prepared by a polycondensation reaction of the hydroxyl between cellulose and silatiol. The superhydrophobic cellulose materials were characterized by FTIR spectroscopy, thermogravimetry, and surface analysis (XPS, FESEM, AFM, and contact angle measurements).

Novel thin-film composite membranes with improved water flux from sulfonated cardo poly(arylene ether sulfone) bearing pendant amino groups

A new class of polymeric amine, namely, sulfonated cardo poly(arylene ether sulfone) (SPES-NH2) was synthesized and used for the preparation of thin-film composite membrane. The TFC membranes were prepared on a polysulfone supporting film through interfacial polymerization with trimesoyl chloride (TMC) solutions and amine solutions containing SPES-NH2 and m-phenylenediamine (MPDA). The resultant membranes were characterized with water permeation performance, chemical structure, hydrophilicity of active layer and membrane morphology including top surface and cross-section.

Synthesis and properties of water stable poly[bis(benzimidazobenzisoquinolinone)] ionomers for proton exchange membranes fuel cells

A novel sulfonated tetraamine, di(triethylammonium)-4,4'-bis(3,4-diaminophenoxy)biphenyl-3,3'-disulfonate (BAPBDS), was successfully synthesized by nucleophilic aromatic substitution of 4,4'-dihydroxybiphenyl with 5-chloro-2-nitroaniline, followed by sulfonation and reduction. A high-temperature polycondensation of sulfonated tetraamine, non-sulfonated tetraamine (4,4 -bis(3,4-aminophenoxy)biphenyl) and 1,4,5,8-naphthalenetetracarboxylic dianhydride (a) or 4,4'-binaphthyl-1,1',8,8'-tetracarboxylic dianydride (b) gave the poly[bis(benzimidazobenzisoquinolinones)] ionomers SPBIBI-a(x) or SPBIBI-b(x), where x refers to the molar percentage of the sulfonated tetraamine monomer. Flexible and tough membranes of high mechanical strength were obtained by solution casting and the electrolyte properties of the polymers were intensively investigated. The ionomer membranes displayed excellent dimensional and hydrolytic stabilities.

Synthesis and characterization of soluble poly(amideimide)s bearing triethylamine sulfonate groups as gas dehumidification membrane material

A series of soluble poly(amide-imide)s (PAIs) bearing triethylammonium sulfonate groups were synthesized directly using trimellitic anhydride chloride (TMAC) polycondensation with sulfonated diamine such as 2,2'-benzidinedisulfonic acid (BDSA), 4,4'-diaminodiphenyl ether-2,2'-disulfonic acid (ODADS), and nonsulfonated diamine 4,4-diaminodiphenyl methane in the presence of triethylamine. The resulting copolymers exhibited high molecular weights (high inherent viscosity), and a combination of desirable properties such as good solubility in dipolar aprotic solvents, film-forming capability, and good mechanical properties. Wide-angle X-ray diffraction revealed that the polymers were amorphous. These copolymers showed high permeability coefficients of water vapor because of the presence of the hydrophilic triethylammonium sulfonate groups. The water vapor permeability coefficients (P-w) and permselectivity coefficients of water vapor to nitrogen and methane [alpha(H2O/N-2) and (alpha(H2O/CH4)] Of the films increased with increasing the amount of the triethylammonium sulfonated groups.

Vapor permeation separation of MeOH/MTBE through polyimide/sulfonated poly(ether-sulfone) hollow-fiber membranes

Mixtures of methanol/MTBE were separated with polyimide/sulfonated poly(ether-sulfone) hollow-fiber membranes. The separation was attempted by vapor permeation instead of pervaporation, which had been used by most researchers. The separation properties of the hollow-fiber membranes and operating conditions are discussed. The results showed that separation factors of the blended polyimide/sulfonated poly(ether-sulfone) hollow-fiber membranes were extremely high for the methanol/MTBE mixtures.

Preparation and properties of microporous membrane from poly(vinylidene fluoride-co-tetrafluoroethylene) (F2.4) for membrane distillation

Flat-sheet microporous membranes from F2.4 for membrane distillation (MD) were prepared by phase inversion process. Dimethylacetamide (DMAC) and LiClO(4)(.)3H(2)O/trimethyl phosphate (TMP) were, respectively, used as solvent and pore-forming additives. The effects of casting solution composition, exposure time prior to coagulation and temperature of precipitation bath on F2.4 membrane structure were investigated. The morphology of resultant porous membrane was observed by scanning electron microcopy. Some natures of F2.4 porous membrane after drying in air, such as mechanical properties and hydrophobicity, were exhibited and compared with poly(vinylidene fluoride) (PVDF) membrane prepared by the same ways. Stress-at-break and strength stress of F2.4 microporous membrane are higher than that of PVDF membrane, and elongation percentage of F2.4 membrane at break is about eight-fold as great as that of PVDF membrane. Contact angle of F2.4 microporous membrane to water (86.6 +/- 0.51degrees) was also larger than that of PVDF mernbrane (80.0 +/- 0.78degrees). MD experiment was carried out using a direct contact membrane distillation (DCMD) configuration as final test to permeate performance of resultant microporous membrane.

Preliminary research on microporous membrane from F2.4 for membrane distillation

An asymmetric hydrophobic microporous membrane from the copolymer of tetrafluoroethylene and vinyliden fluoride (F2.4) has been fabricated by phase inversion process. Some characteristics, such as mechanical properties and hydrophobicity, have been examined and compared with polyvinylidenefluoride (PVDF) membrane. Experimental data exhibit F2.4 membrane excellent mechanical properties and hydrophobicity. F2.4 microporous membrane was approximately 6-8 times as high as PVDF membrane in stretching strain and extension ratio at break, and contact angle to distilled water of the fore (88.5degrees) was larger than the latter (80.0degrees), too. The results from membrane distillation (MD) process were well agreed with the fundamental laws of membrane distillation.

A new flow field and its two-dimension model for polymer electrolyte membrane fuel cells (PEMFCs)

A new flow field was designed to search flow fields fitting polymer electrolyte membrane fuel cells (PEMFCs) better due its extensible. There are many independent inlets and outlets in the new flow field. The new flow field we named NINO can extend to be more general when pressures at the inlet and outlet vary and some usual flow fields will be obtained. A new mathematical model whose view angle is obverse is used to describe the flow field.

Factors affecting pore structure and performance of poly(vinylidene fluoride-co-hexafluoro propylene) asymmetric porous membrane

Preparation of poly(vinylidene fluoride-co-hexafluoro propylene) (F2.6) flat-sheet asymmetric porous membrane has been studied for the first time. Factors affecting F2.6 membrane pore structure and permeate performance, such as macromolecule pore formers (polyethylene glycol-400, 1000, 1540, 2000 and 6000), the small molecule former (glycerol), swelling agent (trimethyl phosphate) in casting solution, precipitating bath component and temperature, exposure time and ambient humidity, were investigated in detail. Average pore radius and porosity were used to characterize F2.6 membrane structure, and respectively, determined by ultrafiltration and gravimetric method for the wet membrane. Morphology of the resultant membranes was observed by scanning electronic microscopy (SEM). Final test on permeate performance of F2.6 porous membrane was carried out by a direct contact membrane distillation (DCMD) setup. The experimental F2.6 membrane exhibits a higher distilled flux than PVDF membrane under the same operational situations. The determination of contact angle to distilled water also reveals higher hydrophobic nature than that of PVDF membrane.