Synthesis of sulfated Y-doped zirconia particles and effect on properties of polysulfone membranes for treatment of wastewater containing oil

Polysulfone (PSF) membranes are broadly applied in many fields owing to good physicochemical stability, resistance to oxidation and chlorine. But when treated with wastewater containing oil, PSF membranes are easily contaminated due to their hydrophilicity, causing declining flux and lifespan of the membranes thereby limiting their large scale applications. In order to enhance the hydrophilic and anti-fouling capability of PSF membranes for treating wastewater containing oil, sulfated Y-doped zirconia particles (SO₄²⁻/ZrO₂-Y₂O₃ or SZY particles) were firstly synthesized and then doped into polysulfone to fabricate a novel hybrid membrane (SZY/PSF). The optimum preparation conditions of SZY particles were studied and determined. SZY particles were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR), specific surface area and transmission electron microscopy (TEM). Wastewater containing oil (80 mg/L) was used to investigate the separation properties of SZY/PSF membranes. The results show that the oil concentration in the permeation is 0.67 mg/L, which meets the recycle standard of the Chinese oil-field (SY/T 5329-94, oil concentration <10 mg/L). It is concluded that doping SZY particles into polysulfone can reasonably resist membrane fouling and SZY/PSF membranes can be considered feasible in treating wastewater containing oil.     

TiO_2动态改性膜应用于MBR的研究

采用二氧化钛(TiO_2)纳米粒子对聚偏氟乙烯中空纤维膜微滤膜(PVDF MF,0.1μm)和实验室自制聚砜中空纤维膜超滤膜(PSF UF,0.05μm)进行表面亲水改性,以期提高膜的抗污染能力.采用膜接触角、纯水通量、出水TOC、膜压差和扫描电子显微镜(SEM)进行表征了TiO_2动态膜的性能.将TiO_2纳米颗粒改性后的PVDF MF和PSF UF膜应用于膜生物反应器(MBR)处理模拟焦化废水(TOC=500 mg/L),考察了其对MBR过滤性能的影响.实验结果表明,改性后膜的水接触角明显减小,亲水性增强,TMP升高速率明显降低,模拟焦化废水,TOC的去除率平均可达95%,经返洗及次氯酸钠清洗后膜表面TiO_2层外观没有明显变化.改性后的膜组件较显著地增加了MBR的膜抗污染的优势,且具有一定的稳定性.因此,将TiO_2动态改性耐污染膜应用于MBR是可行的.     

聚砜类合金分离膜研究进展

介绍了 PSF类合金膜的特点、相容性及其对 PSF合金膜结构与性能的影响的研究进展。     

PDMS中空纤维复合膜渗透汽化分离丙酮-水溶液

采用干湿相转化法纺制了聚砜(PSF)中空纤维超滤底膜,并采用溶液浸渍法制备PDMS/PSF中空纤维复合膜.研究了PDMS膜的溶胀性能和PDMS/PSF膜渗透汽化性能,考察了PDMS/PSF膜的稳定性以及料液温度、料液丙酮浓度和渗透物侧压力等因素对膜渗透汽化性能的影响.结果表明,PDMS膜对丙酮有很强的吸附能力而对水的吸附能力则相对较弱,渗透液中丙酮浓度大于膜溶胀液中丙酮浓度,远远大于浸泡液中丙酮浓度,连续操作72 h膜的渗透汽化性能保持稳定,渗透通量随料液温度以及料液浓度的升高而增加,分离系数随料液浓度的增加而降低,基本不受温度的影响.当丙酮质量分数5%、料液温度为60℃时,渗透通量为632 g/(m2.h),分离系数为35.8,丙酮和水的表观活化能分别为45.7和49 kJ/mol.     

陶瓷膜处理炼油厂"三泥"水相的研究

采用陶瓷微滤膜对“三泥”水相进行处理．通过渗透液油含量的测定,证明此方法能明显地降低传统方法仰处理的水相的油,尤其是乳化油的含量．同时,确定了合适的膜孔径,研究了操作压力、膜面流速和操作温度对渗透通量的影响．为炼油厂“三泥”的处理提供了一种新的方法．     

PSF/SPSF合金膜的相容性对膜性能的影响

聚砜(PSF)／磺化聚砜(SPSF)合金膜是采用液相共混及相转换法制成的．本文研讨了PSF/SPSF的相容性与其合金膜性能之间的相关性．根据在不同组成条件下混合熵值的计算结果判断，PSF／SPSF合金是一部分相容的体系．实验结果表明，在本实验范围内随着SPSF含量的增加，PSF／SPSF体系相容性降低，从而引起合金膜的纯水量升高，截留率下降．溶剂的种类及混合溶剂的比例也影响PSF/SPSF的相容性，从而影响膜的性能．在NMP-DMF混合溶剂中，随着DMF含量的增大，PSF/SPSF合金体系的相容性变差，其结果造成膜的通量升高，同时截留率下降．     

NiCo/PTFE复合膜的制备及表征

以N₂H₄ 为还原剂, 采用化学镀和模板技术相结合的方法制备出NiCo/ PTFE 磁性复合膜。研究了磁性复合膜制备的适宜条件, 利用DSC、SEM、XRD、VSM 等手段对膜的结构和磁性能进行表征和测试。结果表明:在Co2+ 0. 14 mol/ L 、Ni2+ 0. 06 mol/ L 、NaOH 1. 00 mol/ L 、N₂H₄ 0. 40 mol/ L 、反应温度70 ℃、反应时间70 min条件下制备的NiCo/ PTFE 磁性复合膜具有较优良的磁性能, 其单位质量磁化率χ_m = 0116 cm3 / g , 饱和磁化强度M_s = 83. 38 Am2 / kg , 剩磁M_r = 29. 31 Am2 / kg , 矫顽力H_c = 111. 47 Oe ; PTFE 膜孔中及膜表面上原位生成与基膜无化学键作用的磁性Ni 、Co 金属粒子。复合膜具有软磁材料的内禀性能。      

外加磁场下聚砜-Fe_3O_4复合超滤膜的孔径变化

以无磁性聚砜超滤膜为对照,采用液-液界面法,以水-正丁醇体系为对象,对不同磁场强度下,聚砜-Fe3O4磁性复合超滤膜的孔径变化规律进行了研究。结果表明,在不同磁场下,2张空白聚砜膜的孔径无显著变化,3张聚砜-Fe3O4复合膜的孔径变化显著且趋势相同,即0T~0.4 T时,平均孔径随场强增大而增大,0.4T~1.2T时,平均孔径随场强增大而减小。纯水通量实验结果显示,不同磁场对膜通量影响的变化趋势与所测孔径变化相吻合。     

磺化聚芳醚酮砜/TiO2复合质子交换膜的制备与性能

为了满足高温燃料电池对质子交换膜的要求,通过溶胶共混法制备了掺有不同含量TiO2纳米粒子的磺化聚芳醚酮(SPAEKS)/TiO2复合膜。红外光谱证实TiO2被引入到SPAEKS共聚物中。扫描电镜(SEM)照片显示,纳米级的TiO2粒子能够均匀地分散在SPAEKS共聚物基体中。通过对复合膜的性能测试发现TiO2的引入,复合膜的热稳定性、吸水率、保水能力及阻醇性能都有所提高。而且SPAEKS/TiO2复合膜的质子传导率高于SPAEKS膜,并在高温时尤为明显,能够满足高温燃料电池的需要。     

Novel sodium alginate composite membranes prepared by incorporating cobalt(III) complex particles used in pervaporation separation of water–acetic acid mixtures at different temperatures

The present paper is our continuing effort to develop a new type of sodium alginate (NaAlg) composite membrane by incorporating cobalt(III)(3-acetylpyridine-o-aminobenzoylhydrazone) (Co-APABZ) complex as filler particles in different ratios. Membranes were prepared by solution casting followed by solvent evaporation and crosslinked with glutaraldehyde. Pervaporation (PV) performance of the prepared composite membranes was assessed in terms of flux and selectivity and these data were compared with the pristine NaAlg membrane in PV dehydration of water–acetic acid mixtures. Pristine Co-APABZ particles in crystalline form were prepared and characterized by the solid state X-ray diffraction (XRD) technique, while the NaAlg/Co(III)composite membranes were characterized by thermogravimetry (TGA) and dynamic mechanical thermal analyzer (DMTA). X-ray crystal structure of Co-APABZ has shown that the complex formed was crystalline in nature with six lattice water molecules, which are interconnected by hydrogen bonds linking together to form cyclic hexamers that are analogous to cyclohexane, creating water channels for an easy transport of water molecules. TGA indicated no changes in thermal stability of the membranes due to the presence of Co-APABZ in the NaAlg matrix. DMTA confirmed NaAlg crosslinking with glutaraldehyde. Effects of Co-APABZ content, membrane thickness, temperature and feed water compositions on membrane performance were investigated to find an optimum PV performance of the membranes developed. NaAlg composite membranes in the presence of Co-APABZ particles preferentially absorbed water molecules to facilitate diffusion of water through the membranes and thus enhance the selectivity to water. However, the amount of Co-APABZ present in the NaAlg matrix and the degree of membrane swelling has an effect on membrane performance. Selectivity of 174 for water with a flux of 0.123 kg/m² h was obtained for 5 wt.% Co-APABZ containing NaAlg matrix, when tested for the feed mixture containing 10 wt % water. The present results are superior to the previously published data based on NaAlg membranes. This article is CEPS communication #110.     

Ultrafiltration Membranes with Structure‐Optimized Graphene‐Oxide Coatings for Antifouling Oil/Water Separation

Fouling of ultrafiltration (UF) membranes in oil/water separation is a long‐standing issue and a major economic barrier to their use in a broad range of applications. Currently reported membranes typically show severe fouling, resulting from the strong oil adhesion on the membrane surface and/or oil penetration inside the membranes. This greatly degrades their performance and shortens service lifetime. Here, the use of graphene oxide (GO) as a novel coating material for the fabrication of fully recoverable, UF membranes with desired hierarchical surface roughness is accomplished by a facile vacuum filtration method for antifouling oil/water separation. The combination of ultrathin, “water‐locking” GO coatings with the optimized hierarchical surface roughness, provided by the inherent roughness of the porous supports and the corrugation of the GO coatings, minimizes underwater oil adhesion on the membrane surface. Cyclic membrane performance evaluation tests revealed approximately 100% membrane recovery by facile surface water flushing, establishing their excellent easy‐to‐recover capability. The novel GO functional coatings with optimized hierarchical structures may have broad applications in oil‐polluted environments.     

纳米SiO2/SPFEK复合质子交换膜的制备及性能

以自制的磺化聚芴醚酮和正硅酸乙酯为原料,采用溶胶凝胶(Sol-gel)法合成了掺杂纳米SiO2的复合质子交换膜,利用能量分散谱(EDS)线扫描、热失重分析法、扫描电镜对膜的结构、热稳定性、微观形态进行了表征。并考察了质子交换膜的各种性能。结果表明,纳米SiO2能提高膜的质子传导率和氧化稳定性能。当SiO2掺杂质量分数为9%时,复合膜的质子传导率在80℃时为5.96×10-2(S/cm),在80℃的Fenton’s试剂(3%的过氧化氢和2 mg/L的FeSO4)中进行氧化稳定性测试,膜在117 min时才开始碎裂,表现出良好的氧化稳定性。     

乙基纤维素/TiO2复合膜的制备及气体渗透性能

以乙基纤维素(EC)和正钛酸丁酯(TBT)为主要原料,通过溶胶-凝胶(Sol-Gel)法制备了EC/TiO2复合膜。研究了TiO2粒子在复合膜中分布形貌、复合膜的结构变化及对气体渗透和分离性能的影响。结果表明,TiO2质量分数达到25%时,微米级的TiO2粒子均匀分散在复合膜中,复合膜形成有机-无机三维网络结构,测试气体在膜中的渗透行为主要受动力学因素控制,其中H2、O2透气系数分别增大至纯EC膜的1.8倍和1.3倍,H2/N2及O2/N2分离性能略有提高。     

Multifunctional Polymer/Porous Boron Nitride Nanosheet Membranes for Superior Trapping Emulsified Oils and Organic Molecules

Effective oil/water separation and removal of organic molecules from water are of worldwide importance for water source protection. Multifunctional sorbent materials with excellent sorption capacity, stability, and recyclability properties need to be developed. Here, flexible and multifunctional polymer/porous boron nitride nanosheets (BNNSs) membranes with high water permeability, exhibiting high effectiveness and stability in the purification of simulated wastewater tainted with either oil/water emulsion or organic molecules, are reported. Remarkably, the flexible nature of these porous membranes enables simplicity of operation for water remediation processing and ease of post‐processing collection. The composite membrane also displays a remarkably high permeability of 8 × 10⁴ L μm m⁻² h⁻¹ bar⁻¹, roughly three orders of magnitude higher than pure polymer, and excellent filter efficiencies for the pharmaceuticals ciprofloxacin, chlortetracycline, and carbamazepine (up to 14.2 L g⁻¹ of BNNSs in the composite membrane for a concentration of 10 mg L⁻¹ ciprofloxacin) and the dye methylene blue (up to 9.3 L g⁻¹ of BNNSs in the composite membrane at a concentration of 30 mg L⁻¹). Exhausted membranes can be readily rejuvenated by simple washing with retention of their high‐performance characteristics. The results demonstrate the potential efficacy and practicality of these membranes for water cleaning.     

改性聚偏氟乙烯膜的油吸附性研究

排除因液体流动和压力梯度造成的浓差极化、油滴形变等影响因素,用静态吸附法考察膜对油分子的吸附规律.结果表明,膜对油分子的吸附属于一级动力学吸附,吸附过程的主要控制步骤是油分子在膜表面及膜孔内的扩散.Freundlich等温方程可以很好地描述膜对油分子的吸附,拟合后的常数K和1/n均较小,证明所用的改性聚偏氟乙烯膜对油分子的吸附能力较小,吸附强度较弱,也即改性聚偏氟乙烯膜耐污染,且易清洗.膜改性可以在处理低浓度含油废水时有效减少由于膜对油分子的吸附而造成的污染.     

高通量抗污染碳量子点/聚砜纳米复合分离膜的制备

先以4-氨基水杨酸(ASA)为原料发生水热反应合成碳量子点(CDs),随后将其共混分散在铸膜液中用非溶剂诱导相分离法制备了PSF/CDs纳米复合膜。透射电子显微镜(TEM)观测和傅里叶变换红外光谱(FTIR)证实,CDs具有小尺寸和大量亲水基团的特点。使用水接触角分析(WCA)、扫描探针显微镜(SPM)和扫描电子显微镜(SEM)对分离膜进行了表征,发现纳米复合膜具有比原始膜更好的亲水性和更多的孔洞,从而使分离膜具有更高的通量和抗污染性能。PSF/CDs膜的通量回复率(FRR)超过90%,总污染率(Rt)低于60%,且可逆型污染为主要污染源。CDs含量(质量分数)为2%的复合膜整体效果最佳。具有更强抗污染能力的纳米复合膜,其水通量甚至为纯PSF膜的3倍。     

陶瓷微滤膜强化过程的工艺条件研究

以钛白粉水洗液为处理对象,利用湍流促进器对陶瓷膜微滤过程进行强化研究,考察了膜孔径、过滤方式以及操作条件（错流速度、过滤压差、温度、浓度）对强化过程的影响,确定了合适的膜孔径和过滤操作参数     

磷钨酸/磺化聚芳醚酮砜复合型高温燃料电池用质子交换膜

为了满足高温质子交换膜燃料电池使用要求,采用溶液铺膜法制备了磺化聚芳醚酮砜(SPAEEKS)与磷钨酸(HPA)复合型质子交换膜。红外光谱证明磷钨酸中的桥氧原子和端氧原子与磺酸基团形成了强烈的相互作用。扫描电镜照片显示磷钨酸粒子能够均匀地分散在聚合物的基体中。磷钨酸的引入提高了复合膜的热稳定性 ,含有 30wt%HPA、SPAEEKS磺化度为0.8的复合膜(HPA30/SPAEEKS-0.8)的玻璃化转变温度达到236℃,质量损失5%时的热分解温度达到了299℃。在相同测试条件下,HPA30/ SPAEEKS-1. 0在80℃时质子传导率高于Nafion 117,而且在120℃ 达到了0.098S/cm。结果表明,HPA30/SPAEEKS-1. 0 有望在高温质子交换膜燃料电池中得到应用。     

纳滤膜分离洁霉素生产废水的试验研究

针对洁霉素生产废水,采用国内外多种纳滤膜在不同工况条件下进行了试验研究,筛选和确定了适用纳滤膜的种类和其最佳工作条件,为纳滤膜的进一步应用奠定了基础。     

钯膜制备及渗氢性能研究

随着膜分离技术的不断发展,渗氢用钯基膜由于具有优异的透氢速率、透氢选择性及良好的化学和热稳定性,已被广泛应用于氢提纯分离领域。介绍了钯透氢膜的种类、透氢机理和制备方法,总结了钯膜从最初的纯钯膜、钯合金膜到钯复合膜的发展历程和氢渗透性能研究,并重点介绍了以铌钯复合膜为代表的新型Pd/bcc型复合膜氢渗透性能的研究进展。