原料颗粒形状对粉煤灰基陶瓷微滤膜通量的影响

以球形颗粒和非球形颗粒粉煤灰为原料,制备了对称陶瓷膜。讨论了膜的渗透性能。结果表明,膜的纯水通量和成膜颗粒的球形度成正比,球形颗粒制备的陶瓷膜平均孔径0.94μm,在0.1 MPa的跨膜压差下,纯水通量为11 306 L/(m²·h),为非球形颗粒制备的陶瓷膜通量的1.13倍。球形颗粒粉煤灰同时表现出低成本原料优势和高通量颗粒形状优势。     

原料颗粒形状对粉煤灰基陶瓷微滤膜通量的影响

以球形颗粒和非球形颗粒粉煤灰为原料,制备了对称陶瓷膜。讨论了膜的渗透性能。结果表明,膜的纯水通量和成膜颗粒的球形度成正比,球形颗粒制备的陶瓷膜平均孔径0.94μm,在0.1 MPa的跨膜压差下,纯水通量为11 306 L/(m~2·h),为非球形颗粒制备的陶瓷膜通量的1.13倍。球形颗粒粉煤灰同时表现出低成本原料优势和高通量颗粒形状优势。     

石英微滤陶瓷膜的制备研究

以石英砂陶瓷支撑体为基体，SiO₂粉体为固相，聚乙烯醇(PVA)为黏结剂，聚丙烯酸和丙三醇为分散相制备涂膜液，采用浸渍提拉法进行微滤膜层的涂覆制备，考察黏结剂添加量、涂膜时间、烧结温度等制备条件对石英微滤陶瓷膜性能的影响，通过孔隙率、纯水通量、SEM等方法对其进行测试和表征。结果表明：石英微滤陶瓷膜涂膜液聚乙烯醇含量为10%,涂膜时间60 s、烧结温度850℃时制备的石英微滤陶瓷膜性能较好，孔径均匀，平均孔径为1.90μm,纯水通量为9.20 m³·m^-2·h^-1·bar^-1,孔隙率为35.58%。     

球形离子筛吸附剂的制备及其锂吸附性能评价

利用琼脂糖溶液的溶胶凝胶性质,通过锐孔凝固浴法,对实验室合成的Li₄Mn₅O₁₂粉体进行成型,制备了粒径2～3 mm的球形颗粒,对球形颗粒进行交联后,用1 mol·L^-1的盐酸对球形颗粒进行酸洗脱锂,最终制得球形锂离子筛吸附剂。考察球形吸附剂制备和交联的影响因素,结果表明：5%的琼脂糖浓度和90 ℃的温度为最佳制备条件,2 ml·g^-1的交联剂用量和6 h的交联时间为最佳交联条件。对球形离子筛吸附剂进行静态评价实验,结果表明锂吸附容量为4.25 mmol·g^-1,吸附速率为1.77×10^-5 s^-1,成型后离子筛吸附量是离子筛粉末的75.6%,吸附速率较粉体（3.29×10^-4 s^-1）下降一个数量级。Li⁺平衡吸附容量随平衡pH值的升高而增加,在pH>12时吸附容量高达5.5 mmol·g^-1。共存离子选择性实验表明,交联球形离子筛吸附剂对Li⁺具有高选择性,成型后离子筛可以用于盐湖卤水或者海水提锂。     

离子筛吸附与陶瓷膜耦合用于盐湖卤水提锂

将锰系离子筛吸附与陶瓷膜耦合,用于高镁锂比盐湖卤水的提锂研究。采用水热法制备了高效锂离子筛H_1.6Mn_1.6O₄,考察离子筛用于卤水提锂效果和陶瓷膜的分离性能。结果表明：制备的离子筛粉体粒径分布在100～500 nm之间,平均粒径为160 nm,用于察尔汗盐湖卤水中对Li⁺吸附容量达到31.44 mg·g^-1;孔径50 nm的陶瓷膜对离子筛的截留率达到100%,膜渗透通量大于150 L·m^-2·h^-1;反冲操作可有效维持吸附-膜分离过程的稳定性,吸附与陶瓷膜的耦合过程对盐湖卤水中的锂提取率超过97%,盐酸和双氧水清洗可有效恢复膜渗透通量。研究结果为高镁锂比盐湖卤水提锂提供了新方法。     

原位制备纳米银/羟基磷灰石/硅藻土复合陶瓷及其杀菌性能

采用原位复合法制备了纳米银/羟基磷灰石/硅藻土复合陶瓷,并对其微观结构、孔径分布、银释放性能及抗菌性能进行了研究。结果表明:纳米羟基磷灰石呈短棒状,分散于硅藻土颗粒表面及孔隙中;纳米银颗粒呈球形,均匀分散于复合陶瓷中,平均粒径为(5.79±2.46)nm。纳米银/羟基磷灰石/硅藻土复合陶瓷有良好的孔隙结构,平均孔径510 nm、中位孔径1 521 nm、孔隙率52.23%。复合陶瓷持续稳定释放的银对大肠埃希氏菌有优异杀菌效果,有望应用于终端水处理领域。     

共聚法制备疏水性SiO2气凝胶

以正硅酸乙酯为原料,应用溶胶-凝胶两步催化,甲基丙烯酸基丙基三甲氧基硅烷作为改性剂,无水乙醇为溶剂,共聚法常压下制备疏水性SiO₂气凝胶。运用原位红外在线监测反应历程,确定制备工艺步骤。运用N₂吸附仪、扫描电镜、红外光谱、TG-DSC对SiO₂气凝胶孔径分布、形貌、表面官能团及热稳定性进行分析。结果表明,经甲基丙烯酸基丙基三甲氧基硅烷改性的SiO₂气凝胶疏水性能良好,疏水的耐温性可达到407℃,比表面积为877.17 m²·g^-1, 由球形纳米颗粒堆积而成,颗粒尺寸范围在10～50 nm,孔径集中分布在1.9相似文献   

陶瓷膜射流法制备单分散异辛烷/甲酰胺乳液的研究

乳液模板法是制备高度有序多孔材料的重要方法之一.采用二次陶瓷膜乳化在射流条件下制备单分散乳液的方法成功制备出一种非水乳液模板.一次射流过程采用平均孔径为0.2 μm的ZrO2陶瓷膜作为乳化介质,二次射流乳化过程采用平均孔径为1.6 μm的α-Al2O3陶瓷膜作为乳化介质.异辛烷/甲酰胺体系为研究对象,三嵌段高分子聚(乙二醇)-聚(丙二醇)-聚(乙二醇)作为乳化剂,制备出平均粒径在1～2 μm的单分散乳液模板,并考察了操作压力、异辛烷浓度对液滴粒径及粘度的影响.     

低温烧结碳化硅陶瓷分离膜的制备及其油水分离性能（英文）

碳化硅陶瓷分离膜具有高亲水性、耐化学腐蚀、抗膜污染等优异性能,在大宗废水、强腐蚀废水、高温废水等的高效处理中受到广泛的关注。然而,碳化硅是典型的强共价键化合物,碳化硅陶瓷膜制备过程具有烧结温度高、制备能耗大等问题。本文采用优选的低熔点化合物作为烧结助剂,经1 000℃烧结制备了高强度、孔径均匀的碳化硅陶瓷分离膜。研究了烧结助剂含量对碳化硅陶瓷膜微观结构、孔径分布、相组成及油水分离性能等的影响。研究表明,低熔点烧结助剂连接碳化硅颗粒形成陶瓷的骨架结构,随着烧结助剂含量从10%（质量分数）增加到30%,碳化硅陶瓷膜的孔隙率从42%降低到35%,同时平均孔径从3.5μm降低到2.1μm,成孔模式由碳化硅颗粒堆积过渡到烧结助剂成孔。纯水实验表明,烧结助剂含量为30%时,随着跨膜压差从0.2 bar增加到0.5 bar碳化硅陶瓷膜的分离通量从120 L/（m²·h）增加到306 L/（m²·h）;油水分离实验表明,当跨膜压力差为0.2 bar时碳化硅陶瓷膜的截留率和分离通量分别为93.3%和123 L/（m²·h）。     

高温除尘碳化硅膜的制备及其抗腐蚀特性

采用喷涂法在碳化硅（SiC）支撑体上覆膜,根据碳化硅材料的氧化特性,设计了有氧烧结和氩气烧结随温度转换的组合烧结制度,并通过优化保温时间降低碳化硅陶瓷膜烧结成本。研究结果表明,新的烧结制度能有效地控制有氧烧结阶段产生的二氧化硅（SiO₂）量,并促进其与烧结助剂氧化锆（ZrO₂）等在气氛烧结阶段的反应,反应生成的锆英石相和添加莫来石相共同形成SiC颗粒连接颈部。制备的碳化硅陶瓷膜平均孔径为3.03 μm,气体通量为175 m³?m^-2?h^-1?kPa^-1。且在100℃的0.25 mol?L^-1的H₂SO₄溶液和0.25 mol?L^-1的NaOH溶液中腐蚀6 h后,膜层表面形貌无明显变化,具有较强的抗腐蚀性能。     

Ion-imprinted silica gel and its dynamic membrane for nickel ion removal from wastewaters

An ion-imprinted sorbent (IIP) was prepared by using Ni²⁺ as template, 3-[2-(2-aminoethylamino) ethylamino] propyl-trimethoxysilane as functional monomer, and silica gel as carrier. The adsorption performance of IIP towards Ni²⁺ was investigated. IIP showed a higher adsorption capacity than that of non-imprinted sorbent, and it also exhibited high selectivity for Ni²⁺ in the presence of Cu²⁺ and Zn²⁺ ions. Then, IIP was used to form a dynamic membrane onto the surface of ceramic membrane for treatment of electroplating wastewater containing Ni²⁺. Compared with ceramic membrane, IIP dynamic membrane had much higher steady membrane flux, and also rejected Ni²⁺ to obtain a lower concentration of Ni²⁺ in the permeate fluid. Perhaps it is suitable for future practice applications.     

聚间苯二甲酰间苯二胺平板膜的制备及其性能研究

以聚间苯二甲酰间苯二胺（PMIA）为制膜原料,氯化锂（LiCl）、聚乙二醇（PEG-400）和聚乙烯吡咯烷酮（PVP）为添加剂,通过非溶剂诱导相转化法制备了PMIA平板膜,系统考察了聚合物浓度、添加剂种类和含量对PMIA膜结构和性能的影响。结果表明,聚合物浓度和LiCl含量增加,铸膜液黏度增大,导致膜孔径减小,纯水通量降低。而PEG含量的增加,使得聚合物链呈现舒展状态,膜孔径增大,纯水通量升高,亲水性增强。随着PVP含量的增加,膜的纯水通量先升高后降低,膜的亲水性变差。当PMIA的质量分数为9%,LiCl的质量分数为2.8%,PVP的质量分数为1.2%时,膜的纯水通量高达1421.55 L·m^-2·h^-1·bar^-1,对牛血清蛋白（BSA）的截留率为80%,展现出较高的渗透性,为制备高性能膜材料提供了新的思路。     

One-electron reducibility of isolated copper oxide on alumina for selective NO–CO reaction

The H₂-TPR (temperature-programmed reduction) study was performed for supported copper oxide catalysts with low loading (0.5 wt% as copper). Among the various kinds of support materials (γ-Al₂O₃, TiO₂, ZrO₂, SiO₂, ZSM-5), alumina-supported copper oxide indicated a one-electron reduction behavior of Cu²⁺ into Cu⁺ ions in the presence of H₂. The reduction of the isolated Cu²⁺ species in a tetragonally distorted octahedral symmetry into the low coordinated Cu⁺ ions was identified by means of X-ray absorption spectroscopy (XANES and EXAFS). The isolated Cu⁺ ions hosted by γ-Al₂O₃ surface were prevented from further reduction into metallic Cu⁰ state under reducing condition with H₂ at 773 K. Less dispersed supported copper oxide species were easily reduced to Cu⁰ metal particles with H₂ at 573 K regardless of the kinds of support materials. It is suggested that the one-electron redox behavior of the isolated copper oxide species over γ-Al₂O₃ promotes the catalytic reduction of NO with CO in the presence of oxygen on the basis of redox-type mechanism between Cu²⁺ and Cu⁺ in atomically dispersed state.     

Cr2O3 promoted skeletal Cu catalysts for the reactions of methanol steam reforming and water gas shift

Promotional effects of chromia on the structure and activity of skeletal copper catalysts for methanol steam reforming and water gas shift have been studied. Catalysts were prepared by leaching CuAl₂ alloy particles in aqueous NaOH solutions containing sodium chromate at various concentrations. XPS spectra showed that the surface of the resulting catalysts mainly consisted of Cr³⁺ compounds and Cu⁰. Cu⁺ and/or Cu²⁺ were not observed by XPS.

Increasing the concentration of chromate in the leach liquor resulted in decreases in pore diameter and copper crystallite size but significant enhancement of BET surface area was observed while the total pore volume was maintained. The addition of small amounts of chromate to the leach liquor significantly enhanced the Cu surface area. However, higher concentrations of chromate in the leach liquor decreased the Cu surface areas although the total surface areas increased.

The activities of Cr₂O₃ promoted skeletal copper catalysts for both methanol steam reforming and water gas shift reactions were determined separately. The results indicated that deposition of Cr₂O₃ on skeletal copper catalysts significantly improved the specific activities for these reactions. Chromia is found to act as a structural and catalytic promoter for these reactions.     

聚间苯二甲酰间苯二胺平板膜的制备及其性能研究

以聚间苯二甲酰间苯二胺（PMIA）为制膜原料,氯化锂（LiCl）、聚乙二醇（PEG-400）和聚乙烯吡咯烷酮（PVP）为添加剂,通过非溶剂诱导相转化法制备了PMIA平板膜,系统考察了聚合物浓度、添加剂种类和含量对PMIA膜结构和性能的影响。结果表明,聚合物浓度和LiCl含量增加,铸膜液黏度增大,导致膜孔径减小,纯水通量降低。而PEG含量的增加,使得聚合物链呈现舒展状态,膜孔径增大,纯水通量升高,亲水性增强。随着PVP含量的增加,膜的纯水通量先升高后降低,膜的亲水性变差。当PMIA的质量分数为9%,LiCl的质量分数为2.8%,PVP的质量分数为1.2%时,膜的纯水通量高达1421.55 L·m^-2·h^-1·bar^-1,对牛血清蛋白（BSA）的截留率为80%,展现出较高的渗透性,为制备高性能膜材料提供了新的思路。     

陶瓷膜短流程工艺处理重金属废水

针对电镀行业重金属废水常规处理方法存在的药剂投加量大、污泥产量多、水质波动影响大等不足,本文提出了一种新工艺-陶瓷膜短流程处理工艺,即废水通过调节pH值使重金属离子形成相应的氢氧化物絮体后,直接进入陶瓷膜组件过滤,同时辅以曝气缓解膜污染。通过实验室小试研究了pH值、重金属质量浓度和曝气量等因素对重金属(Cu²⁺、Cr³⁺和Ni²⁺)去除效果以及陶瓷膜跨膜压差的影响,并进行现场中试验证。试验结果表明:pH=10时,Cu²⁺、Cr³⁺和Ni²⁺的去除率分别达到99.8%、99.7%和99.9%,耐冲击负荷强,原水重金属离子质量浓度为500mg/L时出水也能满足要求。气水体积比值为15时,能在保证出水水质的前提下显著缓解膜污染。该工艺中陶瓷膜的污染主要为可逆污染,可以通过水力反冲洗去除。在pH=10、气水体积比值为15和膜通量为80L/(m²·h)时,现场中试工艺出水中Cu²⁺、Cr³⁺和Ni²⁺的质量浓度分别低于0.15mg/L、0.3mg/L和0.1mg/L,而且跨膜压差保持稳定。     

Active sites of Cu-ZSM-5 for the decomposition of acrylonitrile

The catalytic decomposition of acrylonitrile (AN) over Cu-ZSM-5 prepared with various Cu loadings was investigated. AN conversion, during which the nitrogen atoms in AN were mainly converted to N₂, increased as Cu loading increased. N₂ selectivities as high as 90–95% were attained. X-ray diffraction measurements (XRD) and temperature-programmed reduction by H₂ (H₂-TPR) showed the existence of bulk CuO in Cu-ZSM-5 with a Cu loading of 6.4 wt% and the existence of highly dispersed CuO in Cu-ZSM-5 with a Cu loading of 3.3 wt%. Electron spin resonance measurements revealed that Cu-ZSM-5 contains three forms of isolated Cu²⁺ ions (square-planar, square-pyramidal, and distorted square-pyramidal). The H₂-TPR results suggested that in Cu-ZSM-5 with a Cu loading of 2.9 wt% and below, Cu⁺ existed even after oxidizing pretreatment. The activity of AN decomposition over Cu/SiO₂ suggested that CuO could form N₂, but, independent of the CuO dispersion, nitrogen oxides (NO_x) were formed above 350 °C. Cu⁺ and the square-pyramidal and distorted square-pyramidal forms of Cu²⁺ showed low activity for AN decomposition. Temperature-programmed desorption of NH₃ suggested that N₂ formation from NH₃ proceeded on Cu²⁺, resulting in the formation of Cu⁺. The Cu⁺ ions were oxidized to Cu²⁺ at around 300 °C. Thus, high N₂ selectivity over Cu-ZSM-5 with a wide range of temperature was probably attained by the reaction over the square-planar Cu²⁺, which can be reversibly reduced and oxidized.     

合成气经二甲醚羰基化及乙酸甲酯加氢制无水乙醇的研究进展

合成气经二甲醚羰基化及乙酸甲酯加氢路线制无水乙醇技术因具有诸多优点而备受市场关注。本文综述了该工艺的核心反应机理和最近研究进展。主要探讨了丝光沸石8元环与12元环对羰基化反应的作用。阐明了如何通过调变丝光沸石8元环与12元环的活性位来提高羰基化催化剂的活性与稳定性。评述了铜纳米粒子的粒径、分散度以及Cu⁺与Cu⁰的分布等特点对铜基催化剂加氢催化活性的影响。提高乙醇选择性与催化剂稳定性是该研究的重点与难点。指出羰基化催化剂的优化重点是调变丝光沸石的孔道结构,加氢催化剂的发展方向是构建高分散度的铜纳米粒子,并在反应过程中保持稳定。     

海胆状Fe3O4@TiO2磁性纳米介质对Pb2+的选择吸附特性

耦合溶胶-凝胶技术与水热法,制备具有核壳结构的海胆状Fe₃O₄@TiO₂磁性纳米介质（sea urchin magnetic nanoparticles,SUMNPs）。采用TEM、SEM等方法对SUMNPs的形貌等性质进行表征,证实该材料呈现出以Fe₃O₄为核,以TiO₂为壳的海胆状结构,壳层直径约400 nm,比表面积高达236.082 m²·g^-1,表面孔径约6.274 nm。SUMNPs对重金属离子选择吸附的结果表明,基于Pb²⁺离子半径大、电子层数多等物化特点,在Pb²⁺、Cu²⁺、Ni²⁺、Zn²⁺、Cd²⁺ 5种金属离子混合体系中,SUMNPs可以高容量、高选择性快速吸附Pb²⁺,而对其他4种重金属离子几乎无吸附活性。单一Pb²⁺吸附可在5 min内快速平衡,平衡吸附容量为283 mg·g^-1。吸附过程符合Langmuir等温吸附模型,SUMNPs对Pb²⁺的最大饱和吸附容量为458.72 mg·g^-1。经EDTA二钠解吸,NaOH再生后的SUNMPs可以重复使用8次以上。SUMNPs对Pb²⁺具备优异的选择性吸附性能,在处理水体铅污染、恢复水体生态领域具有良好的应用前景。     

高浓度含铜电镀废水膜电解处理与回用

随着电镀行业的发展，电镀废水排放造成的污染问题一直困扰着研究者。而针对其中高浓度含铜电镀废水少污染、可回收的目标，开发了单膜双室膜电解法处理并回收铜的新工艺，本实验研究了其运行方式、回收效果与机理并对回收的产物进行表征。在一个电解槽内阴阳两极之间放入一张阴离子交换膜，研究了初始Cu²⁺浓度、电流密度、pH、极板间距、温度和添加剂等运行参数对铜回收率和能耗的影响。在Cu²⁺初始浓度50g/L，阴极板电流密度400A/m²，温度40℃，极板间距30mm，阴极室pH=6.5，添加1g/L硝酸铵的最优工况下，测得铜回收率可以达到96.1%，电流效率超过70%，并且反应能耗为5737kWh/t。同时通过表征分析在最佳工艺条件下电解回收的铜，发现其颗粒较小、大小均匀、棱角分明，且其纯度高，具有较高的经济价值。