用于燃烧前CO2捕集的微孔Nb2O5膜的制备及其水热稳定性能

以五正丁氧基铌为前驱体,通过溶胶-凝胶法制备出稳定的Nb₂O₅聚合溶胶,详细考察了溶胶制备过程参数(体系酸度、水解比、反应温度、反应时间和螯合剂用量)对溶胶尺寸、稳定性以及制备重复性的影响。采用平均粒径为4.8 nm的Nb₂O₅溶胶,通过浸浆法在平均孔径为3 nm的γ-Al₂O₃中孔膜上制备出Nb₂O₅微孔膜。利用TG、XRD、NH₃吸附-脱附、CO₂吸附、吡啶吸附傅里叶变换红外光谱(Py-IR)和单组分气体渗透实验等手段对Nb₂O₅粉体及微孔膜的性能进行了表征,结果表明:在200℃、0.3 MPa条件下,350℃烧成的微孔Nb₂O₅膜对H₂的渗透率和H₂/CO₂的理想分离因子分别为3.1×10^-9 mol·m^-2·s^-1·Pa^-1和21。此外,微孔Nb₂O₅膜经150 kPa的水蒸气处理8 h后,膜的渗透性能以及H₂/CO₂理想选择性基本保持不变。     

镍掺杂SiO_2膜的制备及CH_4/CO_2气体分离性能

以正硅酸乙酯(TEOS)为前驱体,六水合硝酸镍(Ni(NO3)2·6H2O)为镍源,采用溶胶--凝胶法制备镍掺杂SiO2膜。研究了水用量及镍含量对镍掺杂SiO2膜的结构及形貌的影响,并对其进行CH4、CO2气体渗透性能测试。结果表明:水酯比为5.5时,制备的10%Ni掺杂SiO2膜具有良好的微孔结构,且孔径约为1.16nm,孔隙率为64.9%。一部分Ni元素以Ni和NiO晶体形式填充于SiO2孔道内,另一部分以Si—O—Ni形式进入SiO2骨架。Ni掺杂SiO2膜在84h内能够保持良好的气体渗透性能,表现出比纯SiO2膜更好的水热稳定性。CH4和CO2的气体渗透通量分别为1.56×10--7和0.64×10--7 mol/(m2·s·Pa),CH4/CO2气体分离因子达到2.43。     

TiO_2中孔膜的制备及对Ni~(2+)的截留性能

以钛酸四异丙酯为前驱体,通过颗粒溶胶路线制备出平均粒径为41nm的TiO2溶胶,并以此溶胶制备出稳定的制膜液。采用浸浆法,经过一次涂膜和在400～600℃烧成,在平均孔径约为70nm的片状α-Al2O3支撑体上制备出完整无缺陷的截留分子量小于10000的TiO2中孔膜。考察了烧成温度对非担载TiO2粉末和TiO2中孔膜性能的影响。结果表明:在400℃烧成3h可制备出孔径为4.7nm的TiO2中孔膜,其对PEG的截留分子量为8150,在0.8MPa,20℃下,纯水渗透通量为30L/(m2·h),对pH=3的Ni(NO3)2溶液的截留率达到95.14%。     

ZrO2中孔膜的制备及其耐酸碱腐蚀性能

以正丙醇锆为前驱体,通过颗粒溶胶路线制备ZrO2溶胶,并以此溶胶制备出稳定的制膜液. 采用浸浆法,经过一次涂膜,在平均孔径约为70 nm的片状a-Al2O3支撑体上制备出完整无缺陷的孔径小于10 nm的中孔ZrO2陶瓷膜,详细考察了烧成温度对ZrO2粉末和ZrO2中孔膜性能的影响. 在450℃的烧成温度下制备出孔径约为7 nm的ZrO2中孔膜,该膜对PEG的截留分子量为19500,在原料液侧压力为0.76 MPa、温度(23±1)℃条件下,纯水渗透通量为30~35 L/(m2×h). 经HNO3(pH=2)和NaOH(pH=13)溶液动态腐蚀后的ZrO2中孔膜对PEG截留分子量的变化表明,所制ZrO2膜具有较高的耐酸碱腐蚀性能.     

Ti/Zr复合纳滤膜的制备及其性能

通过聚合溶胶路线制备出稳定的Ti/Zr(摩尔比=1:1)复合溶胶。采用浸浆法,在平均孔径为5～6 nm的片状a-Al₂O₃/g-Al₂O₃载体上制备出完整无缺陷的Ti/Zr复合纳滤膜。详细考察了焙烧温度对Ti/Zr粉体的影响,并考察了Ti/Zr复合纳滤膜的性能。结果表明:在较高烧成温度下(500℃),Ti/Zr粉体依然呈无定形态且保持微孔结构。在400℃烧成温度下制备出孔径为1.49 nm的Ti/Zr复合纳滤膜,该膜的截留分子量(MWCO)为880,纯水通量为4.3 L·m^-2·h^-1·MPa^-1。在pH=6,压力0.8 MPa的条件下,该膜对0.005 mol·L^-1的MgCl₂、CaCl₂的截留率分别为85%和78%。     

浸渍工艺及烧成温度对SiO2纳滤膜微观结构的影响

以平均粒径为10 nm和80 nm的硅溶胶为主要原料,采用浸渍提拉法在50 nm超滤支撑体上制备了SiO2纳滤膜.研究了烧成温度对膜层密度和气孔率、物相组成、热膨胀及显微结构的影响,探讨了溶胶浓度与膜厚度的关系,确定了合适的烧结温度和镀膜工艺.结果表明:随烧结温度升高至800℃以上时,SiO2纳滤膜的密度显著提高,在850℃以上会析出方石英相,导致其在200℃左右因方石英相变而出现膨胀突变;600℃和700℃分别是10 nm和80 nm硅溶胶制备的SiO2纳滤膜的合适烧结温度;以浓度为16.9wt％的10 nm硅溶胶镀膜在600℃烧成后可以形成微结构均匀、厚度约1μm的SiO2纳滤膜.     

γ-Al2O3中孔陶瓷膜的制备及表征

以粒径为0.3～0.4 μm的α-Al2O3为原料,通过悬浮液真空抽吸法,制备出平均孔径约为70 nm的完整无缺陷的片状α-Al2O3支撑体;以仲丁醇铝为前驱体,采用颗粒溶胶路线制备出稳定的Boehmite溶胶,以此溶胶采用浸浆法,在制备的α-Al2O3支撑体上制备出完整无缺陷的γ-Al2O3中孔膜,并考察了烧成温度对γ-Al2O3中孔膜性能的影响.结果表明,本文制备出的γ-Al2O3膜的孔径约为3 nm,对PEG的截留分子量为2800～5300,纯水渗透通量为11.5～25.9 L·m-2·h-1[7.6×105 Pa,(14±1)℃].说明在孔径为70 nm左右的载体上直接制备孔径为3 nm的完整的中孔膜是可行的.     

SiO2基多孔陶瓷膜支撑体的制备

以海泡石矿物为原料,通过干压成型制备了氧化硅( SiO2)基多孔陶瓷膜支撑体,研究了烧成温度对制备试样的物相组成、微观结构、平均孔径、孔隙率、纯水渗透通量和抗弯强度的影响.结果表明,经1100 ～ 1200℃保温2h烧成制备的SiO2基多孔陶瓷支撑体试样主要由石英主晶相和少量滑石晶相组成,具有良好的结构与性能,可用于SiO2复合陶瓷膜的制备.1200℃烧成制备的试样孔隙率和平均孔径分别为31.4％和1.72 μm,其水通量和抗弯强度分别可达到20.30 m3·m-2·h-1·bar-1和61.0 MPa.     

骨质瓷用纳米SiO_2/Al_2O_3复合釉的制备及性能研究

研究了六偏磷酸钠对纳米SiO2、Al2O3在水中和骨质瓷釉料中的分散性以及纳米SiO2/Al2O3对骨质瓷成品性能的影响。采用了吸光度实验、釉料流变性、烧成温度、疏水性测试手段。结果表明,在实验条件下,纳米SiO2、Al2O3在水中最佳分散条件均为:0.25%六偏磷酸钠,0.5%纳米粉,pH为10。纳米SiO2/Al2O3在骨质瓷基釉中最佳分散条件为:0.25%六偏磷酸钠,2%纳米SiO2/Al2O3(按釉料化学组成比混合),pH为10,基釉200mL。以此釉料烧成的骨质瓷制品,烧成温度降低约30℃,表面由亲水性变为疏水性。     

耐酸ZrO2·SiO2涂层材料的低温合成研究

采用溶胶-凝胶法,添加适量的矿化剂V2O5,在1300℃以下,合成微米级ZrO2·SiO2涂层。研究了矿化剂添加量、烧成温度和保温时间等因素对ZrO2·SiO2合成以及涂层抗酸腐蚀的影响作用关系,为ZrO2·SiO2涂层的合成与制备提供了可靠的实验依据。     

Gas separation using sol-gel derived microporous zirconia membranes with high hydrothermal stability☆

A microporous zirconia membrane with hydrogen permeance about 5 × 10?8 mol·m?2·s?1·Pa?1, H2/CO2 permselectivity of ca. 14, and excellent hydrothermal stability under steam pressure of 100 kPa was fabricated via polymeric sol–gel process. The effect of calcination temperature on single gas permeance of sol–gel derived zirconia membranes was investigated. Zirconia membranes calcined at 350 °C and 400 °C showed similar single gas permeance, with permselectivities of hydrogen towards other gases, such as oxygen, nitrogen, methane, and sulfur hexafluoride, around Knudsen values. A much lower CO2 permeance (3.7 × 10?9 mol·m?2·s?1·Pa?1) was observed due to the interaction between CO2 molecules and pore wall of membrane. Higher calcination tem-perature, 500 °C, led to the formation of mesoporous structure and, hence, the membrane lost its molecular siev-ing property towards hydrogen and carbon dioxide. The stability of zirconia membrane in the presence of hot steam was also investigated. Exposed to 100 kPa steam for 400 h, the membrane performance kept unchanged in comparison with freshly prepared one, with hydrogen and carbon dioxide permeances of 4.7 × 10?8 and~3 × 10?9 mol·m?2·s?1·Pa?1, respectively. Both H2 and CO2 permeances of the zirconia membrane de-creased with exposure time to 100 kPa steam. With a total exposure time of 1250 h, the membrane presented hydrogen permeance of 2.4 × 10?8 mol·m?2·s?1·Pa?1 and H2/CO2 permselectivity of 28, indicating that the membrane retains its microporous structure.     

基于纯硅沸石修饰层的钯复合膜制备方法研究

以大孔α-Al_2O_3陶瓷管(平均孔径为3μm)为载体,采用水热合成法在其表面形成一层纯硅沸石(Silicalite-1)修饰层,利用化学镀法在经过纯硅沸石修饰后的载体表面成功制备出致密钯复合膜,钯膜厚度约为5 μm.利用SEM对复合膜的结构和形貌进行了分析,并在350～500℃范围内对基于纯硅沸石修饰层的钯复合膜进行气体渗透测试表明,该沸石层修饰法制备的钯复合膜具有良好的氢渗透性.在500℃时,氧气渗透通量可达为0.12mol/(m~2·s),理想气体分离因子α(H_2/N_2)达到420.并对该钯膜与在载体表面直接制备的钯复合膜性能的差异进行了讨论.     

改性高岭土捕集CdCl2、PbCl2蒸气

针对两种重金属氯化物PbCl₂、CdCl₂,探究高岭土表面羟基对吸附重金属的作用。对高岭土进行煅烧及水热改性,并在两段式管式炉上进行高岭土捕集重金属氯化物蒸气实验,并使用原子吸收分光光度计（AAS）测量吸附剂中的重金属氯化物含量。吸附数据表明对于PbCl₂及600～700℃的CdCl₂吸附,高岭土经过煅烧吸附效率大幅降低,水热重新赋予羟基后吸附效率有所提升,但仍低于原高岭土。结合热重（DTG）及红外谱图（FTIR）分析可知,高岭土经800℃煅烧脱除全部羟基,经水热重新获得部分羟基,且所获数量随水热程度的加深而增多,结合XRD谱图可知羟基促进了高岭土与重金属氯化物的吸附反应;800℃以上高温下原高岭土吸附效率逐渐低于煅烧高岭土和水热高岭土,结合核磁共振谱图（NMR）分析可知其原因在于,高岭土经煅烧改性及水热改性,Al原子配位数降低,活性增强,更易与重金属氯化物蒸气结合。     

Effect of calcination temperature of kaolin as a support for zeolite membranes

Ceramic membranes specially zeolite membranes are usually used for dewatering of organics by pervaporation. In the previous work, it was observed that kaolin calcined at 1050 °C has a separation factor 19.25 while kaolin calcined at 800 °C does not show any separation activity and its separation factor is equal to 1. In this research, effect of calcination temperature on flux and separation factor of kaolin modules that prepared by electrophoresis as a support of zeolite membranes was investigated. By increasing the kaolin calcination temperature, the flux of membrane increases due to many pores created in the module. This was confirmed by SEM micrographs. The highest flux was about 18 kg/m² h for modules calcined at 1200 °C with ethanol 95%. Their separation factors were almost the same for each module. It was very low but comparable with some porous and non-porous polymeric membranes. Increasing calcination temperature causes module strength to enhance. It was found that the module calcined at 1200 °C may be suitable as a support for zeolite A membranes.     

载体焙烧温度对Ni/SiO2-Al2O3催化剂稳定性的影响

为了获得高水热稳定的负载Ni催化剂,延长催化剂在含水液相体系中的使用寿命,以不同温度焙烧的SiO₂-Al₂O₃为载体,采用浸渍法制备Ni/SiO₂-Al₂O₃催化剂,通过吡啶-原位傅立叶变换红外光谱、X射线衍射、NH₃-程序升温脱附和H₂-程序升温还原等方法进行表征,以水相1,4-丁炔二醇加氢为探针反应,研究载体焙烧温度对Ni/SiO₂-Al₂O₃催化剂催化加氢性能及含水体系中稳定性的影响。结果表明,在(400~800) ℃,随着载体焙烧温度升高,活性组分Ni存在状态及催化剂加氢活性变化较小,但催化剂的水热稳定性下降,造成这一现象的原因是随着载体焙烧温度升高,载体表面SiO₂聚集,暴露的Al³⁺增加,载体水合程度增大。载体焙烧温度400 ℃时,Ni/SiO₂-Al₂O₃催化剂表现出最佳的水热稳定性。     

Influence of the intermediate layer on the hydrothermal stability of sol-gel derived hybrid silica membranes

The hydrothermal stability of microporous silica hybrid sol-gel derived membranes is often only tested for either the mesoporous intermediate membrane layer or the microporous separation layer. In this work an investigation is done on the interaction between the intermediate γ-alumina layer and the hybrid (BTESE-derived) silica separation layer during hydrothermal treatment. Although bare γ-alumina is degraded during a hydrothermal treatment, a coating of hydrophobic BTESE on γ-alumina retains its gas separation performance, albeit with a lower mechanical adhesion between the hybrid silica separation layer and the γ-alumina intermediate layer. Applying a monoaluminumphosphate (MAP) coating between the α-alumina support and the γ-alumina layer stabilizes the γ-alumina membrane. A BTESE coating on a MAP modified γ-alumina membrane did not show any signs of delamination after hydrothermal testing. Moreover, a significant increase in the H₂^/N₂ (perm)selectivity, factor 3, was observed for these membranes.     

ZSM-5分子筛膜的形成过程及其影响因素

采用打磨法在多孔-αAl2O3载体上引入尺寸为100 nm的分子筛晶种,再用水热法合成了ZSM-5分子筛膜。考察了合成液中硅铝比、水硅比和碱度等对成膜的影响,并对合成的膜进行SEM、XRD表征。结果表明,在反应液配比为n(SiO2)∶n(Al2O3)∶n(Na2O)∶n(NBA)∶n(H2O)=100.0∶1.0∶9.0∶20.0∶3 000.0时,合成分子筛膜最好,膜厚约为11μm。并通过不同时间下的膜的SEM图表征膜的成膜过程,成膜主要是液相机制起作用,即存在于溶液中硅酸根和铝酸根离子在晶种的表面上缩聚使晶体长大。     

以正硅酸乙酯和1,2-二(三乙氧基硅基)乙烷为前驱体制备微孔SiO2复合膜及其气体分离性能

This paper reports on ¬¬¬a new microporous composite silica membrane prepared via acid-catalyzed polymeric route of sol-gel method with tetraethylorthosilicate (TEOS) and a bridged silsesquioxane [1, 2-bis(triethoxysilyl)ethane, BTESE] as precursors. A stable nano-sized composite silica sol with a mean volume size of ~5 nm was synthesized. A 150 nm-thick defect-free composite silica membrane was deposited on disk support consisting of macroporous α-Al2O3 and mesoporous γ-Al2O3 intermediate layer by using dip-coating ap-proach, followed by calcination under pure nitrogen atmosphere. The composite silica membranes exhibit molecular sieve properties for small gases like H2, CO2, O2, N2, CH4 and SF6 with hydrogen permeances in the range of (1-4)107 mol•m2•s1•Pa1 (measured at 200 C, 3.0×105 Pa). With respect to the membrane calcined at 500 C, it is found that the permselectivities of H2 (0.289 nm) with respect to N2 (0.365 nm), CH4 (0.384 nm) and SF6 (0.55 nm) are 22.9, 42 and >1000, respectively, which are all much higher than the corresponding Knudsen values (H2/N2 3.7, H2/CH4 2.8, and H2/SF6 8.5).