冶金固体废弃物精细化利用过程中中间体的聚合行为

对冶金固体废弃物精细化利用过程中中间体?含镁、铝离子硅酸体系中硅酸胶凝时间、单硅酸聚合速度及溶胶胶粒生长进行了研究. 结果表明,在pH<4的酸性范围内,Mg2+与Al3+离子促进硅酸的聚合反应,在反应初期Al3+已明显促进反应进行. 且Al3+与硅酸负离子、OH-的结合能力均强于Mg2+,其对硅酸的促凝作用较强;Mg2+和Al3+等浓度共存时,促凝效果介于单金属离子之间;Mg2+与Al3+促进了硅酸体系中溶胶胶粒的生长及SiO2粒子的长大,Al3+进入凝胶内部取代硅形成四面体配位;凝胶后所得SiO2为非晶态结构.     

镁铝离子共存硅酸体系的聚合行为

通过对镁铝离子共存硅酸体系中硅酸胶凝时间、单硅酸聚合反应速率以及凝胶热性能的研究,得出:在pH4的微酸性条件下,硅酸体系的胶凝时间随镁铝离子共存浓度的增大而减小,且铝离子在对硅酸体系的促凝过程中起主要作用。镁铝离子共存硅酸体系的单硅酸反应速率常数比不含金属离子硅酸体系的有所增大,计算得出MA0.1+0.1硅酸体系的单硅酸平均速率常数为:0k=7.28×10?4,1k=5.62×10?4。镁铝离子共存硅酸体系凝胶的晶化转变温度与晶型转变温度,相较于不含金属离子硅酸体系的均有所降低,根据热重曲线计算出MA0.1+0.1硅酸体系水合二氧化硅的化学式为:SiO2·0.556 H2O。     

溶胶-凝胶法制备Fe_2O_3/Al纳米复合材料

采用溶胶-凝胶法和真空干燥法制备了Fe2O3/Al纳米复合材料。用扫描电镜、红外光谱、X射线衍射仪(XRD)、BET比表面分析仪对原料和产物的结构和性能进行了表征。结果表明,纳米复合材料的宏观粒子平均粒径为2μm,纳米铝粉均匀分布在Fe2O3凝胶体系中,平均粒径为40nm。空白Fe2O3干凝胶比表面积达64.6m2/g,填充铝粉后样品的比表面积为1.1m2/g。撞击感度试验表明,Fe2O3凝胶与纳米铝粉复合后,特性落高由30.5cm提高到100.3cm,表明FeO凝胶可降低纳米铝粉的冲击感度。     

制备条件对钴掺杂二氧化硅溶胶胶粒粒径和膜孔结构的影响

以正硅酸乙酯(TEOS)为前驱体,六水合硝酸钴(Co(NO_3)_3·6H_2O)为钴源,十六烷基三甲基溴化铵(CTAB)为模板剂,通过溶胶-凝胶-模板技术制备了不同条件下的微孔钴掺杂二氧化硅膜。研究了酸量、水量、钴掺杂量、焙烧温度对溶胶胶粒粒径及膜材料孔结构的影响。结果表明:酸和水添加量以及焙烧温度相对于钴掺杂量是主要的影响因素。溶胶胶粒粒径随着酸量的增多先减小后增大,在HNO_3/TEOS摩尔比为0.055时溶胶胶粒粒径达到最小值;随着水量的增大而粒径增大,且粒径分布变宽,在H_2O/TEOS摩尔比为10时最明显;随着酸量和焙烧温度的增大,膜材料的比表面积和微孔孔容先增大后降低,在HNO_3/TEOS摩尔比为0.085时,450℃焙烧的膜材料的比表面积和微孔孔容达到最大值。     

Ca2+,Al3+对不含Na+硅酸体系聚合行为的影响

为排除Na+对硅酸聚合的影响,用酸解水淬硅酸钙制备了不含金属离子的硅酸溶液及含Ca2+, Al3+的硅酸溶液,研究了加入Ca2+, Al3+对体系聚合行为的影响. 结果表明,加入Ca2+后体系pH值略微降低,加入Al3+后体系pH值显著降低. 初始pH≤2时,Al3+对硅酸聚合起促凝作用,初始pH>2时,Al3+起缓凝作用. Ca2+对硅酸聚合影响不大. 硅酸凝胶后,含Al3+硅酸体系中形成Al?O?Si键,阻碍了凝胶结构水脱附;Ca2+则阻碍凝胶的晶化转变过程,且凝胶中的结构水变少. 不含金属离子、含Ca2+、含Al3+体系的化学式分别为SiO2×0.52H2O, SiO2×0.36H2O, SiO2×1.50H2O.     

镁铝离子共存硅酸体系的聚合行为

通过对镁铝离子共存硅酸体系中硅酸胶凝时间、单硅酸聚合反应速率以及凝胶热性能的研究,得出：在pH<;4的微酸性条件下,硅酸体系的胶凝时间随镁铝离子共存浓度的增大而减小,且铝离子在对硅酸体系的促凝过程中起主要作用。镁铝离子共存硅酸体系的单硅酸反应速率常数比不含金属离子硅酸体系的有所增大,计算得出MA_0.1+0.1硅酸体系的单硅酸平均速率常数为：k₀=7.28×10^-4,k₁=5.62×10^-4。镁铝离子共存硅酸体系凝胶的晶化转变温度与晶型转变温度,相较于不含金属离子硅酸体系的均有所降低,根据热重曲线计算出MA_0.1+0.1硅酸体系水合二氧化硅的化学式为：SiO₂·0.556 H₂O。     

Fe/TiO2/MCM-41复合光催化材料的制备及表征

采用溶胶-凝胶法制备了掺杂与负载相结合的光催化剂Fe/TiO2/MCM-41,通过考察掺杂金属种类和掺杂量,探讨了制备条件对复合材料性能的影响,并用XRD、BET、TEM和XPS对其进行表征。结果表明,Fe3+掺杂量为0.05%时,光降解初始浓度为25 mg/L的甲基橙溶液30 min后脱色率达到95%以上。Fe/TiO2/MCM-41是一种比表面积达349.77 m2/g的介孔材料,具有锐钛矿和金红石相的混晶结构;光催化剂中铁以+3价形式存在,表面羟基氧所占比例为37%,掺杂铁抑制了TiO2粒子的生长。将Fe/TiO2/MCM-41用于光催化氧化水中的对硝基苯甲酸,当催化剂投加量为0.5 g/L、对硝基苯甲酸初始pH为5、浓度为2×10-4mol/L时,紫外光照30 min后,对硝基苯甲酸降解率达到58%以上。     

溶胶凝胶水热法制备Fe~(3+)掺杂纳米TiO_2的应用研究

钛酸正丁酯为前驱体、聚乙二醇(PEG-4000)为模板剂,溶胶凝胶水法制备Fe3+掺杂纳米二氧化钛,考察其对苯酚光催化降解性能。在水量2mL、乙醇量45mL、冰醋酸2.5mL、pH值1.5和Fe3+掺杂量0.07%(Fe3+/Ti4+物质的量比)条件下,可得到平均孔径为3.73nm、孔径分布范围2.8~11.4nm、孔容为0.412cm3/g和比表面积为108.794m2/g的Fe3+掺杂纳米二氧化钛粉末,对苯酚降解率达到87.6%,比未掺杂提高了18.3%。     

溶胶-凝胶法制备粒径可控的纳米钛酸铅

纳米钛酸铅是一种应用广泛的压电材料。采用溶胶-凝胶法研究了纳米钛酸铅的制备,考察了凝胶的煅烧温度、反应物的浓度及溶胶的反应温度对纳米颗粒粒径的影响和变化规律。研究表明,控制钛酸丁酯-醇溶液浓度为0.100～1.000 mol/L、醋酸铅-醋酸浓度为0.500～1.500 mol/L、溶胶反应温度为70～90℃、凝胶煅烧温度为400～800℃,可制备出平均粒径在20～50 nm范围的近似球形的四方相纳米钛酸铅。制备条件对纳米钛酸铅的粒径有显著影响:随溶胶反应温度和凝胶煅烧温度的升高,所制备纳米钛酸铅平均粒径增大;当醋酸铅-醋酸溶液浓度为1.500 mol/L,随钛酸丁酯-醇溶液浓度由0.100 mol/L增大至1.000 mol/L,所制备纳米钛酸铅粒径先增大后减小。制备粒径可控的纳米钛酸铅对其性能及应用具有重要的价值。     

制备方法对Al/Fe_2O_3纳米铝热剂性能的影响

分别采用超声共混法、机械球磨法和溶胶-凝胶法制备出Al/Fe2O3纳米铝热剂。研究了3种制备方法对纳米铝热剂晶型、平均粒径、形貌、比表面积和热反应性能的影响。结果表明,超声共混法只能使两组分简单地混合在一起;机械球磨法通过机械作用力使两组分混合均匀,但部分Al颗粒破裂,平均粒径减小;溶胶-凝胶法制备的Fe2O3凝胶均匀包裹着Al颗粒,形成核壳结构的Al/Fe2O3纳米铝热剂,有效地保护了Al颗粒,同时纳米铝热剂具有高的比表面积,固—固反应放热量为896J/g。     

核桃青皮醇提物对棉织物染色性能的研究

为解决天然染料核桃青皮染色色调单一的问题,以颜色特征值和染色牢度为指标,通过单因素和正交实验优化了影响染色效果的温度、时间、pH值及核桃青皮色素染液的质量浓度等因素,比较了单金属盐的不同媒染方法和双金属盐复配对纯棉织物染色性能的影响。结果表明,核桃青皮色素染色的优化条件为：温度90oC、质量浓度71.40 g/L、染浴pH=4.0、时间140 min。核桃青皮提取液染色棉织物色谱的范围广,耐摩擦牢度好;耐皂洗牢度上单金属盐媒染是后媒＞前媒＞同浴＞直接染色,双金属盐复配及Fe3+、Fe2+、Cu2+、Al3+、Cr6+等单金属盐媒染的耐皂洗色牢度均能达到3级以上。X-射线衍射分析表明棉织物内部结构未受影响,Fe3+、Fe2+、Cr6+、Sr2+、Na+和K+等单金属盐和Fe2+/Cu2+、Fe2+/Ti4+、Cu2+/Ti4+、Cu2+/Sn2+、Al3+/Cr6+、Cr6+/Ti4+和Cr6+/Sn2+等双金属盐媒染后的棉织物紫外线防护能力增强。     

TiO2掺杂粉体的溶胶-凝胶和水热合成及其光降解甲醛

为了研究不同掺杂对二氧化钛光化学活性的影响,采用溶胶-凝胶,水热法,由TiOCl2成功制备了掺杂氮原子的二氧化钛样品,并制备了掺杂0.5%(摩尔分数)Fe3 ,Gu2 ,V5 ,Pd2 等金属离子的可见光响应型介孔材料.样品经由X射线衍射,透射电镜,Brunauer-Emmett-Teller(BET)比表面积,Barrett-Joyner-Halenda孔径分布,紫外可见光谱,光电子能谱和荧光光谱等表征;以荧光灯为光源(入射光波长λ≥410 nm),光催化降解甲醛为模式,评价了样品的催化活性.结果表明:掺杂Fe3 ,Cu2 ,V5 ,Pd2 的二氧化钛和单一掺氮的二氧化钛样品的粒径均为10 nm左右,BET比表面积为130 m2/g左右,均为锐钛矿相二氧化钛;Fe/TiO2,Cu/TiO2,V/TiO2,Pd/TiO2和TiO2/N样品的带隙能依次为:2.99,2.93,2.36,2.92 eV和2.87 eV,其在可见光下的光催化降解速率常数分别为:0.006 3,0.008 6,0.004 9,0.003 l/min和0.003 3/min.Cu/TiO2较高的荧光强度和较大的比表面积,导致了其较高的可见光光解活性.     

铜渣铁基类沸石地质聚合物吸附Pb2+、Cu2+、Zn2+性能及机理

以铜渣为原料，在NaOH+工业水玻璃活化条件下制备出了铜渣Fe3O4@铁基类沸石地质聚合物（F3O4@GM），并将其用于三种重金属Pb2+、Cu2+、Zn2+吸附。探究了溶液pH、吸附剂投加量和初始浓度对Pb2+、Cu2+、Zn2+吸附性能的影响，并通过吸附动力学、热力学以及XRD、FTIR、SEM、BET、XPS等表征手段对其吸附机理进行探讨。结果表明，F3O4@GM对Pb2+、Cu2+、Zn2+的吸附符合Langmuir模型，吸附容量分别为555 mg/g、489 mg/g、125 mg/g；吸附过程符合拟二级动力学模型。F3O4@GM高比表面积提高了材料的吸附性能，吸附机理主要为离子交换、静电吸引、表面络合和孔隙固定作用。F3O4@GM为重金属污染处理提供了一种价格低廉、制备方便的选择，同时实现了铜渣资源化和无害化处理，具有良好的经济效益和环境效应。     

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。     

Interactions in the Silicon Carbide–Polyacrylic Acid–Yttrium Ion System

Interactions in the SiC powder–polyacrylic acid (PAA, dispersant)–Y³⁺ ion (sintering additive) system were investigated in the pH range from 2 to 6. The amount of Y³⁺ ions adsorbed on SiC particles increased with an increase of pH because of the electrostatic attraction between the negatively charged SiC surface and Y³⁺ ions. On the other hand, the amount of PAA adsorbed on SiC particles decreased with increasing pH because of the electrostatic repulsion between the negatively charged SiC surface and dissociated PAA. The addition of PAA to the SiC suspension with Y³⁺ ions increased the amount of Y³⁺ ions fixed to SiC particles through the strong interaction between Y³⁺ ions and PAA adsorbed on SiC particles. The above-described interactions in the SiC–PAA–Y³⁺ ions system were closely related to the coagulation of SiC particles and the rheology of SiC suspensions. The coagulation of SiC particles through the adsorbed Y³⁺ ions decreased the specific surface area of SiC powder after calcination in an argon atmosphere. The addition of PAA to the SiC suspensions with Y³⁺ ions kept the SiC particles separate during calcination, i.e., the PAA addition contributed to enhancement of the driving force of sintering (no decrease of specific surface area) and to control of the amount of Y³⁺ ions uniformly fixed to the SiC surface.     

DETERMINATION OF THE OPTIMUM PREPARATION CONDITION OF THE SOL-GEL SiO2 USING THE RESPONSE SURFAC METHODOLOGY

A typical sol - gel process consists of the liquid reaction, the solution gelation, and followed by the dehydration. The surface properties of silica gel such as surface area, pore volumes, and the pore diameter were affected by the manufacturing variables including pH values, gelation and dehydration temperatures. The objective of this study is to determine the optimum preparation conditions to maximize a response of surface area, or minimize its pore diameter. In addition, interactions between process variables were studied and their significance to the surface properties was also weighted. It was found that the surface area of silica gels increased with an increasing amount of NH₄OH to a maximum value and then decreased. As a drying temperature kept constant, the surface area and the pore volume increased with an increasing gelation temperature. However, the pore diameter was not influenced by this factor and the pore size was almost uniform at a low NH₄OH concentration. For a higher NH₄OH concentration, the pore volume and the pore diameter became larger but the surface area became smaller as the gelation temperature increased. By means of the response surface methodology analysis, the optimum processing condition was found to be 0.0155 mole of NH₄OH, 80,3°C for gelation temperature, and 63.2°C for the dehydration. As a result the maximum surface area corresponding to the optimum preparation conditions was 818.9 (m²/g) as expected.     

DETERMINATION OF THE OPTIMUM PREPARATION CONDITION OF THE SOL-GEL SiO2 USING THE RESPONSE SURFAC METHODOLOGY

A typical sol - gel process consists of the liquid reaction, the solution gelation, and followed by the dehydration. The surface properties of silica gel such as surface area, pore volumes, and the pore diameter were affected by the manufacturing variables including pH values, gelation and dehydration temperatures. The objective of this study is to determine the optimum preparation conditions to maximize a response of surface area, or minimize its pore diameter. In addition, interactions between process variables were studied and their significance to the surface properties was also weighted. It was found that the surface area of silica gels increased with an increasing amount of NH₄OH to a maximum value and then decreased. As a drying temperature kept constant, the surface area and the pore volume increased with an increasing gelation temperature. However, the pore diameter was not influenced by this factor and the pore size was almost uniform at a low NH₄OH concentration. For a higher NH₄OH concentration, the pore volume and the pore diameter became larger but the surface area became smaller as the gelation temperature increased. By means of the response surface methodology analysis, the optimum processing condition was found to be 0.0155 mole of NH₄OH, 80,3°C for gelation temperature, and 63.2°C for the dehydration. As a result the maximum surface area corresponding to the optimum preparation conditions was 818.9 (m²/g) as expected.     

Fe~(3+)@酵母菌非均相UV-Fenton降解染料废水

以球形酵母菌为生物载体,饱和吸附Fe3+后,获得了Fe3+@酵母菌核壳微球。SEM,EDS及FT-IR对微球的结构进行了表征。实验研究了Fe3+@酵母菌非均相UV-Fenton降解碱性嫩黄O染料废水,考察了H2O2浓度、Fe3+@酵母菌催化剂的投加质量浓度、pH值、碱性嫩黄O染料的初始质量浓度等对反应的影响。结果表明,微球的直径在3.1—3.3μm,具有较好的球形形貌和壳壁强度。核壳结构的形成主要源自于生物吸附作用。当H2O2浓度为3.5 mol/L,pH值为3—4,催化剂质量浓度为5.5 g/L时,Fe3+@酵母菌非均相UV-Fenton降解碱性嫩黄O染料废水表现出了较好的去除效率。