基于本质安全的微反应器中苯乙烯聚合的数值模拟

重大化工事故往往是由多米诺效应引发的一连串故障而导致的。为实现苯乙烯聚合反应的本质安全,采用本质安全设计原则,设计了T型微反应器以替换传统釜式反应器。先通过计算流体力学(CFD)方法建立了三维稳态模型,再通过UDF(User Defined Functions)添加组分输运方程源项和能量方程源项,对苯乙烯自由基聚合反应进行了数值模拟,研究在微尺度条件下,反应温度、混合反应管道长度及形状对反应结果的影响。结果表明:由于微反应器可提高传热传质效率,在一定范围内反应温度可以控制在3 K以内;反应管道由0.15 m增长至1.5 m后,转化率可提高2倍左右;0.15 m直管形状改进为螺旋状后,转化率可至少提升4%。     

阳离子絮凝剂P(AM-DAC)的合成、表征及应用

以丙烯酰胺(AM)和丙烯酰氧乙基三甲基氯化铵(DAC)为单体,过硫酸钾(KPS)为引发剂,通过水溶液聚合的方法合成了阳离子絮凝剂P(AM-DAC)。探讨了单体配比、单体浓度、引发剂用量、反应时间、反应温度等因素对阳离子聚丙烯酰胺(CPAM)主要性能的影响。实验得出了较佳的反应条件:聚合温度为70℃,引发剂用量为0.16%,单体配比m(AM):m(DAC)=1:8,总单体浓度为20%,反应时间3 h。在上述条件下,所得阳离子聚丙烯酰胺絮凝剂的特性黏数为18.692 4 dL/g,在其加入量为0.003%的条件下处理巡司河污水,上层清液透光率达90.7%,污泥脱水率达89.2%。并对该聚合物絮凝剂的结构和热行为进行了表征。     

微胶囊化新型聚硫橡胶密封剂的性能试验与评估

目的研发新型聚硫橡胶密封剂,并对其性能进行综合评估。方法基于原位聚合技术,制备以脲醛树脂为壁材,液态聚硫橡胶为囊芯的微胶囊。通过考察微胶囊密封剂的稳定可靠性、力学性能(力矩和拉伸性能)等,系统评价新型微胶囊密封剂的综合性能。结果通过聚硫密封剂微胶囊化,可将其装配工序由5步简化成1步,实现密封剂的预涂覆功能。微胶囊密封剂的稳定可靠性实验结果表明,长期储存后,微胶囊颗粒形貌不变,芯材聚硫橡胶未泄露和变性,保持良好的化学反应活性。力学性能试验结果表明,与原密封剂相比,微胶囊密封剂的破坏力矩、拆卸力矩、拉伸强度和断裂拉伸强度明显提高,断裂伸长率有所下降。结论通过脲醛原位聚合技术成功制备出形貌规整、粒径分布单一的聚硫密封剂微胶囊,实现聚硫密封剂包得住、不变性的目的。囊壁材料的引入对于密封剂力学性能有较大影响。     

阳离子乳液型清水剂的制备及其在油田污水处理中的应用

以二甲基二烯丙基氯化铵(DMDAAC)为阳离子单体,苯乙烯、丙烯酸丁酯为疏水单体,十六烷基三甲基溴化铵和聚氧乙烯辛基苯酚醚-10(OP-10)为乳化剂,过硫酸铵为引发剂,采用乳液聚合法制备乳液型清水剂。优化了制备清水剂的工艺条件,考察了清水剂对油田污水的处理效果。实验结果表明:在x(DMDAAC)小于20%、n(苯乙烯)∶n(丙烯酸丁酯)为2∶1、乳化剂占单体质量分数为5%、引发剂占单体质量分数为0.5%的优化条件下可制备形成稳定的阳离子乳液清水剂;分子量越大、x(DMDAAC)越大,清水剂的除油效果越好;在x(DMDAAC)为20%、其他最优条件不变的情况下制备的Q20清水剂使用浓度为30 mg/L时可使油田污水含油量从295 mg/L降至13 mg/L。自制清水剂的除油效果好于市售清水剂。     

聚合铝形态分布特征及转化规律

采用多种实验方法,对Al(Ⅲ)的水解—聚合—沉淀反应特征及其转化规律、形态分布及规范分子量大小进行了研究,同时应用X-射线衍射光谱仪和红外光谱仪对聚合铝形态进行了表征。由研究结果似可推断,Al(Ⅲ)水解—聚合过程的形态转化过程为线型→环型→体型。其聚合形态分布取决于翔/铝比值或pH值以及其它因素。在一定羟/铝比值时,聚合铝溶液中可划分为三种类型的形态分布。提出了相应的形态转化模式来表达聚合铝的形态及转化规律。     

活性炭纤维电极法处理印染废水的应用研究

采用新型催化电极处理了１８种水溶性及水不溶性染料液，并应用于数种实际扎染残液的处理，脱色率可达到９５％￣１００％，ＣＤＣｃｒ去除率达到４０％￣７０％。初步探讨了该电化学处理系统的反应机理，推论整个处理为吸附，自由基聚合和絮凝反应相结合的过程。     

Synthesis and identification of graft copolymers of wood pulp and styrene

Based on the graft copolymerization reactions of lignin and vinyl monomers, a series of graft copolymers of wood pulp and styrene (1-phenylethene) has been synthesized. The wood pulps used in this research are unbleached products produced by chemical, thermal, and mechanical pulping. All of them contain a high content of lignin (25–29 wt%). The grafting reaction is a free radical polymerization coinitiated by calcium chloride, hydrogen peroxide, and wood pulp in dimethylsulfoxide at 30°C. The effect of reaction temperature, reaction time, and the amount of the reactants on the conversion of monomer, yield of product, weight increase of pulp, and grafting efficiency of monomer has been studied. The grafted wood pulp was separated from homopolystyrene formed during the reaction by extraction of the reaction product with benzene in a Soxhlet apparatus for at least 48 h. The results show that after the reaction, the weight of all wood pulps was significantly increased and the weight increase of very high yield sodium bisulfite pulp (VHYS) was 333%. This proves that a part of the polymerized styrene was chemically bound to the wood pulp. The Fourier transform infrared (FTIR) spectra of the extracted products show absorbance peaks characteristic of both wood and polystyrene and, thus, provide strong proof of grafting. Grafting has completely changed the surface properties of the starting wood pulp from hydrophilic to hydrophobic, and under ordinary thermal compression conditions, thermoplastic composite objects of good uniformity can be made directly from reaction products which contain up to 52 wt% wood pulp.     

Enzyme-Based Vinyl Polymerization

In vitro enzyme-mediated polymerization of vinyl monomers is reviewed. Oxidoreductase enzymes have been used for the polymerization of styrene, derivatives of styrene, acrylates, and acrylamide in water and water-miscible co-solvents. Kinetic and mechanistic studies revealed that a ternary system (horseradish peroxidase, H₂O₂, initiator, or -diketone) is required for efficient polymerization and the initiator controls the polymer characteristics.     

Degradation of Cellulosic Materials Under the Alkaline Conditions of a Cementitious Repository for Low- and Intermediate-Level Radioactive Waste. II. Degradation Kinetics

The degradation of cellulosic materials, differing mainly in the degree of polymerization and the number of reducing end groups, was studied under the alkaline conditions similar to those existing in a cementitious repository for low- and intermediate-level radioactive waste (pH 13.3, T = 25°C). The kinetics of alkaline degradation (peeling-off reaction) were studied and the data analyzed by the model of Haas et al. [13]. The observed kinetic parameters for the propagation reaction and overall stopping reaction were compared with literature data. Although measured under different experimental conditions, literature data and data from this study show a consistent picture. Differences in the extent of degradation observed for the different cellulosic materials could be satisfactorily explained by differences in reducing end group content and, consequently, by differences in the degrees of polymerization. Besides the number of reducing end groups, the degree of amorphousness also plays an important role. The main degradation products formed under the experimental conditions used are - and -(gluco)isosaccharinic acid. This is in agreement with many other studies on alkaline degradation of cellulose. The two isomers are formed in roughly equal amounts.     

基于电聚合作用的脂质体免疫传感器检测水体中毒莠定的实验研究

利用脂质体包埋亚铁氰化钾,通过戊二醛交联毒莠定兔抗制成免疫脂质体,开发快速检测水中毒莠定的夹心型免疫传感器.在修饰电极的成分等方面优化传感器的工作参数,确定了Nation、多壁碳纳米管(multiwalled carbon nanotubes, MWCNTs)和毒莠定兔抗浓度的最优值分别为0.5%、10mg·mL-1、50μg·mL-1.免疫传感器的制作及测定过程如下:采用循环伏安法促使3,4-乙烯二氧噻吩(3,4-ethylendioxythiophene, EDOT)发生电聚合作用,将毒莠定兔抗直接固定到被修饰的玻碳电极上,电极再依次与待测水样和毒莠定兔抗修饰的免疫脂质体培育一定时间,最后利用TfitonX-100溶解与抗原结合的免疫脂质体,采用方波伏安法检测还原电流以反映毒莠定浓度,整个检测过程可以在70rain内完成.在0.1 mol·-1,的H3PO4中浸泡5 rain,可实现该传感器的良好再生.结果表明,毒莠定的检测下限达到了10-10mol·L-1,线性区间为10-10～10-4mol·L-1,适合饮用水中毒莠定浓度的检测要求.