甲基磺酸催化高酸值地沟油酯化反应动力学研究

为研究地沟油中的长链脂肪酸酯化反应动力学以及反应条件对反应速率的影响,以甲基磺酸催化高酸值地沟油与甲醇的酯化反应为研究体系,反应中甲醇被持续通入地沟油中,同时不断蒸出未反应完的甲醇与生成的水。测定地沟油与甲醇酯化反应速率常数,结果表明,甲基磺酸催化高酸值地沟油与甲醇的酯化反应为一级反应,反应活化能为76.06 kJ·mol^-1,提高甲醇流量、催化剂用量和反应温度都能提高反应速率。     

对乙酰氨基酚合成工艺研究

以对氨基酚和醋酐为原料,以活性炭为脱色剂,以水浴锅为反应设备,通过正交实验,探讨反应物的摩尔比、反应溶剂、反应温度、反应时间等不同反应条件对收率的影响,并比较以水浴锅和超声仪为反应设备对收率的影响。实验结果表明,当对氨基酚和醋酐摩尔比为1∶1.3,反应介质为纯化水,反应温度为80℃,反应时间为30 min,反应设备为超声仪时,对乙酰氨基酚收率最高61.74%。     

聚甲醛二甲醚反应热力学分析

聚甲醛二甲醚(DMM2—8)是一种有潜在应用价值的绿色柴油添加剂,可以采用三聚甲醛和甲醇为原料合成。用基团贡献法对聚甲醛二甲醚合成反应体系中主要反应的反应焓变、反应Gibbs自由能变和反应平衡常数以及多种基础热力学数据进行了估算。结果表明:在298.15—473.15 K,反应体系中三聚甲醛分解为甲醛单体的反应为吸热反应,升高温度有利于反应的进行,而甲醛与甲醇反应生成DMM2—8的反应为放热反应,随温度升高反应逐渐向不可自发进行转变;以上两步反应耦合后,在整个温度范围内为放热反应,升高温度使反应平衡常数减小,但反应均可自发进行。     

超临界CO_2中甲苯氧化为苯甲醛的研究

以超临界CO_2为反应介质,用过氧化氢作为氧源,使甲苯在反应釜内发生均相氧化反应。反应结束后,将产物蒸馏回收,得到未反应的甲苯和苯甲醛产品．CO_2循环利用。研究发现,反应的最优化条件为反应压力25MPa,反应温度180℃,反应时间4h,苯甲醛的收率为1．535%,过氧化氢与甲苯的最佳物质的量比为2．5,氧化反应为一级反应,反应活化能为76kJ/mol。     

碱性条件下NaY分子筛水热交换反应的研究

对碱性条件下的分子筛离子水热交换反应进行了研究。结果表明,离子交换反应为吸热反应,交换反应等温线为d型,交换反应为一级反应,表观活化能Ea为10．05kJ／mol。     

利用改进的重氮化反应法制备对氟苯甲醛的研究

以对甲基苯胺为主要原料,通过重氮化反应、氯代反应及水解反应制备对氟苯甲醛。重氮化反应在液化的无水氟化氢中进行,重氮盐产物可以不经分离制得对氟甲苯,可实现连续操作。重氮化反应条件为:n(亚硝酸钠):n(对甲基苯胺)=1.2,反应温度为-10~5℃,热分解温度为40℃。在优化反应条件下重氮化反应的收率为84%,高于传统的重氮化反应。氯代反应采用过氧化苯甲酰作为催化剂,通过加热和光照使侧链的氯代反应得以顺利进行。对氟苯甲醛的总收率为69%。     

α-异佛尔酮异构化反应研究

以α-异佛尔酮为原料,4A分子筛为催化剂,通过异构化反应制备β-异佛尔酮,考察了温度和催化剂用量对反应的影响,并对反应进行了热力学研究.实验结果表明:该反应的最佳反应温度为210℃,催化剂用量为反应原料的10％,反应时间为6h.a-异佛尔酮异构化生成β-异佛尔酮反应的焓变为55.4 kJ/mol.     

硅烷封端聚氨酯热熔胶反应动力学的研究

采用自制聚酯A与甲苯二异氰酸酯(TDI)进行反应,合成了聚氨酯(PU)预聚体,再与3-N(苯基)氨基丙基三甲氧基硅烷进行封端反应,合成了硅烷封端聚氨酯热熔胶(SPUR)。通过化学分析法分别研究了PU预聚体和SPUR的反应动力学。结果表明,聚酯A与TDI的预聚反应为二级反应,反应活化能Ea为33.82kJ/mol,75℃下反应速率常数k为0.00732g/(mol.min),反应末期由于粘度增大和支化反应,偏离了二级反应;PU预聚体与3-N(苯基)氨基丙基三甲氧基硅烷的反应也为二级反应,反应速率常数k为0.0827g/(mol.min),反应速率快,可在室温下快速反应。     

微波作用下的乙酸乙酯合成反应动力学

为揭示微波辐射效应对非均相酯化反应动力学的影响,研究了微波加热催化合成乙酸乙酯的酯化反应动力学,并与常规动力学作了对比.在自制微波功率连续可调、红外测温已校正的反应装置中,重复测定了反应温度为60,65,70和75℃时的正、逆反应速率常数,得到了Arrhenius方程参数.微波加热下的反应活化能为51.719 kJ/mol,指前因子为582.9:常规水浴加热下的反应活化能为48.581 kJ/mol,指前因子为169.2.研究结果表明,在研究的反应温度范围内,微波改变了反应动力学,加快了反应速率,存在微波非热效应,但并不改变反应平衡常数.     

TOME环化反应热力学分析及反应动力学研究

采用基团贡献法对四甲基-酮-癸烯酸甲酯（TOME）环化反应进行了热力学分析。结果表明,标准压力下该反应为吸热反应,温度高于403 K范围内反应为自发过程;反应的Gibbs自由能变随温度的升高而减小,升温有利于反应正向进行。通过间歇实验研究了非催化条件、常压、463~493 K温度范围内TOME环化反应动力学。动力学拟合结果表明,该反应为一级反应,升温能明显加快反应速率,在所研究温度范围内反应活化能为143.72 kJ?mol ^-1。     

Inorganic/organic nanocomposite coatings: The next step in coating performance

Inorganic/organic hybrid materials have considerable promise and are beginning to become a major area of research for many coating usages, including abrasion and corrosion resistance. Our primary approach is to prepare the inorganic phase in situ within the film formation process of the organic phase. The inorganic phase is introduced via sol-gel chemistry into a thermosetting organic phase. By this method, the size, periodicity, spatial positioning, and density of the inorganic phase can be controlled. An important aspect of the inorganic/organic hybrid materials is the coupling agent. The initial task of the coupling agent is to provide uniform mixing of the oligomeric organic phase with the sol-gel precursors, which are otherwise immiscible. UV-curable inorganic/organic hybrid systems have the advantages of a rapid cure and the ability to be used on heat sensitive substrates such as molded plastics. Also, it is possible to have better control of the growth of the inorganic phase using UV curing. It is our ultimate goal to completely separate the curing of inorganic and organic phases to gain complete control over the morphology, and hence optimization of “all” the coating properties. Thus far, it has been found that concomitant UV curing of the inorganic and organic phases using titanium sol-gel precursors afforded nanocomposite coatings which completely block the substrate from UV light while maintaining a transparent to visible light. Also, it has been found that the morphology of the inorganic phase is highly dependent on the concentration and reactivity of the coupling agent. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004, in Chicago, IL.     

Analyse Expérimentale et Numérique du Comportement de Membranes Thermoplastiques en ABS et en HIPS dans le Procédé de Thermoformage

In this work, we are interested, on the one hand in the characterization of circular polymeric ABS and HIPS membrane under biaxial deformation using the bubble inflation technique, on the other hand in modelling and numerical simulation of the thermoforming of ABS and HIPS materials using the dynamic finite element method. Hyperelastic models (Mooney‐Rivlin, Ogden) are considered. First, the governing equations for the inflation of a flat circular membrane are solved using a variable‐step‐size‐finite difference method and a modified Levenberg‐Marquardt algorithm to minimize the difference between the calculated and measured inflation pressure. This will determine the material constants embedded within the models used. For numerical simulation, the lagrangian formulation together with the assumption of the membrane theory is used. Moreover, the influence of the hyperalastic model on the thickness and on the stress distribution in the thermoforming sheet are analysed for ABS and HIPS materials.     

ACR对PVC加工性能的影响

详细研究了丙烯酸酯类PVC加工助剂———ACR的特性黏度、组成对PVC共混物加工性能的影响。结果表明,随着甲基丙烯酸甲酯用量的下降和丙烯酸丁酯用量的提高,其塑化速度增大,但熔体强度降低,在组成相同的情况下,特性黏度越大,塑化越慢,熔体强度越大;丙烯酸酯类加工助剂对PVC制品的拉伸强度和维卡软化点无明显影响,高黏度的加工助剂有提高PVC制品拉伸强度和维卡软化点的趋势。     

Kinetics of organic solvent-soluble and native lipase

Organic solvent-soluble lipase was prepared with a synthetic detergent. The solvent-soluble lipase was presumed to be a complex of the enzyme and the detergent. To investigate the effect of the detergent attachment to the enzyme on the reaction properties, the kinetics of the solvent-soluble lipase and of the native lipase were estimated by using glycerides in a homogeneous solution of buffer and tetrahydrofuran. Analysis of the direct interaction between the enzyme and the substrate could serve to characterize the steric structure around the active site of the lipase. The K_m values also differentiated the solvent-soluble lipase from the native lipase. These findings show for the first time that the detergent surrounding the enzyme molecule may affect not only the solubility of the enzyme, but its kinetics as well.     

液滴撞击微结构疏水表面的动态特性

对去离子水滴撞击不同几何尺寸显微结构方柱和方孔状疏水表面的动态特性进行了研究。结果表明：当液滴以不同速度撞击微方柱疏水表面时,液滴展现铺展和回缩过程,且随着韦伯数（We数）增大,最大铺展直径增大,并伴随卫星液滴出现,但到达最大铺展直径的时间一致;而当液滴以相同的速度（We数相同）撞击间距不同的微方柱疏水表面时,液滴的最大铺展直径随着间距的增大而减小,且铺展过程会液滴浸润状态变得不稳定,发生由Cassie向Wenzel状态的浸润转变。当微方柱间距较小时,液滴受到的黏附功越小,越易发生向Cassie状态的转变;液滴撞击微方孔疏水表面时,液滴以规则的圆环状向外铺展和回缩,最后呈现近似规则的椭球状,不会发生向Wenzel状态的浸润转变,利用建立的物理模型对前述现象进行了分析。     

一种自适应柱状密封气膜特性分析

提出一种自适应柱状气膜密封,构建气膜-密封环为研究对象,考虑了偏心间隙发散问题,并定义Rayleigh台阶对气膜周期的突变性,建立了气膜雷诺方程和膜厚变化函数关系式的动力润滑数值模型,获得了摩擦副气膜润滑特性,研究结果表明：气膜力随转速和压力升高而增加,泄漏量随压力升高而增加但是随转速增加而下降,说明密封内部压力流占主导地位。随后,利用曲面槽型雕刻技术,结合高速试验台对密封进行测试,结果表明：理论计算模型与试验结果吻合度较高,斜槽区域存在更多擦痕与磨损,说明斜槽浮动性弱于直列槽;但斜槽的切向流动小于直列槽,导致斜槽泄漏量小于直列槽。该研究成果为自适应柱状气膜密封的气体流动规律和应用提供了理论基础。     

Lipid distribution on textiles in relation to washing with lipases

Effectiveness of lipase in detergency was studied using three test soils (lard, artificial sebum, and olive oil) on a woven cotton fabric. Distribution of oily soil on fabrics was determined for three different treatments (unwashed, washed with detergent without lipase, and washed with detergent plus lipase). Osmium tetroxide was used to label lipid soil for analysis in the scanning electron microscope. Both longitudinal and cross-sectional backscattered electron images for unwashed samples showed that soil was present on surfaces of the cotton fibers and in interfiber spaces of the yarn bundle. Lard soiled samples had large deposits on the fabric surfaces, while artificial sebum and olive oil appeared more uniformly distributed throughout the textile. Oil was deposited in the interfiber capillaries of the yarn bundle and in the crenulation, secondary walls, and lumen of the fibers. Energy dispersive X-ray microanalysis was used to determine relative concentrations of oil at selected morphological locations within the fiber structure and at the fiber surface. Soil distributions within the fibrous structures differed with type of soil and laundry treatment. Backscattered electron images dramatically demonstrated the effect of lipase on cleaning. After washing with detergent plus lipase, yarn surfaces had much less residual soil; residual soil that remained was in the irregularities of the cotton fiber surfaces. Concentrations of oil in the secondary walls, crenulations, lumen, and the fiber surfaces were lower after lipase treatment for all three soils. While washing with detergent removed soil from the yarn and fiber surfaces and the crenulation of the cotton fiber, only the samples washed with detergent plus lipase had lower concentrations of soils within the secondary wall and lumen of the cotton fibers. Fabrics soiled with olive oil and washed with detergent plus lipase had the lowest concentrations of residual soil across the textile structure; the residual soil observed was mainly in the irregularities on the fiber surfaces.     

水平及竖直基底上微小固着液滴的蒸发特性分析

为揭示非水平表面上微小蒸发液滴的传热传质特性,本文在准稳态模型的假设下构造三维液滴模型,综合考虑了蒸气扩散、蒸发冷却以及气相域中的自然对流这3种传输机理,对水平以及竖直基底上液滴的蒸发过程进行数值研究。通过分析气液界面上温度分布、蒸发通量分布及总蒸发率的变化,重点探究了基底过热度以及重力的改变对液滴蒸发特性的影响。结果表明：与水平基底上温度的对称分布不同,竖直基底上气液界面温度分布表现出明显的非对称性,且非对称性随基底过热度的升高而增强,最低温度点不再位于液滴顶点,而向一侧偏移。此外,水平基底上气液界面局部蒸发通量呈对称分布,各截面分布相似,而竖直基底上局部蒸发通量分布则呈现出显著的非对称性以及各截面异性,非对称性随着基底过热度的升高而增强,这是重力改变后气相域自然对流发生改变的结果。与水平基底相比,竖直基底上蒸发率更高,总蒸发时间更少。最后,基底由水平变为竖直时,液滴内部流场由对称双涡转变为非对称单涡,单涡流速显著大于双涡流速,液滴内流速随基底过热度的上升而增大,单涡环流造成了气液界面温度分布的改变以及最低温度点的偏移。     

二氧化钛改性α-氧化铝载体对银催化剂催化乙烯环氧化反应性能的影响

为了排除载体孔结构变化对催化性能的影响,研究了二氧化钛改性α-氧化铝载体对银催化剂催化乙烯环氧化反应性能的影响。研究结果表明,二氧化钛表面改性α-氧化铝载体对载体的比表面积、孔结构无明显影响;载体表面改性导致催化活性组分银在载体表面均匀分散,分散状况明显改善;经二氧化钛改性后载体表面与银的相互作用增强;对单负载银催化剂,由改性载体制备的银催化剂的活性和选择性均下降,改性对催化性能明显不利;对于共浸渍法制备的多组分银催化剂,低温焙烧对催化性能不利,而由经1000℃高温焙烧的二氧化钛改性载体制备的银催化剂的催化活性明显提高。研究表明,载体表面等电点降低及其与银的强相互作用是造成催化剂上金属银良好分散的主要原因;此外,银催化剂助剂的存在减弱了二氧化钛改性载体与银之间的强相互作用、抑制了环氧乙烷（EO）深度反应的活性,两者协同作用提升了多组分银催化剂的催化反应性能。     

煤油贮箱冷氦鼓泡增压过程数值研究

火箭飞行过程中,约90 K的低温氦气用以加压室温下的煤油贮箱使煤油流出,保障发动机燃料供应。为尽可能减少氦气用量,设计低温氦气从液相中喷入,使得氦气在贮箱内上升过程先和液态煤油充分换热升温,再进入气相空间增压。但该过程可能引起两个不利的结果,首先浸没在煤油中的低温氦气管路表面可能结冰,结冰沉底或可能堵塞发动机滤网;其次氦气可能被煤油携带,从而排出口位置可能出现气液两相流。这两种情况都对火箭发动机稳定运行造成负面影响,因此是不允许的。对低温氦气在贮箱中心喷入和环向多孔喷入两种结构的气液两相流过程进行了数值研究,构建了基于Euler-Euler模型的两相传热非稳态模型,数值结果与地面实验观察到的现象进行了定性对比,定性验证了模型的准确性。重点考察了煤油排出过程两种喷入结构的气液两相流分布以及煤油结冰可能性。研究结果从机理上解释了实验现象,并为煤油贮箱增压排出方案设计提供了参考。