Two‐phase production of cyclohexene and cyclooctene oxides in water as an approach to pollution prevention

Liquid–liquid two‐phase epoxidation from cyclohexene and cyclooctene in aqueous potassium peroxymonosulfate (commercially available as Oxone^®) solution was studied as an application in pollution prevention. To avoid potential emissions of volatile organic compounds an aqueous solution was employed to replace the usual chlorinated solvents used in epoxide production. A droplet column reactor and stirred tank reactor were used to investigate two‐phase synthesis of epoxide. An aqueous Oxone^® solution was used to oxidize a dispersion of alkene droplets and form epoxide. The study of aqueous epoxidation in both reactors showed that the epoxidation of alkenes can be represented as a first order reaction with respect to alkene. The salting out effect of Oxone^® concentration was studied in both reactors and found to be very similar at optimal conditions. In comparing the two reactors, it was found that the droplet column reactor produces larger quantities of product per unit reactor volume for the same reaction time. The objective of this study is to provide an alternative reactor design and synthesis route that can meet pollution prevention goals. Copyright © 2004 Society of Chemical Industry     

Active set truncated-Newton algorithm for simultaneous optimization of distillation column

An active set truncated-Newton algorithm (ASTNA) is proposed to solve the large-scale bound constrained sub-problems. The global convergence of the algorithm is obtained and two groups of numerical experiments are made for the various large-scale problems of varying size. The comparison results between ASTNA and the subspace limited memory quasi-Newton algorithm and between the modified augmented Lagrange multiplier methods combined with ASTNA and the modified barrier function method show the stability and effectiveness of ASTNA for simultaneous optimization of distillation column.     

化学反应和气相色谱法联合测定含烯汽油中共轭二烯烃含量

建立了利用共轭二烯烃与马来酸酐的Ｄｉｅｌｓ－Ａｌｄｅｒ特性反应和１ｍ×１．７ｍｍ（ｉｄ）非极性固定液ＳＥ－３０填充柱气相色谱法联合分析含烯汽油中的共轭二烯烃含量的方法。该柱能用低碳数的正构烷烃如正十一烷作内标物，内标物与油样组份分离很好，色谱分析一次４ｍｉｎ，油样的相对标准偏差为１．７％。在一定的化学反应条件下，用Ｉ２和ＡｌＣｌ３作催化剂，当Ｉ２、ＡｌＣｌ３与共轭二烯烃的物质的量比分别为０．８×１０－５和（１～２）×１０－３时，异戊二烯有最高的转化率分别为６８．５１％和９８．１８％，回流反应装置的挥发损失率为０．２８％。     

Characterization and modification of fillers for paints and coatings

This paper highlights the possibility of inverse gas chromatography for the surface characterization of common fillers (CaCO₃, talc, SiO₂,) for paints and coatings. Divided solids are described, on the one hand, by the dispersive component of their surface energy and, on the other, by a specific parameter indicating their acid-base interaction potential. The role of the surface morphology at a molecular level is also examined. It is demonstrated that steric effects play an important role in the adsorption of probes on lamellar solids like talc. The consequences of surface treatments as well as examples of practical applications are also reported.     

棉铃宝高效液相色谱分析方法研究

本法采用同一色谱条件反相高效液相色谱法测定棉铃宝中甲基对硫磷和辛硫磷的含量，方法简单易行，具有较高的精密度和准确度，其回收率分析为甲基对硫磷９９．５９％，辛硫磷１０１．０％。     

燃料型减压塔汽提段工艺参数对拔出率的影响

探讨减压塔汽提与闪蒸的关系,分析汽提对蜡油拔出率及减压渣油中500 ℃以下馏分含量等技术指标的影响.通过模拟计算和现场数据说明,汽提段内采用填料较塔盘更具优势.与塔盘相比,填料具有压力降小、理论板数多的特点,可以显著提高拔出率,降低减压渣油中500 ℃以下馏分含量.基于汽提段结焦的机理,澄清了汽提段填料层易结焦的误区,提出了解决结焦问题的具体措施.     

润滑油型常减压蒸馏装置扩能改造

通过对中国石油大连石化分公司Ⅱ套蒸馏装置扩能改造的设计实践，总结归纳了在老工艺装置上采用立体传质塔盘等新技术、新设备的应用成果。改造后的标定数据表明，改造后装置处理能力可达5．1Mt／a，常、减压系统主要产品质量满足设计要求，装置能耗在386.94—406.60MJ／t，低于设计值。     

多维气相色谱快速测定汽油中的烯烃、芳烃和苯含量

针对车用无铅汽油国家标准GB17930-1999中对烯烃，芳烃和苯含量提出的明确限值要求，以及现有标准方法和其它分析技术在分析汽油组成时存在的问题，结合国外汽油分析的发展趋势及我国汽油生产的工艺和汽油组成分布特点，提出了一套新的多维气相色谱技术测定汽油中烯烃。芳烃和苯含量的方法。并研制了新的烯烃捕集阱，可捕集汽油中高达70%的烯烃，且具有良好的可逆性和使用寿命，提出的方法可以在12min内通过一次色谱进样实现汽油中烯烃总量，芳烃总量和苯含量的测定。试验结果与荧光指示剂吸附法（FIA，GB/T11132-1989）相比具有很好的一致性。但分析速度和方法的再现性得到明显改善。试验成本也大大降低。     

二甲基甲酰胺溶剂回收装置焦油塔减压改造方案

实验研究了纯二甲基甲酰胺(DMF)水溶液和焦油塔进料在不同减压压力条件下的水解变化规律,确定了焦油塔减压操作的适宜操作压力和减压操作方案。     

香豆胶衍生物的化学结构及稳定性研究

将市售商品溶于水,用异丙醇沉析提纯,溶于0.1 mol/L NaNO3纯水溶液中,经0.5μm滤膜过滤后用水相凝胶渗透色谱法(GPC)测定,测得香豆胶(FG)、羟丙基香豆胶(HPFG)、阳离子香豆胶(CFG)的数均、重均相对分子质量Mn、Mw分别为:1.19×105、3.36×105,8.52×104、2.85×105,9.33×104、2.87×105。用甘露聚糖链在碱性条件下醚化时发生降解,解释两种改性FG的相对分子质量较FG低而多分散性(Mw/Mn)较FG高的测试结果。认为商品FG的1%水溶液黏度(1300 mPa.s)高于商品HPFG和CFG(分别为705和610 mPa.s)的原因是前者相对分子质量较高且残渣含量也较高(~10%,后二者为1%~2%)。HPFG的取代度为0.12,根据文献发表的13C-NMR数据确认HPFG分子链上羟丙基取代位置为C6。讨论了香豆胶(半乳甘露聚糖)的化学结构。热重分析法测定的热稳定性,HPFG高于CFG,CFG又高于FG。图6表3参13。