高纯乙酰氯生产工艺的改进

通过对国内乙酰氯现有生产工艺的考察、研究,对传统的醋酸和三氯化磷合成法进行了工艺改进,改进后工艺的产品收率比原来提高近6%,达到96.3%以上,产品质量达到99.0%以上,反应条件更加温和,操作容易控制,基本无三废产生,生产成本明显降低。     

锂离子电池正极材料LixMn2O4研究进展

总结了锂离子电池正极材料LixMn2O4的合成方法，归纳了造成容量衰减问题的原因和目前为解决该问题所采用的各种方法，并且对下一步的研究工作进行了展望。     

Flow Characterization of a Three‐Phase Circulating Fluidized Bed Using an Ultrasonic Technique

The axial and radial distributions of solid and gas holdups were investigated in an air‐water‐glass bead circulating fluidized bed (GLSCFB) using a new ultrasonic technique, with a new method based on signal fluctuations. The cross‐sectional averaged gas and solid holdups measured at two axial positions appear to be similar at all studied operating conditions. The radial non‐uniformity decreases with increasing liquid velocity but does not change with an increasing solid circulating rate. The radial distribution of gas holdup was more uniform for 1.3 mm beads than for 433 µm glass beads.     

生物基燃料乙醇生产工艺的能耗分析与节能技术综述

针对如何高效、经济和可持续发展生物质液体燃料这一问题,考察了淀粉质原料生产燃料乙醇的整个流程,从原料预处理到酒精脱水,尤其针对蒸馏、蒸煮液化等耗能较大的阶段,对不同的生产工艺技术进行了能耗比较,分析了不同的节能技术。通过大量的数据分析评述了最佳的技术路线,为燃料乙醇生产系统的节能降耗提出建议。     

采用不同锰源合成尖晶石LiMn2O4正极材料

The spinel LiMn2O4 cathode material was synthesized with the solid-state reaction method. Four manganese compounds including electrolytic manganese dioxide (EMD), MnCO3, Mn3O4 and nano-EMD were used as Mn sources while LiOH·H2O was used as the uniform Li source. The crystal structure characteristics of these samples produced were investigated by means of XRD, SEM, particle size distribution analysis and specific surface area testing. Their electrochemical properties were also studied by comparing their specific capacity, charge and discharge efficiency and cycle performance.     

Free‐radical grafting of acrylic acid onto isotactic polypropylene using styrene as a comonomer in supercritical carbon dioxide

Free‐radical grafting of acrylic acid (AAc) onto isotactic polypropylene (iPP) using styrene (St) as a comonomer in supercritical carbon dioxide (SCCO₂) medium was studied. The effects of temperature and pressure of reaction on functionalization degree (grafting degree of AAc) of the products were analyzed. The increase of reaction temperature increases the diffusion of monomers and radicals in the disperse reaction system of SCCO₂. In addition, the increase of temperature accelerates the decomposition rate of 2,2′‐azobisisobutyronitrile (AIBN), thus promoting grafting reaction. It was also observed that functionalization degree of the products decreases with the increase of pressure of SCCO₂ in the range of experiment. The effects of comonomer St on the functionalization degree of the products were investigated. The AAc graft degree of the resulting polymer was drastically higher in the present of St. It reached a maximum when the mass ratio of St and AAc was about 0.7 : 1. Because AAc is not sufficiently reactive toward iPP macroradicals, it would be helpful to use a second monomer that can react with them much faster than AAc. St preferentially reacts with the iPP macroradicals to form more stable styrene macroradicals, which then copolymerize with AAc to form branches. The highest functionalization degree was obtained when the AIBN was 0.75 wt %. When the initiator was used excessively, the functionalization degree decreased because of severe chain degradation of the iPP backbone. The morphologies of pure iPP and grafted iPP are different under the polarizing optical microscope. The diameter of the pure iPP spherulites is 20–38 μ and that of the grafted iPP spherulites is reduced with the increase of the functionalization degree of the products. This is proposed to be because the polar grafts formed during the reaction would have a tendency to associate in the hydrophobic PP environment. This might preserve some of the local crystalline order that existed during the reaction in the swollen iPP phase. It can be proven by a DSC cooling investigation that the crystallization temperature increased as the functionalization degree increased. This is proposed to be because the side‐chain of grafting polymer helps to bring about the heterogeneous nucleation in grafting polymer. Therefore, a large number of nuclei can emerge to a lesser supercooling degree. It can be also proven that the percent crystallization decreased as the functionalization degree increased, probably due to the grafted branches, which disrupted the regularity of the chain structure and increased the spacing between the chains. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2203–2210, 2004     

烧碱生产用水的综台利用

阐述了河北盛华化工有限公司综合利用烧碱生产用水的意义，介绍了所采取的措施及效果。     

Preparation of hyperbranched polymers by atom transfer radical polymerization

A cheap acrylic AB* monomer, 2‐(2‐chloroacetyloxy)‐isopropyl acrylate (CAIPA), was prepared from 2‐hydroxyisopropyl acrylate with chloroacetyl chloride in the presence of triethylamine. The self‐condensing vinyl polymerization by atom transfer radical polymerization (ATRP), a “living”/controlled radical polymerization, has yielded hyperbranched polymers. All the polymerization products were characterized by proton nuclear magnetic resonance spectroscopy (¹H NMR). CAIPA exhibited distinctive polymerization behavior that is similar to a classical step‐growth polymerization in the relationship of molecular weight to polymerization time, especially during the initial stage of the polymerization. However, a significant amount of monomer remained present throughout the polymerization, which is consistent with typical chain polymerization. Also, if a much longer polymerization time was used, the polymer became gel. As a result of the unequal reactivity of group A* and B*, the polymerization is different from an ideal self‐condensing vinyl polymerization: the branch structures of polymers prepared depend dramatically on the ratio of 2,2'‐bipyridyl to CAIPA. Hyperbranched polymers exhibit improved solubility in organic solvent, however, they have lower thermal stability than their linear analogs. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2114–2123, 2002     

TRANSIENT ANALYSIS OF CRYSTALLIZATION: EFFECT OF THE SIZE DEPENDENT GROWTH RATE

The dynamics of the crystal size distribution in a continuous mixed suspension, mixed product removal crystallizer is modeled stochastically. The model is fairly general in that it involves a size-dependent growth rate function: this size-dependent growth rate as a possible cause of deviation on the behavior of the crystallizer from that of an idealized or simplified counterpart has been investigated based upon the model.     

Kinetics of and catalyst decay accompanying the gas phase rearrangement of cyclohexanone-oxime over a hy ultrastable zeolite

The kinetics of the rearrangement of cyclohexanone-oxime has been studied in a fixed bed, glass tubular reactor at atmospheric pressure and temperatures of 240, 270, 300 and 335°C, using ultrastable HY zeolite catalyst. Several kinetic models, including the Langmuir-Hinshelwood type, have been derived and the best statistical fit has been obtained with a pseudo-first order kinetic equation. The rate constants and activation energies for the formation of the products caprolactam, cyclohexanone and 5-cyanopent-l-ene have been calculated. Based on the evolution of the selectivity with temperature, and the I.R. spectra of the poisoned catalyst, different decay models have been deduced and discussed.