Study of direct and indirect naphtha recycling to a resid FCC unit for maximum propylene production

To satisfy the increasing propylene demand, direct and indirect naphtha recycling schemes around an existing resid fluid catalytic cracking (FCC) unit were investigated. To this aim, light cracked naphtha (LCN), heavy cracked naphtha (HCN) and a PolyNaphtha (PN) oligomerisation product were cracked under a wide range of operating conditions over a commercial Y zeolite based equilibrium catalyst. Experimental data were acquired in three different units: a fixed bed bench scale unit, a fixed fluidised bed unit and an adiabatic circulating fluidised bed pilot plant. It was shown that FCC naphthas require high operating severities to crack, and that even then their conversion remains relatively moderate. Hence, direct recycling to the main riser does not seem a viable pathway to increase propylene product. Feeding FCC naphthas to a second reaction zone operating at high severity allows to increase the propylene yield in a significant manner. Increasing conversion, however, not only leads to higher LPG and propylene yields, but also results in very high dry gas yields. An alternative scheme was proposed, in which the olefinic C₄ and C₅ fractions are converted into a naphtha fraction through oligomerisation in a dedicated unit before being recracked in the secondary riser. As the highly olefinic oligomerised effluent mainly consist of dimerised and trimerised butenes and pentenes, this feed is more easily cracked and high conversions can be achieved. This indirect interconversion of butenes and pentenes into propylene therefore effectively allows to convert these butenes and pentenes into propylene, resulting in a significant increase in propylene yield. Each of the three main naphtha recycle options (directly to the main riser, directly to a secondary riser or indirectly via a light olefin oligomerisation unit) have been analysed and compared to a base case. In the evaluation of each of these schemes, all heat balance effects, both on the riser and the regenerator side, have been accounted for. The proposed process scheme with an indirect recycle via an oligomerisation unit enhances the already inherent flexibility of the FCC unit. The naphtha recycle can be turned on or off, the second reaction zone can be used to crack naphtha or to crack resid feed to maximise throughput, while the effluent of the oligomerisation unit can be recycled to the FCC unit for propylene production or hydrogenated and sent to gasoline and kerosene pool.     

环氧氯丙烷下游产品生产现状及市场前景

论述了环氧氯丙烷的主要下游产品环氧树脂、合成甘油、氯醇橡胶等的生产现状、市场前景等,指出:我国氯碱行业应该重视这些环氧氯丙烷下游精细化工产品的开发,以促进我国环氧氯丙烷的发展。     

催化热裂解工艺机遇及影响因素

分析了催化热裂解过程的反应机理及乙烯和丙烯形成的反应，乙烯和丙均可通过热裂解和催化裂解生成，讨论了影响乙烯，丙烯产率的因素：与USY和REY相比，使用ZSM－5催化剂能够提高乙烯，丙烯产率，磷改性ZRP－1经碱土金属改性后，可进一步提高乙烯和丙烯的产率，提高反应温度和降低剂油比，能够提高热裂解和催化裂解的比例，有利于乙烯产率的提高；增强蒸汽量能够减少焦炭产率，提高乙烯和丙烯产率。     

Propylene epoxidation over Ti/MCM-41 catalysts prepared by chemical vapor deposition

Ti-containing mesoporous catalysts were prepared by chemical vapor deposition (CVD) of TiCl₄ on silica MCM-41 in the 700–900 °C temperature range. These samples were characterized (with XRD, ICP, nitrogen adsorption, FT-IR, ESCA, and TEM) and evaluated for the epoxidation of propylene with two alkyl hydroperoxides. The increase of CVD temperature resulted in the decrease of titanium content, catalyst hydroxyl population, crystallinity, and surface area. Catalyst selectivity to the desired product – propylene oxide – was highly sensitive to the deposition temperature. The best Ti/MCM-41 catalyst was prepared at the temperature of 800 °C, which had the maximum propylene oxide yield of 94.3%.     

环氧丙烷生产工艺进展

综述了近年来环氧丙烷合成工艺的新进展,包括对现有环氧丙烷生产工艺的革新、直接氧化法、光催化环氧化等方法,并对各种方法的特点和发展前景进行了讨论.     

Propylene epoxidation in a microreactor with electric heating

Gas phase propylene epoxidation on gold catalysts has attracted wide attention from industry and academia due to its high selectivity. However, it suffers from low propylene conversion and rapid catalyst deactivation. Experiments showed that propylene conversion could be increased by raising H₂, O₂, or C₃H₆ concentration in the feed, but the feed compositions were within the explosion limit. It was also shown that the activity of the used catalyst could be fully recovered, but the regeneration temperature was 280 °C, much higher than that for reaction. Therefore a microchannel reactor was devised to suppress explosion and was constructed with Fecralloy, to raise the temperature rapidly for catalyst regeneration by electric heating. In two minutes the temperature of the reactor could be raised from 50 to 300 °C. Catalysts were coated on the alloy belt by dip coating, and the performance of the reactor was evaluated under different operating conditions. Results showed that in the microreactor the overall reaction rate was controlled mainly by the intrinsic reaction rate, and also influenced by film diffusion to a certain extent. The deactivated catalyst was regenerated in the microchannel reactor and the activity was fully recovered.     

提高丙烯和混合碳四产品收率的对策与措施

中国石油化工股份有限公司茂名分公司化工事业部乙烯装置随着运行周期的延长，高低压脱丙烷塔和脱丁烷塔结垢严重，分离效果变差，造成丙烯和混合碳四产品的收率降低。通过分析丙烯和混合碳四产品损失大、收率低的原因，提出对策并采取相应措施，从而有效地提高了丙烯和混合碳四产品的收率。     

丙二醇单甲醚丙酸酯合成体系的气相色谱分析

自行研制了氰乙基(25%,质量分数)甲基硅橡胶(XE-60)石英毛细管色谱柱。建立了对含游离酸的丙二醇单甲醚丙酸酯的色谱分析方法。该法具有分离效果好,分析速度快的优点。     

膜分离技术在丙烯尾气回收中的应用

分析了聚丙烯生产过程中压缩 /冷凝法丙烯尾气回收的不足 ,介绍了压缩 /冷凝 /有机蒸汽膜法在丙烯尾气回收中的应用     

A high propylene productivity over B2O3/SiO2@honeycomb cordierite catalyst for oxidative dehydrogenation of propane

Boron-based metal-free catalysts for oxidative dehydrogenation of propane (ODHP) have drawn great attention in both academia and industry due to their impressive activity and olefin selectivity. Herein, the SiO₂ and B₂O₃ sequentially coated honeycomb cordierite catalyst is designed by a two-step wash-coat method with different B₂O₃ loadings (0.1%–10%) and calcination temperatures (600, 700, 800 °C). SiO₂ obtained by TEOS hydrolysis acts as a media layer to bridge the cordierite substrate and boron oxide via abundant SiOH groups. The well-developed straight channels of honeycomb cordierite make it possible to carry out the reactor under high gas hourly space velocity (GHSV) and the thin wash-coated B₂O₃ layer can effectively facilitate the pore diffusion on the catalyst. The prepared B₂O₃/SiO₂@HC monolithic catalyst exhibits good catalytic performance at low boron oxide loading and achieves excellent propylene selectivity (86.0%), olefin selectivity (97.6%, propylene and ethylene) and negligible CO₂ (0.1%) at 16.9% propane conversion under high GHSV of 345,600 ml·(g B₂O₃)⁻¹·h⁻¹, leading to a high propylene space time yield of 15.7 g C₃H₆·(g B₂O₃)⁻¹·h⁻¹ by suppressing the overoxidation. The obtained results strongly indicate that the boron-based monolithic catalyst can be properly fabricated to warrant the high activity and high throughput with its high gas/surface ratio and straight channels.