Pt-Sn-K/Al2O3催化剂上长链烷烃(C17～C20)脱氢反应工艺条件

以C17～C20重蜡脱氢为探针反应,考察反应温度、反应压力、氢烃体积比及空速等工艺参数对Pt-Sn-K/γAl(2)O(3)催化剂脱氢反应性能的影响.结果表明,C17～C20脱氢反应适宜的工艺条件为:反应压力0.14 MPa,氢烃体积比600:1,空速20 h-1和反应温度高于440℃,此条件下,转化率达14%以上.     

Reprint of: Oxidative dehydrogenation of cyclohexane and cyclohexene over supported gold, –palladium catalysts

Supported gold, palladium and gold–palladium catalysts have been used to oxidatively dehydrogenate cyclohexane and cyclohexenes to their aromatic counterpart. The supported metal nanoparticles decreased the activation temperature of the dehydrogenation reaction. We found that the order of reactivity was Pd ≥ Au–Pd > Au supported on TiO₂. Attempts were made to lower the reaction temperature whilst retaining high selectivity. The space-time yield of benzene from cyclohexane at 473 K was determined to be 53.7 mol/kg_cat/h rising to 87.3 mol/kg_cat/h at 673 K for the Pd catalyst. Increasing the temperature in this case improved conversion at a detriment to the benzene selectivity. Oxidative dehydrogenation of cyclohexene over AuPd/TiO₂ or Pd/TiO₂ catalysts was found to be very effective (conversion >99% at 423 K). These results indicate that the first step in the reaction sequence of cyclohexane to cyclohexene is the slowest step. These initial results suggest that in a fixed-bed reactor the oxidative dehydrogenation in the presence of oxygen, palladium and gold–palladium catalysts are readily able to surpass current literature examples and with further modification should yield even higher performance.     

铂系丙烷脱氢催化剂助剂研究进展

铂基催化剂用于丙烷催化脱氢的主要缺点是稳定性差、选择性低,通过添加助剂可以大大改善该催化剂的脱氢性能.针对催化剂助剂,综述了铂基丙烷脱氢催化剂的研究现状,分别介绍了碱金属、碱土金属、稀土金属和过渡金属作为助剂对铂基催化剂的影响,探讨了所添加助剂的作用机制,并对铂基催化剂研究前景进行了展望.     

丙烷脱氢制丙烯低温分离工艺分析

为确立丙烷脱氢制丙烯工艺中低温分离单元的最佳制冷流程,采用PRO/Ⅱ8.2化工流程模拟软件,对低温分离单元进行模拟计算,考察了温度和压力对低温分离效果的影响,分析并确立了最佳分离温度和压力范围;在分离效果相同的前提下,分别比较了丙烯+乙烯级联制冷、丙烯预冷+混合制冷和丙烯预冷+富氢气膨胀制冷3种制冷流程的公用工程消耗以及各自的优缺点。结果表明:产品压缩机出口压力对分离效果影响较小,在确保下游装置能够正常操作的情况下,分离压力应尽可能低;分离温度是影响分离效果的主要因素,较为经济的分离温度为-90—-100℃;相对于其他2种流程,丙烯+乙烯级联制冷流程具有技术成熟、能耗低和操作简单等优点,更适合于丙烷脱氢制丙烯工艺。     

Methylcyclohexane dehydrogenation for hydrogen production via a bimodal catalytic membrane reactor

The dehydrogenation of methylcyclohexane (MCH) to toluene (TOL) for hydrogen production was theoretically and experimentally investigated in a bimodal catalytic membrane reactor (CMR), that combined Pt/Al₂O₃ catalysts with a hydrogen‐selective organosilica membrane prepared via sol‐gel processing using bis(triethoxysilyl) ethane (BTESE). Effects of operating conditions on the membrane reactor performance were systematically investigated, and the experimental results were in good agreement with those calculated by a simulation model with a fitted catalyst loading. With H₂ extraction from the reaction stream to the permeate stream, MCH conversion at 250°C was significantly increased beyond the equilibrium conversion of 0.44–0.86. Because of the high H₂ selectivity and permeance of BTESE‐derived membranes, a H₂ flow with purity higher than 99.8% was obtained in the permeate stream, and the H₂ recovery ratio reached 0.99 in a pressurized reactor. A system that combined the CMR with a fixed‐bed prereactor was proposed for MCH dehydrogenation. © 2015 American Institute of Chemical Engineers AIChE J, 61: 1628–1638, 2015     

Copper(I)‐Catalyzed Dehydrogenative Amidation of Arenes Using Air as the Oxidant

The copper(I) bromide‐catalyzed intermolecular dehydrogenative amidation of arenes via C H bond activation assisted by a 2‐pyridyl or 1‐pyrazolyl chelating group using air as the terminal oxidant has been achieved at 140 °C. N‐Aryl amides, N‐alkyl amides, benzamide derivatives, imides, and lactams all are good coupling partners to obtain moderate to excellent yields. The amount of solvent is critical for the transformation: both increasing and decreasing the amount of solvent decreased the yield. Notably, the amidation of bimolecular 2‐phenylpyridine with the dual N H bonds of a primary amide proceeded smoothly in one‐pot to afford a good yield under the same conditions. The amidation can be performed with a good yield at the gram scale.

     

脱氢催化剂使用总结

介绍脱氢的工艺流程,催化剂的装填、使用要求,投运后的运行情况,以及增加脱氢对系统的影响。     

丙烷催化脱氢制丙烯生产技术及工业应用进展

文章介绍了丙烷催化脱氢制丙烯生产技术的特点及工业应用进展,针对中国实际提出了发展建议。     

脱氢用Pd/C催化剂制备及其工艺优化

采用浸渍法制备了一种脱氢专用Pd/C催化剂,研究了其在四氢咔唑脱氢反应中的应用。利用响应面分析法对Pd/C催化剂制备的pH、炭浆体积和反应时间进行了优化,得出最佳工艺条件:pH=7.86,炭浆体积139.76 mL,反应时间75.70 min,咔唑收率接近100%。     

PED-01乙苯脱氢催化剂的评价试验

自主开发的PED-01乙苯脱氢催化剂在100 mL等温评价装置上进行了重复试验和稳定性试验,在反应温度620 ℃、空速1.0 h^-1、水蒸汽与乙苯质量比2∶1和常压条件下,催化剂的乙苯平均转化率为79.51%,苯乙烯平均选择性为95.91%,苯乙烯平均收率为76.25%。侧线装置上条件试验和稳定性试验结果表明,PED-01催化剂的乙苯转化率和苯乙烯平均收率均优于进口催化剂,失活速率比进口催化剂慢,具有更好的稳定性。