沉淀剂对ZnCr氧化物催化剂合成异丁醇性能的影响

为开发高选择性和稳定性的异丁醇合成催化剂,选用了不同的沉淀剂,通过共沉淀法制备了系列ZnCr基氧化物催化剂。采用N_2吸附-脱附、X射线衍射(XRD)、程序升温还原(H_2-TPR)等手段对催化剂织构参数、体相结构、还原性能等进行表征,并研究了其CO加氢制异丁醇的催化性能。表征数据表明:使用碱性较弱的沉淀剂时,制得的催化剂比表面积较大,ZnO和Cr_2O_3形成非计量比尖晶石Zn_xCr_(2/3(1-x))O结构,且颗粒分散度较好,被还原能力较强。使用强碱性沉淀剂时,制得的催化剂比表面积较小,出现相分离现象,且被还原能力较差。研究结果表明,使用(NH_4)_2CO_3沉淀剂制备的ZnCr催化剂表现出了最佳的催化性能。该催化剂在390℃,10000h~(-1),12MPa时,CO单程转化率可达15.3%,醇选择性90.3%,异丁醇选择性33.5%。     

非均相催化臭氧氧化深度处理造纸废水的性能

采用农业废弃物水稻秸秆制备秸秆基活性炭,将其负载过渡金属Mn和Fe作为臭氧催化剂。采用正交试验考察了制备参数对其催化活性的影响,结果表明,最佳制备条件:浸渍时间为12 h,热解温度为500℃,热解时间为3 h。以制备的催化剂催化臭氧氧化深度处理造纸废水,COD和色度平均去除率分别为74.3%和80.5%,处理出水达到《城镇污水处理厂污染物排放标准》(GB 18918—2002)的一级A排放标准。制备的催化剂稳定性高且经济环保,适于造纸废水深度处理的工程应用。     

铜铬类催化剂对HTPE低易损推进剂燃烧性能的影响

采用差示扫描量热仪(DSC)研究了铜铬类燃速催化剂(亚铬酸铜CC01和铜铬复合氧化物CC02)对端羟基聚醚(HTPE)低易损推进剂中的高氯酸铵(AP)、改性硝酸铵(AN)、HTPE黏合剂体系热分解性能的影响。结果表明,加入少量的CC01和CC02均使AP高温分解峰温明显降低了16和29.7℃,AP高温分解活化能依次降低了16.65和22.59kJ/mol,均可提高AP的高温分解反应速率。CC01和CC02均使AN的热分解峰向低温方向依次前移了52.3和53.6℃,均降低了AN的分解活化能,使AN的热分解反应速率提高了3~4倍。CC01和CC02对HTPE黏合剂体系的热分解影响较小。在AP/AN/Al/HTPE低易损推进剂中,分别添加质量分数0.5%的CC01和CC02可显著提高HTPE低易损推进剂在3~15MPa下的燃速,可使推进剂在7MPa下的燃速分别提高34.1%和43.4%,但CC01和CC02对HTPE低易损推进剂在3~9MPa下的压强指数几乎无影响,而9~15MPa下的压强指数有所降低。     

碱性助剂对加氢脱硫催化剂性质及活性的影响

选择了一种碱性有机盐作为助剂合成加氢脱硫催化剂,通过N2吸附-脱附、XRD、CO_2-IR、NH_3-TPD、原位CO-IR和模型化合物加氢及FCC汽油脱硫反应,表征评价了碱性助剂对催化剂性质及反应活性的影响。通过对比发现了由于生成部分微孔导致含助剂催化剂的比表面积有所提高,孔容、孔径有所下降。由于助剂的加入使催化剂具有一定量的碱性吸附位,原位CO-IR表征证实含碱性有机盐助剂催化剂在硫化过程中会更多生成CoMoS相。通过模型化合物加氢反应和工业FCC汽油脱硫反应证实含碱性有机盐助剂催化剂具有一定的加氢异构能力,其在FCC汽油脱硫反应中的选择性更好,更适用于生产高辛烷值汽油。     

硫磺装置尾气提标改造方案的研究

硫磺回收及尾气处理装置烟气中含有高浓度的二氧化硫,比较了动力波烟气洗涤技术、空塔喷淋碱洗技术、喷射文丘里湿气洗涤技术(WGS)、超重力烟气脱硫技术吸收烟气中的二氧化硫,从烟气净化指标、系统压降、核心设备连续运行周期、运行费用和装置投资方面进行比较,得出喷射文丘里湿气洗涤技术(WGS)优于其他三种方案。     

Silver Nanoparticles Loaded Thermoresponsive Hybrid Nanofibrous Hydrogel as a Recyclable Dip‐Catalyst with Temperature‐Tunable Catalytic Activity

Silver nanoparticles (AgNPs) loaded thermoresponsive nanofibrous hydrogel is fabricated by electrospinning the aqueous solution containing the metal nanoparticles and poly((N‐isopropylacrylamide)‐co‐(N‐hydroxymethylacrylamide)) copolymer, followed by heat treatment. To avoid negative effect of the stabilizer or the residual reductant on their performances, the AgNPs of less than 5 nm size are synthesized through reducing Ag⁺ ions in the spinning solution by UV irradiation. The prepared nanofibrous hydrogel with desirable stability in aqueous medium has significant thermoresponsive property, and can reach its swelling or deswelling equilibrium state within 15 s with the medium temperature changing between 25 and 50 °C alternately. The smart nanofibrous hydrogel as a dip‐catalyst has the catalysis for the reduction of 4‐nitrothiophenol to 4‐aminothiophenol by NaBH₄, and its catalytic activity can be rapidly tuned by temperature. Moreover, it can be facilely recycled from the reaction system at least four times, without any loss of its catalytic activity.     

Toward understanding the mechanism of improving the production of volatile fatty acids from activated sludge at pH 10.0

A well-defined fractionation approach for sludge flocs was applied to a better understanding of the underlying mechanism of improving the production of volatile fatty acids (VFA) in the hydrolysis and acidification processes at pH 10.0. Specifically, sludge flocs were fractionated through centrifugation and ultrasound into four fractions: (1) slime, (2) loosely bound extracellular polymeric substances (LB-EPS), (3) tightly bound EPS (TB-EPS) and (4) pellet. Result showed that during 20 days of fermentation, the total VFA production at pH 10.0 was higher, from 2 to 34 times, than that at pH 5.5. At pH 10.0, however, the enzyme activities (i.e. protease, alpha-amylase, alkaline phosphatase and acid phosphatase) in all fractions of sludge flocs were all lower than pH 5.5, which strongly suggests that the biotic effect was not the leading cause of the VFA improvement. Further investigation suggests that pH 10.0 could significantly improve the VFA production through the break of sludge matrix which is usually hydrolyzed by the extracellular enzymes embedded in itself, increase the effective contact between extracellular organic matters and enzymes, and create a favorable environment for microbes to accumulate VFA. Hydrolysis and acidification at pH 10.0 can be considered as part of an appropriate solution for tertiary treatment and contribute to the headway toward the goal of sustainable water treatment technologies.     

Hydrometallurgical route to recover molybdenum, nickel, cobalt and aluminum from spent hydrotreating catalysts in sulphuric acid medium

This work describes a hydrometallurgical route for processing spent commercial catalysts (CoMo and NiMo/Al₂O₃), for recovering the active phase and support components. They were initially pre-oxidized (500 °C, 5 h) in order to eliminate coke and other volatile species present. Pre-oxidized catalysts were dissolved in H₂SO₄ (9 mol L⁻¹) at 90 °C, and the remaining residues separated from the solution. Molybdenum was recovered by solvent extraction using tertiary amines. Alamine 304 presented the best performance at pH around 1.8. After this step, cobalt (or nickel) was separated by adding aqueous ammonium oxalate in the above pH. Before aluminum recovery, by adding NaOH to the acid solution, phosphorus (H₂PO₄⁻) was removed by passing the liquid through a strong anion exchange column. Final wastes occur as neutral and colorless sodium sulphate solutions and the insoluble solid in the acid leachant. The hydrometallurgical route presented in this work generates less final aqueous wastes, as it is not necessary to use alkaline medium during the metal recovery steps. The metals were isolated in very high yields (>98 wt.%).