闪锌矿浮选的活化与去活化研究进展

重点综述了闪锌矿活化与去活化的研究进展,讨论了闪锌矿活化离子的来源,指出闪锌矿活化受矿浆电位、pH值、活化剂浓度和晶格缺陷等因素影响,铜氨络离子对闪锌矿及铁闪锌矿具有良好的活化效果,能降低选矿药剂成本,改善锌精矿质量;去活化作用通过清除闪锌矿表面活化层或在其表面生成亲水薄膜实现;从回水利用、矿物的内外部环境和新药剂等方面预测了多金属硫化矿石的选矿理论与实践的发展方向.     

废弃选择性催化还原催化剂混掺对新催化剂脱硝性能的影响

采用"混炼-挤出-干燥-煅烧"工艺制备了不同废弃选择性催化还原（SCR）催化剂混掺比例的新催化剂样品,在自制实验台架上进行了脱硝性能和脱硝寿命评估实验。实验表明,当废催化剂混掺比例小于5%时,样品脱硝性能相比无混掺样品有轻微下降,催化剂脱硝效率随运行时间的衰减速率正常;当混掺比例大于5%时,催化剂样品脱硝性能大幅衰减,催化剂寿命缩短。结合N₂吸附-脱附、扫描电子显微镜（SEM）、X射线荧光光谱（XRF）、X射线衍射（XRD）等表征手段分析,废催化剂的掺入会将碱金属、As等有害物质带入到高混掺量的样品中,导致催化剂脱硝性能下降;混掺比例高达15%时,15-cat样品表面复杂程度大幅下降,不利于SCR反应进行。实验论证了较高废弃催化剂混掺比例会严重影响制备所得新催化剂的脱硝性能。     

A kinetic model for the enzyme-catalyzed self-epoxidation of oleic acid

This paper reports a kinetic model for the selfepoxidation of oleic acid with toluene as solvent and Novozym 435 (a commercially available preparation of immobilized Candida antarctica lipase) as catalyst at 30°C. The effects of various parameters on the conversion and rates of reaction were studied. Both the initial rate and the progress curve data were used to fit an ordered bi-bi model. At low temperatures, the rate of epoxidation was faster than the rate of deactivation of the enzyme by hydrogen peroxide.     

Deterioration Mode of Barium-Containing NOx Storage Catalyst

Barium-containing NO _x storage catalyst showed serious deactivation under thermal exposure at high temperatures. To elucidate the thermal deterioration of the NO _x storage catalyst, four types of model catalyst, Pt/Al₂O₃, Ba/Al₂O₃, Pt–Ba/Al₂O₃, and a physical mixture of Pt/Al₂O₃ + Ba/Al₂O₃ were prepared and their physicochemical properties such as BET, NO TPD, TGA/DSC, XRD, and XPS were evaluated while the thermal aging temperature was increased from 550 to 1050°C. The fresh Pt–Ba/Al₂O₃ showed a sorption capacity of 3.35 wt%/g-cat. but the aged one revealed a reduced capacity of 2.28 wt%/g-cat. corresponding to 68% of the fresh one. It was found that this reduced sorption capacity was directly related to the deterioration of the NO _x storage catalyst by thermal aging. The Ba on Ba/Al₂O₃ and Pt–Ba/Al₂O₃ catalysts began to interact with alumina to form Ba–Al solid alloy above 600°C and then transformed into stable BaAl₂O₄ having a spinel structure. However, no phase transition was observed in the Pt/Al₂O₃ catalyst having no barium component, even after aging at 1050°C.     

Kinetic modeling of Fe‐BEA as NH3‐SCR catalyst—effect of phosphorous

The focus of this work is to investigate whether a previously developed microkinetic deactivation model for hydrothermally treated Fe‐BEA as NH₃‐SCR catalyst can be applied to describe chemical deactivation of Fe‐BEA due to phosphorous exposure. The model describes the experiments well for Fe‐BEA before and after phosphorous exposure by decreasing the site density, representing deactivation of sites due to formation of metaphosphates blocking the active iron sites, while the kinetic parameters are kept constant. Furthermore, the results show that the activity for low‐temperature selective catalytic reduction (SCR) is very sensitive to loss of active monomeric iron species due to phosphorous poisoning compared to high‐temperature SCR. Finally, the ammonia inhibition simulations show that exposure to phosphorous may affect the internal transport of ammonia between ammonia storage sites buffering the active iron sites, which results in a lower SCR performance during transient conditions. © 2014 American Institute of Chemical Engineers AIChE J, 61: 215–223, 2015     

甲烷化催化剂及其失活研究进展

阐述甲烷化催化剂活性组分、载体和助剂种类对催化性能的影响。分析催化剂失活的主要原因为中毒失活、积炭失活和烧结失活。目前在国内外工业装置上得到应用的主要为Al2O3、镁铝尖晶石类负载的Ni基甲烷化催化剂。通过载体改性、助剂添加及调配提升催化剂性能是催化剂研发的主要方向。复合载体可以形成特定的稳定结构,提高催化剂的热稳定性;其较高的比表面积利于Ni的分散;碱金属、碱土金属和稀土金属的添加,可以调变载体表面酸性和电负性,减小Ni晶粒尺寸,降低积炭的可能性。     

Cu-K/Al_2O_3催化剂上溴甲烷合成二甲醚的失活动力学研究

采用Cu-K/Al2O3催化剂,在固定床积分反应器上进行溴甲烷合成二甲醚的动力学实验,反应温度(463.15~523.15)K条件下,得出主反应的宏观动力学方程:r=1.1+2.8×10-3T-4.4exp(-21.5/RT)pCH3Br,主反应的活化能约为21.5 k J·mol-1。对主反应宏观动力学方程进行统计检验,结果表明,在给定99%的置信度下,方程显著、可信。失活前后的XRD表征结果表明,催化剂晶相由Cu O转变为Cu Br2是导致催化剂失活的主要原因。采用独立失活机理描述催化剂失活速率方程,通过回归得到各项参数,建立了适用于Cu-K/Al2O3催化剂上溴甲烷合成二甲醚的失活动力学方程:r=[-1.1+2.8×10-3T-4.4exp(-21.5/RT)pCH3Br]×exp(-2.1×10-3t)。     

乙炔法合成氯乙烯用无汞催化剂的失活原因与再生

对近几十年乙炔氢氯化合成氯乙烯用非均相无汞催化剂失活的原因和再生方法进行总结。乙炔法合成氯乙烯催化机理分先吸附乙炔和先吸附氯化氢两类。催化剂活性组分锡、铋和钯流失,氧化态铂和金被乙炔分子还原至低价或金属态,活性组分分散不均和晶粒长大均容易导致催化活性下降。先通入乙炔或乙炔进料过量、表面短链类聚乙烯或聚乙炔过渡态化合物难脱附、不同的载体及其表面性质均会诱导生成积炭物质。制备复合催化剂、添加碱土或稀土金属助剂有助于协同催化和自行还原再生。表面改性能改变吸附顺序,在线通入适量NO以及时去除积炭,可提高催化剂的稳定性。离线有氧烧炭再生含碳载体效果较差,而硝酸加热处理或王水处理失活的贵金属催化剂能恢复初始或接近初始催化活性。并对乙炔氢氯化无汞催化剂的发展进行展望。     

Oxygen Storage Behavior of Ceria–Zirconia-Based Catalysts in the Presence of SO2

This paper investigates the effect of the presence of SO₂ in the dynamics of oxygen storage on ceria and ceria–zirconia. The introduction of SO₂ under reaction conditions at T<873 K negatively affects CO conversion under oscillating conditions on all the supports studied, owing to the formation of sulfate species. Deactivation is observed on all supports and activity is recovered only after desorption of SO₂, which occurs at 950<T<1000 K, depending on catalyst composition (Ce/Zr ratio) and treatment atmosphere. The amount of sulfur adsorbed is higher over solid solutions, reaching a maximum with Ce _x Zr_1–x O₂ (0.5<x<0.68). However this does not adversely affect activity compared to ceria. In the presence of Rh and Pd, reactivation is favored under reaction conditions. More generally, it appears that the removal of sulfates is facilitated in reductive atmospheres (both hydrogen and CO) over mixed oxides. No differences are observed following regeneration under oxidizing conditions.     

Effects of acid strength and micro pore size on -caprolactam selectivity and catalyst deactivation in vapor phase Beckmann rearrangement over acid solid catalysts

The vapor phase Beckmann rearrangement of cyclohexanone oxime (CHO) over solid acid catalysts including zeolites was carried out to elucidate the effects of the acid strength and the micropore size of the catalysts on the selectivity of -caprolactam (CL) and the catalyst deactivation rate. It was found that the catalyst deactivation rate was strongly dependent on the acid strength of the acid catalysts. The improvement of catalyst life was achieved by using MFI-type metallosilicates having weak acid sites. The CL selectivity decreased over the acid catalysts with micropores larger than those of the MFI zeolites. Furthermore, using methanol and carbon dioxide as the diluent solvent and diluent gas improved CL selectivity and catalyst life, respectively.