加氢裂化催化剂的失活与再生研究

为了研究催化剂失活原因,并为提高催化剂效率和使用寿命提供参考,对一种用于两段式加氢裂化工业装置的失活和再生后的加氢裂化催化剂进行了表征。结果表明,失活催化剂上有明显的积碳、有机硫氮吸附和金属沉积,活性金属团聚、分子筛结构破坏、金属沉积等造成的失活是无法恢复的。再生后,与新鲜催化剂相比,催化剂的比表面积、孔容、活性金属分散性和酸性均有明显下降。小试评价结果表明,再生催化剂的加氢裂化活性降低,反应温度比新鲜剂高2℃左右。原料性质较好、床层温度较低的二段再生催化剂,其理化性质和活性都优于一段再生催化剂。     

常温COS水解催化剂的再生

利用常压微反装置对失活的COS水解催化剂进行了再生研究。结果表明,当失活催化剂在550℃焙烧3h,然后浸渍再生剂、干燥、焙烧再生后,再生催化剂具有足够高的转化率（可达新鲜催化剂90％以上）和良好的活性及稳定性。     

丙烷选择氧化制丙烯酸催化剂失活及再生研究

研究了丙烷氧化制丙烯酸复合金属氧化物催化剂失活的原因,探讨了失活催化剂的再生方法。结果表明,丙烷氧化制丙烯酸复合金属氧化物催化剂失活的原因主要是由于金属Te的流失造成的。进一步的实验证明,通过对失活的催化剂单独浸渍Mo、V、Te、Nb四种金属后的评价结果发现,失活的催化剂浸渍Te后丙烯酸收率有所提高,由原来的1.4%分别上升到4.2%,仍远远低于新鲜催化剂的活性,而失活的催化剂单独浸渍Mo、V、Nb后,活性没有变化。     

TH-3型脱氢催化剂失活原因探讨

用X射线荧光分析法（XRF）、X射线光电子能谱法（XPS）、红外光谱法（IR）、热重法（TG）及相关化学方法对工业应用失活的TH-3型脱氢催化剂进行了表征和评价。结果显示,催化剂失活的主要原因为硫中毒。通过新型的常温液相再生方法,可以使工业失活催化剂的活性基本恢复至新鲜催化剂的水平。     

常温COS水解催化剂的再生与应用

分析了COS水解催化剂失活的原因 ,给出了再生处理流程 ,对失活的、再生后的和国内新鲜催化剂在不同温度和空速下进行了活性对比试验 ,并介绍了工业试生产及工业应用过程     

关于精对苯二甲酸(PTA)生产用钯碳催化剂的制备研究

本文主要对精对苯二甲酸(PTA)生产用钯碳催化剂的制备与再生进行了分析。首先对新鲜催化剂制备与催化剂活性评价进行了分析,接着对制备过程对催化剂活性的影响进行了分析,主要是吸附周期及还原过程的影响,最后对钯催化剂寿命延长及再生进行了研究,钯碳催化剂寿命延长失活与钯碳催化剂再生能够再生失活钯碳催化剂。     

常温DOS水解催化剂的再生与应用

分析了COS水解催化剂失活的原因,给出了再生处理流程,对失活的、再生后的和国内新鲜催化剂在不同温度和空速下进行了活性对比试验,并介绍了工业试生产及工业应用过程。     

工业加氢裂化催化剂失活原因分析

采用200 m L加氢评价装置对一种中油型加氢裂化催化剂和其在工业装置运转4年后的再生后催化剂进行对比评价。结果表明,失活催化剂经再生后加氢裂化活性明显降低,反应温度比新鲜催化剂高5℃,生成油产品分布和主要性能都略变差。采用XRD、IR和ICP等手段对再生前后催化剂性能进行表征,分析探讨催化剂的失活原因,结果表明,加氢裂化催化剂经工业应用后,炭的沉积使其暂时性失活,而重金属沉积、金属活性组分聚集和分子筛结构烧结使催化剂部分活性永久丧失。     

四氢糠醇合成吡啶催化剂MoO_3-NiO/γ-Al_2O_3的失活和再生

采用新鲜的及再生的MoO_3-NiO/γ-Al_2O_3催化剂,催化生物质四氢糠醇合成吡啶,考察其催化性能的差异及催化剂失活的原因,并通过氮气物理吸附测试(BET)、元素分析仪(EA)、场发射扫描电子显微镜(SEM)、场发射透射电子显微镜(TEM)、X射线衍射分析仪(XRD)、激光拉曼光谱仪(LRS)、X射线光电子能谱仪(XPS)、热重分析仪(TG)以及吡啶原位红外吸收光谱仪(PY-IR)对失活催化剂进行表征分析。发现失活催化剂有两种形态的碳,即无定形碳和石墨化碳,催化剂失活的原因不是活性组分的变化或流失,而是由积碳引起的。积碳堵塞了催化剂的孔道和比表面积,并且覆盖了活性组分以及酸性位,降低了活性位点的有效利用率。针对催化失活,尝试了在线燃烧的方法使失活催化剂在空气中再生,发现再生后的催化剂与新鲜催化剂的催化活性基本一致,并且也可以保持50 h内吡啶收率大于80%。     

加氢裂化催化剂失活与再生

利用XRD、XPS、TPR、ICP、IR、TEM 等技术, 测试和表征几种不同类型新鲜的、失活的和再生后工业用非贵金属加氢裂化催化剂的性能, 找出该催化剂失活的主要原因。经研究发现,加氢裂化预精制催化剂主要失活原因是积炭和金属聚集; 加氢裂化催化剂主要失活原因是积碳、所含沸石倒塌、金属聚集、孔结构堵塞及倒塌, 对于单段加氢裂化催化剂失活原因, 还包括酸中心中毒等。本文还探讨了器内与器外再生方式利弊及今后发展趋势。     

柴油加氢裂化装置加氢裂化催化剂失活分析

在某炼油厂柴油加氢裂化装置停工换剂时,取样分析加氢裂化催化剂。对所取裂化剂进行甲苯抽提、再生后,采用比表面积及孔径分析仪、碳硫分析仪(C-S)和X射线衍射仪(XRD)等手段进行检测。结果表明,失活裂化剂的比表面积、孔容等孔结构性能参数明显降低。在最优的再生条件下,再生裂化剂上的C含量降至0.360%,裂化剂的表面或其它位置未发现杂质的明显沉积。再生裂化剂的比表面积损失约21.5%,其中微孔比表面积的损失约占87.2%,孔容损失约17.4%。加氢裂化催化剂长期在高温等条件下反应,造成分子筛晶粒的烧结、团聚等是导致其比表面积等孔结构性能降低的主要原因。     

NTP再生La改性多级孔HZSM-5及催化提质生物油的试验研究

以氧气为气源，利用低温等离子体（NTP）喷射系统，在不同温度下对结焦失活的La改性多级孔HZSM-5分子筛进行再生，采用TG、XRD、Py-IR及N₂吸附-脱附等测试技术对再生前后催化剂的理化性质进行表征，并利用再生催化剂进行在线催化提质生物油试验。结果表明，再生温度为250℃时，失活La改性多级孔HZSM-5分子筛再生效果最好，去除了97.4%的积炭，其表面结晶度、酸性、比表面积和孔容恢复程度最高。再生温度上升至300℃时，O₃分解较多，此时O₃分解已经成为积炭氧化分解的限制因素，排气中CO₂和CO浓度峰值减小，失活催化剂再生效果有所下降。再生温度为250℃时，再生催化剂催化性能恢复最好，制得的生物油高位热值最大（36.48 MJ/kg），烃类含量最高（40.51%），其理化性质与新鲜催化剂制得的生物油理化性质最接近。     

长链烷烃脱氢失活催化剂的表征及其烧炭再生温度研究

以N2物理吸附-脱附、压汞、热重和CO脉冲化学吸附催化剂物化表征手段对工业失活长链烷烃脱氢催化剂进行表征,并考察烧炭再生温度对催化剂活性的影响.结果表明,与新鲜催化剂相比,失活催化剂比表面积和总孔容略有下降,孔径分布向小孔方向移动.通过氧化烧炭可使催化剂活性部分恢复.O2-N2混合气(O2体积分数1%)气氛氧化烧炭适宜...     

柴油加氢反应器不同位置精制剂的失活分析

针对某炼油厂柴油加氢裂化装置停工换剂时发现加氢精制反应器床层顶部的精制剂表面覆盖垢物的现象,对不同位置的精制剂进行取样分析。对所取精制剂进行甲苯抽提、再生后采用比表面积及孔径分析仪、碳-硫分析仪（C-S）和扫描电子显微镜（SEM）等手段进行检测。结果表明：不同位置的失活精制剂上积炭量均较低,而比表面积等孔结构参数均显著降低,尤以装填位置靠上的精制剂更为明显,失活精制剂的再生效果均不理想;再生精制剂上出现磷酸铝特征衍射峰,精制剂表面沉积含磷、硅、铁和少量砷元素的无机物,或少量进入精制剂孔道,其是导致精制剂失活的主要原因,而且沿着物流自上而下的流向精制剂上杂质的沉积量逐渐减少,催化剂的失活程度减弱。     

Regeneration of Lamina TS-1 Catalyst in the Epoxidation of Propylene with Hydrogen Peroxide

The deactivation and regeneration of the lamina titanium silicalite (TS-1) catalyst for the epoxidation of propylene with dilute H₂O₂was investigated in a fixed-bed reactor. In the scale-up experiment, the dosage of the lamina TS-1 catalyst is 2. 5 kg, after 1000 h reaction the catalyst still exhibits good performance and further increases the reaction time, the conversion of H₂O₂begins to decrease. TG and BET analyses of the deactivated catalysts show that the main species occluded within the zeolite pore are propylene oxide oligomers, and these species occupying the active Ti site and blocking the pores of the lamina TS-1 are the main reason for the deactivation of catalyst. The deactivated catalyst can be regenerated by different regeneration methods. The activity of deactivated catalysts regenerated by dilute H₂O₂or heat treatment by using air or nitrogen as a calcination media can be fully recovered, but a decline in propylene oxide (PO) selectivity of the regenerated catalyst has been observed during the first hours of reaction. However, water vapor treatment of the deactivated catalyst can improve the PO selectivity with the same activity as that of the fresh lamina TS-1 catalyst.     

Deactivation and regeneration of TS-1/SiO2 catalyst for epoxidation of propylene with hydrogen peroxide in a fixed-bed reactor

TS-1/SiO₂ catalyst for the epoxidation of propylene with hydrogen peroxide in a fixed-bed reactor has been investigated. The catalyst activity decreases gradually with the online reaction time, but the selectivity of propylene epoxide is kept at about 93%. The fresh, deactivated and regenerated catalysts were characterized with X-ray diffraction, Fourier transform infrared spectroscopy, ultra-violet-visible diffuse reflectance, Brunner-Emmett-Teller method and thermogravimetric analysis, and the deactivated catalyst was regenerated with H₂O₂/methanol solution. Compared with the fresh catalyst, both the framework structure and the content of titanium in the framework of the deactivated and regenerated TS-1/SiO₂ catalysts were not changed. The major reason of the catalyst deactivation was the blockage of the channels of the catalyst by bulky organic by-products, which covered the active centers of titanium in TS-1. The deposited materials on the deactivated TS-1/SiO₂ catalyst could be removed by treatment with hydrogen peroxide/methanol solution or pure methanol; the higher the treatment temperature and the higher the concentration of H₂O₂ in methanol, the higher the extent of the regeneration. The regeneration treatment did not influence the product selectivity in the propylene epoxidation.     

异丙苯合成分子筛催化剂的水蒸汽再生

研究了中试失活的M-92异丙苯合成催化剂上积炭的性能及在不同温度下的H₂O-O₂-N₂烧炭再生。对再生后催化剂的活性、酸性、比表面积和结晶度等性能进行了考察和测定。结果表明,催化剂上的积炭有两种形态,低温炭和高温炭。再生温度及再生时间对催化剂再生性能有重要影响,水蒸汽再生温度可控制在450 ℃以下。在适宜再生条件下,催化剂活性能够恢复,且稳定性比新鲜催化剂的更好。     

Supercritical fluid CO<Subscript>2</Subscript>-extraction regeneration of nickel–molybdenum catalyst for hydrotreatment

Results from studying the supercritical fluid СО₂-extraction regeneration of DN-3531 industrial nickel–molybdenum hydrotreatment catalyst in the temperature range of 323.15–383.15 K, at pressures of up to 30 MPa, and with modification of the basic extragent with such polar compounds as chloroform, methanol, ethanol, acetone, and dimethylsulfoxide (DMSO), are presented. The order of modifiers corresponds to the increase in the solubilizing ability of modified supercritical carbon dioxide (SC-СО₂) with respect to catalyst- deactivating deposits. With DMSO as the most efficient modifier, however, not only are deactivating compounds removed but nickel and molybdenum as well, considerably reducing the final activity of a regenerated sample. During extraction regeneration, the content of coke in the catalyst is reduced by two-thirds, while the specific surface area and the pore volume grow. The activity of the deactivated catalyst in dibenzothiophene hydrodesulfurization (HDS) and naphthalene hydrogenation grows by several hundred per cent after one-time SC-CO₂ treatment and is 2.5 times higher than for a sample regenerated using the traditional oxidative method.     

One Step Preparation of Sulfonated Solid Catalyst and Its Effect in Esterification Reaction

A carbon-based sulfonated catalyst was prepared by direct sulfonation and carbonization （in moderate conditions：200 ＆#176;C, 12 h） of red liquor solids, a by-product of paper-making process. The prepared sulfonated cata-lyst （SC） had aromatic structure, composed of carbon enriched inner core, and oxygen-containing （SO3H, COOH, OH） groups enriched surface. The SO3H, COOH, OH groups amounted to 0.74 mmol·g^-1, 0.78 mmol·g^-1, 2.18 mmol·g^-1, respectively. The fresh SC showed much higher catalytic activity than that of the traditional solid acid catalysts （strong^-acid 732 cation exchange resin, hydrogen type zeolite socony mobile-five （HZSM-5）, sulfated zir-conia） in esterification of oleic acid. SC was deactivated during the reactions, through the mechanisms of leaching of sulfonated species and formation of sulfonate esters. Two regeneration methods were developed, and the catalytic activity can be mostly regenerated by regeneration Method 1 and be fully regenerated by regeneration Method 2, respectively.