Modeling of ethylbenzene dehydrogenation catalyst deactivation on an industrial scale

The performance of an ethylbenzene dehydrogenation industrial reactor was studied for about 800 days and a catalyst deactivation model was derived. The results showed that the proposed model can predict catalyst deactivation significantly better than standard models, with only 2.5% prediction error after 800 days of operation. Moreover, the optimal path for increasing the temperature of the styrene production reactor was introduced for the first time to maximize styrene production.     

Effects of cracking and coke formation on the selectivity of iron oxide catalysts in the dehydrogenation of methylbutenes to isoprene

The contributions of cracking and coke formation reactions to a decrease in the selectivity of domestic and imported catalysts for the dehydrogenation of methylbutenes (isopentanes and isoamylenes) into isoprene have been determined. It has been found that hydrothermal treatment in industrial reactors favorably affected an increase in the catalytic characteristics of a domestic iron oxide catalyst for dehydrogenation. The conditions for catalyst activation have been optimized with respect to the temperature and duration of hydrothermal treatment.     

无铬、氧化铁系催化剂用于对乙基甲苯脱氢的催化性能考察

探讨了乙苯脱氢的氧化铁系催化剂用于对乙基甲苯脱氢制取对甲基乙烯的可能性。对四种脱氢催化剂(无铬210、XH-02、315以及G64I)进行了比较,考察了操作条件对无铬210催化性能的影响,认为在一定条件下,无铬210对于乙基甲苯脱氧有较好的活性(转化率60—80％)和选择性(80—90％)。反应产物中乙基甲苯异构体分布取决于原料的异构体分布,操作条件对此并无明显影响。     

Heterogeneous dynamic modeling and simulation of an industrial ethylene oxide reactor experiencing catalyst deactivation

This paper investigates steady-state and dynamic simulation of an industrial fixed-bed ethylene oxide reactor. A mathematical heterogeneous one-dimensional model is developed for simulation of reactor performance in the presence of long term deactivation of silver/a-alumina catalyst. In this paper, steady-state model of the reactor is solved and results of steady state simulation are fed to dynamic simulator as initial condition. When results of dynamic simulation are compared with industrial reactor data, it is found that there were good agreements between simulation results and industrial data. The proposed model is also validated by industrial process data for a period of 1100 operating days.     

氧化铁尺寸对铁系乙苯脱氢催化剂性能的影响

采用干混法,以超微细（Ф1～10um）或颜料级（Ф0．1～0．9mm）氧化铁红（黄）的不同搭配为主要原料制备出几种乙苯脱氢催化剂,并对催化剂的物性和活性进行了分析评价。结果表明,超微细氧化铁的颗粒尺寸能够符合高活性催化剂孔径应达到300nm的要求,所制备催化剂的侧压强度、孔径均大于采用颜料级氧化铁红（黄）制得的催化剂,且前者的乙苯转化率和苯乙烯收率均比后者高出约1个百分点。     

异丁烷脱氢制异丁烯Pt-Sn催化剂的宏观失活动力学

在固定床反应器上研究了异丁烷脱氢制异丁烯时Pt-Sn催化剂的失活动力学。结果表明,外扩散对异丁烷脱氢反应的影响不大,可以忽略不计,异丁烷相对浓度差为0.2%～0.6%,温度差为0.30～0.55℃;内扩散对脱氢反应速率有一定影响,温度差为0.10～0.25℃,效率因子为0.80～0.95;催化剂的使用寿命约为1 d,在0～17 h区间催化剂的活性缓慢下降,17 h后催化剂的活性迅速下降。     

工业甲醇合成催化剂的失活与再生研究

经研究铜基催化剂的失活原因及再生方法 ,发现失活催化剂中有硫、镍和积炭存在 ,表面出现铜粒长大现象。采用H2 O、CO、CO2 、H2 、NH3 、H2 O2 、HNO3 处理 ,二氧化碳、乙醚超临界洗涤等方法对失活催化剂进行再生 ,其催化活性有一定程度提高 ,酸溶后再制备是较好的再生方法。     

乙苯脱氢催化剂产品质量的改进

在乙苯脱氢LH 365催化剂的工业放大生产中,采用将氧化铁的加入量在原配方量的基础上提高3.5%～5.0%,微量元素氧化物（氧化钴、氧化钛、氧化锡、氧化锰等）采用捏合加入方式,催化剂采用两步法干燥及调整催化剂活化工艺等手段,可生产出质量稳定的催化剂.结果表明,该产品达到了合同指标,同时接近小试催化剂的性能.     

Effect of temperature on deactivation models of alumina supported iron catalyst during Fischer-Tropsch synthesis

Determination of catalyst deactivation model plays prominent role in process controlling. The aim of this study is to investigate deactivation models of Fe/Al₂O₃ catalyst at different temperature during the Fischer-Tropsch synthesis. Data analysis determined the suitability of second-order GPLE model to describe deactivation behavior of the catalyst. Comparing model parameters at different conditions demonstrated that the catalyst deactivation rate increased by temperature elevation. Analysis of the models also revealed that the catalyst deactivation involves two stages, the first stage occurs at high temperatures while the next step happens at low temperatures, and the deactivation energy of both stages was calculated.     

CNY-102型乙醇脱氢制取乙酸乙酯催化剂研究

研究了一种新的乙醇脱氢制乙酸乙酯催化剂。研究表明，用无水乙醇和含水５％的工业乙醇为原料时的结果基本一致，即乙醇单程转化率约６０％（ｍａｓｓ），乙酸乙酯收率约５０％（ｍａｓｓ）。较之以往的催化剂更具有工业开发前景。     

CNY－101型乙醇脱氢制取乙酸乙酯催化剂研究

研究了一种乙醇脱氢法制取乙酸乙酯的催化剂，研究结果：使用无水乙醇原料时，单程转化率＞６０％，乙酸乙酯收率＞５０％（ｍａｓｓ），副产物为较为纯净的氢气。乙醇脱氢法将在某些地区可能取代传统的酯化法，具有工业化开发前景。     

CNY－101型乙醇脱氢制取乙酸乙酯催化剂研究

研究了一种乙醇脱氢法制取乙酸乙酯的催化剂，研究结果：使用无水乙醇原料时，单程转化率＞６０％，乙酸乙酯收率＞５０％（ｍａｓｓ），副产物为较为纯净的氢气。乙醇脱氢法将在某些地区可能取代传统的酯化法，具有工业化开发前景。     

丁烯氧化脱氢制丁二烯微球催化剂的制备与性能

以共沉淀-喷雾干燥法制备了丁烯氧化脱氢制丁二烯微球催化剂,表征了其物理化学性质,并且与粉碎成型催化剂作了对比分析,同时研究了微球催化剂的反应性能。结果表明:微球催化剂的主要活性组分为ZnFe₂O₄和α-Fe₂O₃;与粉碎成型催化剂相比,微球催化剂含有大量的介孔结构,比表面积较大,还原能力较强;在进料体积空速为400 h-1,反应温度为360℃,水蒸气/重碳四烃中烯烃(摩尔比)为12,氧气/重碳四烃中烯烃(摩尔比)为0.65的最佳条件下,丁烯转化率达到85.7%,丁二烯选择性为96.3%,丁二烯收率(摩尔分数,下同)为82.5%,碳氧化合物收率不高于5%。     

乙苯脱氢催化剂在苯乙烯装置中的应用

大庆石油化工总厂化工厂苯乙烯装置是引进美国Badger工艺,自开工至今已经连续运行10 a,先后应用了5批乙苯脱氢催化剂.通过对每批催化剂的运行数据进行分析,总结出乙苯脱氢催化剂的使用经验,对同类装置的运行具有借鉴和指导作用.     

铜基甲醇合成催化剂失活的研究

用Ｘ射线衍射、小角Ｘ射线散射、ＢＥＴ流动色谱及化学分析等方法，对工业甲醇合成催化剂在失活前后的物相、晶粒度、孔径分布和比表面积等物化性质进行测定。与新鲜催化剂对比后发现，失活催化剂有硫中毒现象。在ＨＣｌ＋Ｈ２Ｏ２的混合溶液不溶物残渣中，有Ｃ和ＡｌＶ２Ｏ４晶相出现，且残渣的含量增多。氧化态时，催化剂的孔径主要分布在ｄ≤１０ｎｍ的微孔区，在经过Ｈ２还原后，孔径分布发生变化，有相当部分转变为ｄ＞１０ｎｍ的过渡孔。晶粒度测定结果表明，催化剂中Ｃｕ（１１１）晶面的平均线宽约为２７ｎｍ，在失活前后变化不大；而ＺｎＯ（１１０）晶面的平均线宽在失活后有显著长大，从８．９ｎｍ变为１５．８ｎｍ。对催化剂的失活原因进行了分析。     

Chemical group composition of residue in processing atmospheric resid over iron oxide catalyst

Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 6, pp. 23–25, November–December, 1995.     

Elemental composition of deposits on natural iron oxide catalyst in processing medium-sulfur feed

Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 6, pp. 28–30, November–December, 1995.