轻汽油醚化工艺中分馏塔设备选型及工艺设计

分馏塔在轻汽油醚化装置中的主要任务是将催化汽油中初馏点至75℃馏分中的叔戊烯、叔己烯和叔庚烯分离出来(轻汽油),并将其作为汽油醚化的原料.轻汽油在酸性树脂催化剂的存在下与甲醇进行醚化反应,从而降低汽油中的烯烃含量.本分馏塔设计是选用浮阀塔盘结构的板式塔,主要涉及到塔的总体结构设计、塔板数的确定.     

兰州石化50万t/a催化轻汽油醚化装置运行与优化

采用中国石油自主研发开发的催化轻汽油醚化工艺(LNE)技术,兰州石化建成50万t/a轻汽油醚化装置并投产成功。装置数据表明,C5、C6叔碳烯烃转化率分别为72%~77%、50%~60%,催化轻汽油烯烃减少量为18.0个百分点以上,醚化产品油中总醚化物含量为46%~60%,醚化产品油辛烷值(RON)为98~100,目前该装置已不间断平稳运行1年以上。醚化装置运行效果良好,产生了显著的经济效益和社会效益。     

无醇乙基叔丁醚的合成

用乙醇和叔丁醇在稀疏酸催化下得乙基叔丁醚粗产物。再经多次水洗、干燥、金属钠回流后，重蒸，即得无醇的乙基叔丁醚。     

流化催化裂化轻汽油组合式醚化工艺的模拟

提出了预反应与反应精馏相结合,预反应器环境适合C6烯烃醚化,反应精馏塔环境适应C5烯烃醚化的组合式FCC轻汽油醚化新思路.运用过程模拟软件Aspen Plus 10.2,对上述组合式醚化新工艺进行了模拟优化分析.模拟时采用平衡级模型RadFrac作为反应精馏模型,并使用Visual Fortran 6.5编写了动力学子程序接口.其中的相平衡计算,采用了UNIF-DMD活度系数模型,对于Aspen数据库中缺失而又鲜有文献报道相关组分的热力学性质,采用了Bcnsonhe Joback等基团贡献法进行了估算,得到了常压下各叔烯烃不同温度下醚化反应的Gibbs自由能变化以及各醚化反应的平衡常数.结果证实,在优化的工艺操作条件下,组合式FCC轻汽油醚化工艺,可以解决现行醚化工艺烯烃转化率较低的问题,使FCC轻汽油产品可使烯烃体积分率从42.40%降低至25.40%,辛烷值提高2.74个单位.     

催化轻汽油溶剂抽提脱硫工艺与醚化LNE-2工艺在轻汽油醚化装置上的联合应用

介绍了催化轻汽油溶剂抽提脱硫工艺和醚化LNE-2工艺,并分别对抽提脱硫单元和醚化单元的操作参数及标定情况进行了分析。应用结果表明,醚化装置运行周期中期仍能保持较高的转化率,C5、C6叔碳烯烃转化率分别为92. 95%、63. 72%。醚化轻汽油产品硫含量可降至4. 5μg/g,烯烃质量分数降低了17. 12%,很好地满足了生产国Ⅴ汽油的需求,并将甲醇调合到汽油中,发挥了增值效应。     

扩孔剂对β沸石催化剂FCC轻汽油醚化性能的影响

制备了催化裂化轻汽油β分子筛醚化催化剂。在小型连续流动固定床反应装置进行了催化裂化轻汽油的醚化反应。考察了催化剂成型过程中，不同分子量和不同质量分数的聚乙二醇(PEG) 、浸渍氧化物方式、挤条成型与浸渍先后顺序对Hβ沸石的醚化反应活性影响, 同时还考察了醚化反应温度、压力、醇烯比和空速对醚化反应的影响。实验结果表明，添加质量分数为10%的扩孔剂PEG-4000成型，再共同浸渍氧化物制备的Hβ分子筛催化剂具有最佳的醚化反应活性。在最佳反应条件（温度70 ℃，压力0.8 MPa，空速1.0 h^－1,醇烯摩尔比1.0）下，叔碳烯烃转化率达到62.93%。     

不同方法合成β沸石的FCC反应性能

报道了不同方法合成β沸石的FCC反应性能,并考察了β沸石的硅铝比对FCC反应产品分布的影响。结果表明：β沸石应用于FCC,与高硅ZSM-5相比,具有提高汽油产率及辛烷值的功能;另外β沸石较高硅ZSM-5表现出更强的异构化功能,具有提高异丁烷和轻汽油异构烯烃（或叔碳烯烃）产率的作用,可丰富烷基化技术和醚化技术的原料来源。     

成型和改性β沸石对催化裂化轻汽油的醚化作用

制备了催化裂化轻汽油β分子筛醚化催化剂，在小型连续流动固定床反应装置上进行了催化裂化轻汽油的醚化反应。考察了催化剂成型过程中，双组分MoO3／P2O5含量，不同相对分子质量和不同质量分数的聚乙二醇（PEG）、黏结剂r-Al2O3，胶溶剂浓删伤，浸渍氧化物方式、挤条成型与浸渍先后顺序对醚化反应活性的影响。实验结果表明，添加质量分数为10％的扩孔剂PEG-4000。质量分数为20％的黏结剂r-Al2O3，质量分数为10％的浓HNO3，均匀混合挤条成型，再共同浸渍MoO3（1％）／P2O5（3％）制备的Hp分子筛催化剂具有极佳的醚化反应活性。在最佳反应条件（温度70℃，压力0．8MPa，空速1．0h～，醇烯比1．0）下叔碳烯烃转化率达到62．93％，主要醚TAME产率也较高，有良好应用前景。     

碳五烯烃醚化合成甲基叔戊基醚的现状与展望

甲基叔戊基醚（TAME）是高辛烷值汽油添加剂，本文分析近几年有关TAME的生产技术与其密切相关的动力学研究状况，指出TAME反应动力学的机理模型，同时对我国进一步开发与研究TAME提供参考性意见。     

轻汽油醚化工艺技术开发成功

由齐鲁石化研究院开发成功的轻汽油醚化工艺技术 ,近日在京通过鉴定。该技术是将ＦＣＣ轻汽油馏分 (≤ 75℃ )经水洗和选择性加氢处理 ,以满足醚化工艺对原料的质量要求 ,然后经串联的醚化反应器和催化蒸馏塔进行醚化反应。目前 ,该工艺已完成中试。结果表明 ,叔戊烯的总转化率≥ 91% ,ＴＡＭＥ的选择性≥ 99% ;叔己烯的总转化率≥ 4 1% ,甲基叔己基醚的选择性达 10 0 %。经醚化的轻汽油馏分与重汽油馏分调和后的汽油烯烃含量降低 5.4个质量百分点 ,蒸汽压降低 10 .5% ,辛烷值 (ＲＯＮ)提高 1个单位 ,氧含量约达 1.14%。该技术达到了目前国…     

醚化工艺及催化剂新进展

对几种以异构烯烃和醇的醚化工艺作了综述。指出 NEXETHERS和 DET是扩大异构烯烃来源 ,增加醚类产品的重要途径之一。与传统磺化离子交换树脂催化剂相比较 ,沸石具有高热稳定性和无酸流失、高叔烷基醚选择性、对醇 /异构烯烃比不敏感性、易再生特点 ,是醚化催化剂的发展方向     

庆阳石化国Ⅵ汽油升级研究

国家已颁布第六阶段汽油质量标准,对苯、烯烃和芳烃含量有更严格的要求。分析庆阳石化公司汽油生产现状,发现其国Ⅵ汽油生产存在辛烷值不足和烯烃含量过高的问题。经过多方案对比,确定异构化+醚化+烷基化路线是适合庆阳石化公司国Ⅵ汽油升级路线。分析国家对国Ⅵ汽油的升级安排和庆阳石化公司的现实需求,建议采用分步分期实施的方案:先建设异构化装置,提高汽油池辛烷值,减少乙醇汽油调合组分油产量;其次建设醚化装置,大幅降低汽油池烯烃含量,满足满足国ⅥA阶段汽油的要求;最后建设烷基化装置,增产汽油并进一步稀释汽油池烯烃含量,生产国ⅥB阶段汽油。     

Equilibrium of the simultaneous etherification of isobutene and isoamylenes with ethanol in liquid-phase

The simultaneous etherification of isobutene and isoamylenes with ethanol has been studied using macroreticular acid ion-exchange resins as catalyst. Most of the experiments were carried out over Amberlyst-35. In addition, Amberlyst-15 and Purolite CT-275 were also tested. Chemical equilibrium of four chemical reactions was studied: ethyl tert-butyl ether formation, tert-amyl ethyl ether formation from isoamylenes (2-methyl-1-butene and 2-methyl-2-butene) and isomerization reaction between both isoamylenes. Equilibrium data were obtained in a batchwise stirred tank reactor operated at 2.0 MPa and within the temperature range from 323 to 353 K. Experimental molar standard enthalpy and entropy changes of reaction were determined for each reaction. From these data, the molar enthalpy change of formation of ethyl tert-butyl ether and tert-amyl ethyl ether were estimated. Besides, the chemical equilibrium between both diisobutene dimers, 2,4,4-trimethyl-1-pentene and 2,4,4-trimethyl-2-pentene, was evaluated. A good agreement between thermodynamic results for the simultaneous etherification carried out in this work and those obtained for the isolated ethyl tert-butyl ether and tert-amyl ethyl ether systems was obtained.     

Solid acid-catalyzed conversion of furfuryl alcohol to alkyl tetrahydrofurfuryl ether

The acidic zeolite HZSM-5 (Si/Al = 25) achieved 58.9% selectivity of methyl furfuryl ether (MFE) and 44.8% selectivity of ethyl furfuryl ether (EFE) from etherification of furfuryl alcohol with methanol and ethanol. MFE and EFE were quantitatively hydrogenated into methyl tetrahydrofurfuryl ether (MTE) and ethyl tetrahydrofurfuryl ether (ETE) using a Raney Ni catalyst.     

合成β-萘乙醚的研究进展

β-萘乙醚是一种很好的香料。合成β-萘乙醚催化剂的研究对于p萘乙醚的生产具有重大影响。评述了近年来合成β-萘乙醚的Williamson法和β-萘酚乙醇醚化法。结果表明,固体酸（对甲苯磺酸、三氯化铁、氯化铜、硫酸铝、硫酸铁和硫酸氢钠等）是由β-萘酚和乙醇醚化合成β-萘乙醚的良好催化剂。     

含水乙醇制备醇醚燃料的工艺研究

以A-15为催化剂,含水乙醇和异丁烯为原料合成乙基叔丁基醚（ETBE）。结果表明：在80℃下,n（乙醇）∶n（异丁烯）=3.0∶1,催化剂用量7 wt%～9 wt%,反应150 min,异丁烯的转化率为90.5%,乙基叔丁基醚（ETBE）的收率为77.2%,水的相对转化率为80.4%。反应产物脱丁烷后进行精馏分离,塔顶可得到高醚含量且易于萃取分离的含醚混合物,塔釜可得到含水量低于0.8%的一元醇产品。     

催化裂化汽油降烯烃研究进展

介绍了降低汽油烯烃的反应原理和方法，其中包括使用降烯烃催化剂和助剂、烷基化、加氢精制、芳构化、轻汽油醚化、汽油回炼及其他工艺技术的改进等。并提出了催化裂化汽油降烯烃的方法应该具有的技术特征。     

Functionalized Multi-Walled Carbon Nanotubes as Heterogeneous Lewis Acid Catalysts in the Etherification Reaction of tert-Butyl Alcohol and Ethanol

Most of the conventional catalysts exhibited limitations in catalyzing etherification reactions. In this study, functionalized multi-walled carbon nanotube (F-CNT) catalyst containing Lewis acid sites were prepared via functionalization with sulfuric acid and the catalytic performances in the etherification of tert-butyl alcohol (TBA) with ethanol were investigated. Characterization of F-CNTs with thermogravimetric analysis, Raman spectroscopy, Fourier transform-infrared spectroscopy, pyridine adsorption, temperature-programmed desorption of ammonia and nitrogen adsorption were performed to correlate the characteristics with the catalytic performances. The catalyst showed a high catalytic performance and high selectivity in the etherification reaction. The best reaction conditions obtained consist of 4 h of reaction time at 140°C, an ethanol:TBA molar ratio of 2:1 and a catalyst loading of 3 wt%. The best conversion of TBA and TBA selectivity toward ethyl tert-butyl ether (ETBE) were 64% and 68%, respectively. No significant degradation of the catalytic performance was observed after four consecutive reactions and the catalyst was easily regained after regeneration. A mechanism for the etherification reaction was also proposed.     

Preparation and characterization of zeolite catalysts for etherification reaction

Catalytic etherification of 2-naphthol with ethanol has been carried out over a series of solid-acid catalysts such as H-Beta, H-MOR and H-ZSM-5 using a flow-type reactor. H-Beta zeolite shows higher conversion and catalytic stability than other catalysts for the production of 2-naphthyl ethyl ether, which may be correlated to the amount and strength of acid sites. H-Beta zeolites with different Si/Al ratios show that conversion decreases with increasing Si/Al ratios. The NH₃-TPD profiles indicate that the weak acidity decreases more sharply with increase in Si/Al ratios, compared with the strong acidity. The influences of ethanol/2-naphthol molar ratios, reaction temperature, and space velocity with respect to catalytic activities are investigated for H-Beta zeolite in the present work.