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。     

甲基叔戊基醚裂解催化剂的催化性能

介绍了SPC-01型催化剂在甲基叔戊基醚(TAME)裂解生产异戊烯中的工业应用。该催化剂具有良好的活性和稳定性,TAME转化率和异戊烯的选择性均超过99%。利用X射线衍射(XRD)、热重分析(TG-DTA)、红外光谱(FT-IR)和孔结构分析对新鲜的和从装置卸出的催化剂进行表征,并对催化剂活性下降的机理进行了讨论。结果表明,在长周期运行中,催化剂比表面下降、结焦和酸性的损失是导致催化剂活性降低的主要原因,最后提出了TAME裂解催化剂的改进方向。     

混合进化算法研究甲基叔戊基醚合成反应动力学

将遗传算法与模拟退火算法相结合,以自适应多重退火交叉策略和自适应多重退火变异策略分别代替传统遗传算法中的单一交叉策略和单一变异策略,在此基础上进一步与进化策略相结合,开发出了一种多进化模式的混合进化算法. 用以上算法对以强酸性阳离子交换树脂A-15为催化剂用甲醇和叔戊醇为原料合成甲基叔戊基醚反应动力学方程中的速度常数、水的阻害系数等参数进行了求解计算,并与传统算法进行了比较. 结果表明：本研究所提出的混合进化算法收敛速度快,估算精度高,有效抑制了早熟现象的发生,所得到的有关动力学参数可靠,模型计算结果与实验结果吻合良好.     

含2—甲基丁烷,甲醇,甲基叔戊基醚体系汽液平衡的测定

含２－甲基丁烷、甲醇、甲基叔戊基醚体系汽液平衡的测定秦金平钱仁渊云志李志宝史美仁（南京化工大学化工分离研究所,南京２１０００９）关键词２－甲基丁烷甲醇甲基叔戊基醚汽液平衡１前言随着对汽油的质量要求越来越高,对无铅汽油抗爆剂进行的研究发现,醚类物质是...     

乙基叔戊基醚的合成及反应动力学研究

用国产NKC－29型强酸性阳离子交换树脂为催化剂，在常液相条件下用乙醇和叔戊醇为原料合成了乙基叔戊基醚。讨论了温度，催化剂浓度，反应物初始摩尔比等参数对反应速度以及反应选择性的影响。结果表明：反应温度升高，将加快反应速度，但是当温度过高将加速叔戊醇的分解，使反应的选择性降低，催化剂浓度与产物的初始生成速率成线性关系，表明反应为动力学控制步骤：增加乙醇与叔戊醇的初始摩尔比，可有效控制叔戊醇分解为水与异戊烯的副反应。与另一种国产S－54型树脂催化剂比较的结果显示：NKC－29的催化活性及选择性优于S－54。根据实验结果并考虑水对催化剂的阻碍效应，建立了该反应的动力学模型，并得到了相应的模型参数，即反应速度常数和水的阻碍系数。实验结果与模型计算值吻合得较好。     

利用夹点技术分析优化甲基叔戊基醚装置换热网络

利用Aspen Plus软件计算出冷流股和热流股的焓变,冷热流股的焓变分别为1.4W和-1.2W,然后运用夹点技术对甲基叔戊基醚固定床装置换热网络进行优化分析.计算结果表明,优化后的换热网络节能效果较好.通过小试数据,可以推断中试乃至工业化装置的换热网络节能情况.     

乙基叔戊基醚合成反应动力学的协同学法分析

用协同学方法分析了乙基叔戊基醚合成反应体系的反应速率问题,通过引入一种非奇异变换将相应的反应速率方程组直接转换成Haken形式,从而发现对系统演化影响较大的序参量,进而通过绝热消去法处理而得到反应体系的各组分浓度与反应时间的演化解析表达式.用该方法求解动力学参数避免了传统方法所遇到的求解微分方程组的困难,计算所得结果与实验值吻合很好.     

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。     

叔戊基蒽醌法双氧水生产过程中部分降解产物的合成

合成了叔戊基蒽醌法生产双氧水工作液中主要的氢化和氧化降解产物。以苯和叔戊基氯为原料,合成了氢化降解产物:2-叔戊基-9-蒽酮、2-叔戊基蒽,当以2-叔戊基蒽醌(20mmol,5.56g)为基准,分12次间隔10min每次加入nHCl∶nSn=5.6mmol∶2.8mmol时,2-叔戊基-9-蒽酮的收率最高,达到65.8%,2-叔戊基蒽的收率达到16.4%;合成了氧化降解产物:2-叔戊基四氢蒽醌环氧化物,当nNaOH∶nH2O2=1∶1时,收率达到95.0%,后处理简单。     

甲基叔丁基醚合成反应器工艺计算

用拟均相一维数学模型对甲基叔丁基醚合成反应器进行电算,并根据电算程序进行优化设计,计算结果与生产数据相吻合。     

Simulation and process integration for tert-amyl-methyl ether (TAME) synthesis

This paper proposes an extended approach to develop a new sustainable process to produce tert-amyl-methyl ether (TAME) using as feedstock enriched C₅ fraction (LCN – light cracking naphtha) from fluid catalytic cracking (FCC). To the best of our knowledge, up to now, different authors developed the separation section without considering all possible options. The main contribution is to bring together for comparison different separation techniques of the given mixture and to develop new configurations for the separation section of the plant. In this respect, pressure swing is combined with liquid–liquid separation. Existing technologies consider methanol (MeOH) separation from reactor effluent only by water extraction, combined with distillation. Conceptual design based on residual curve maps (RCM) analysis, considered in this paper, reveals new possibilities to use pressure swing, eventually combined with liquid–liquid separation. Thus, compared to other results reported in literature, new separation sequences are proposed for TAME synthesis reactor effluent separation, in the frame of an extended and detailed analysis for the whole process.To underline process characteristics, three case studies, with those different configurations are presented and analysed using Aspen HYSYS^® v8.4. Main details are obtained using process simulation, process integration and environmental impact computer tools. In the first case study, classical MeOH separation using water extraction is considered. The second case study is based only on pressure swing distillation to separate the azeotropes between hydrocarbons and methanol. In the third case study, pressure swing distillation is combined with separation based on hydrocarbon–methanol liquid–liquid phase equilibrium. Using process simulation results, setup with Aspen HYSYS^® v8.4, heat integration analysis, performed with SPRINT^® v2.8, is accomplished to exploit energy savings. Environmental impact calculations are performed using WAR algorithm, considering different fuel types for utilities generation. Results show that the elimination of water in separation section and the use of liquid–liquid phase separation ensure lower energy consumption (overall heat recovery in case study 3 is 9.87 MW, compared to 7.47 MW for case study 2) and better environmental performance. Economic indicators calculated with Aspen Process Economic Analyzer^® allow identification of attractive process changes, for the new proposed process configuration.     

高纯度甲基叔丁基醚的研制

工业粗醚用由无机酸为主要成分的去杂试剂处理，水洗、干燥后，再与金属钠回流反应除去少量甲醇和叔丁醇，分馏得到纯度达９９．９％的甲基叔丁基醚．     

Synthesis of tertiary amyl methyl ether (TAME): Equilibrium of the multiple reactions

The octane enhancer tertiary amyl methyl ether (TAME) is produced by liquid phase synthesis from methanol and a mixture of isoamylenes, namely 2-methyl-1-butene and 2-methyl-2-butene, using a sulfonic acid ion exchange resin as catalyst. Three reactions take place simultaneously in TAME synthesis: etherification of the two methylbutenes and their isomerisation. In order to study the equilibrium of the multiple reactions in TAME synthesis, the thermodynamic properties of the compounds in the liquid phase and equilibrium constants were calculated using a modified UNIFAC method to describe the nonideality of the system. Four parameters influencing the equilibrium conversion were derived and discussed in detail. Supplemental experiments were performed at three temperatures in the range from 303 to 343 K and at different initial molar ratios of educts. Equilibrium conversions of methanol were determined from these experiments and compared with calculated values. At 298 K the predicted activity based equilibrium constant was 22.9 for TAME synthesis from 2-methyl-1-butene and 1.6 for TAME synthesis from 2-methyl-2-butene; for isomerisation of 2-methyl-1-butene to 2-methyl-2-butene a value of 14.3 was obtained.     

Liquid-liquid equilibria of water + methanol + (MTBE or TAME) mixtures

Experimental liquid-liquid equilibrium data obtained at various temperatures for water + methanol + methyl tert-butyl ether and water + methanol + tert-amyl methyl ether were satisfactorily fitted by both NRTL and UNIQUAC models using S?rensen's well-known correlation program, which nevertheless performed anomalously when run seeking minimum error in the solute distribution ratio.     

MTBE法合成2,4-二叔丁基苯酚的实验研究

以甲基叔丁基醚（MTBE）为烷基化试剂,通过正交实验研究了苯酚叔丁基化合成2,4-二叔丁基苯酚的反应规律,分别考察了一步法和两步法合成工艺的规律,结果表明：利用一步法,目标产物收率较高,在n（苯酚）：n（MTBE）=1：2．1、反应时间60min、催化剂（浓硫酸）用量1．0mL、反应温度85℃时,目标产物的收率可达61．5％。     

Synthesis of tertiary amyl methyl ether (TAME): Influence of internal and external mass transfer resistance

An experimental set-up is presented for the measurement of reaction rates in the liquid phase synthesis of tertiary amyl methyl ether (TAME) from methanol and a mixture of 2-methyl-1-butene and 2-methyl-2-butene using an acidic ion exchange resin (Lewatit SPC 118) as catalyst. The reaction was performed in a continuous-flow recycle reactor at a temperature of 333.15 K and a pressure of 1.6 MPa. Determination of the age distribution (Fcurve) of the reactor showed that mixed flow is approached at a recycle ratio of R = 10. Experiments were performed to reveal the limits of operating conditions where the various resistances do not affect the rate. In agreement with estimation of Reynolds numbers, hindrance by external mass transfer can be excluded at a volumetric flow rate of 10 ml/min and a recycle ratio of R = 10. The maximum temperature increase of the whole particle resulting from limitation of external heat transfer was estimated to be about 3 K. Variation of the size of resin particles revealed the existence of a critical methanol concentration, above which reaction rates can be determined without influence of internal mass transport phenomena. The maximum temperature increase in the particle was estimated to be 0.3 K.     

Liquid-liquid equilibria of (MTBE or TAME) + ethanol + water mixtures

Experimental liquid-liquid equilibrium data obtained at 25 and 35°C for ternary mixtures of MTBE + ethanol + water, and at 25, 35 and 45°C for ternary mixtures of TAME + ethanol + water, were satisfactorily fitted with NRTL and UNI-QUAC equations using the correlation program developed by Sørensen (1980).