Synthesis of High‐Purity Methylal via Extractive Catalytic Distillation

An integrated continuous process, which combines catalytic distillation and extractive distillation in one column, is investigated for the synthesis of high‐purity methylal from methanol and formalin in the presence of a cation‐exchange resin catalyst. A feed with methanol:formaldehyde 2:1 molar ratio is chosen to evaluate the effects of operating parameters, such as extractant feeding position, ratio of extractant to feed, reflux ratio, and reboiler temperature, on the continuous synthesis of methylal. Under the optimum operating conditions and with water as extractant, the extractive catalytic distillation process operated continuously, producing a methylal purity of 98.7 % (H₂O: < 1.30 %) with 98.0 % formaldehyde conversion.     

连续萃取催化精馏制备高纯度甲缩醛

研究了以甲醇和甲醛为原料,大孔径阳离子交换树脂为催化剂,通过将萃取精馏和催化精馏相耦合的方法制备高纯度甲缩醛,证明了这种工艺的可行性。在内径为35 mm、高为2700 mm的玻璃反应精馏塔内进行实验,考察了总进料量、萃取剂进料位置、醇醛摩尔比、回流比以及用甲醛溶液作为萃取剂对甲醛转化率和甲缩醛纯度的影响。在选定的实验条件下,甲醛的转化率可达到97.82%以上,甲缩醛纯度可达到97.64%（含甲醛0.79%、水1.41%、甲醇0.20%）。     

浆料催化精馏制备甲缩醛

研究了以甲醇和甲醛为原料,以大孔径强酸性阳离子交换树脂为催化剂,通过浆料催化精馏工艺制备甲缩醛的可行性。考察了催化剂含量、进料醇醛比、进料总流量和回流比等因素对该过程的影响。在选定的试验条件下,甲缩醛收率可达89%以上,塔顶甲缩醛的质量分数可达0.99以上。结果表明,该工艺用于制备甲缩醛是可行的。     

反应精馏生产甲缩醛工艺的研究

对合成甲缩醛反应精馏过程进行了模拟和实验,分析了过程操作参数回流比、进料位置、醇醛进料摩尔比的变化结果的影响,模拟结果表明,当精馏段级数为11,反应段级数为26,提馏段为5,回流比为3,甲醇和甲醛的进料位置分别为第37级和第12级,甲醇/甲醛(摩尔比)=2.1时,塔顶可得到质量分数大于99.5%的高纯度甲缩醛。并通过反应精馏实验对模拟结果进行验证,实验结果与模拟结果吻合较好。     

反应精馏制备甲缩醛的过程模拟与优化

使用Aspen Plus11.1模拟甲醇与甲醛反应精馏制备甲缩醛的过程,模拟过程采用了NRTL模型,对进料温度、进料位置、回流比进行了灵敏度分析,得到了较佳工艺参数为:进料温度40℃,进料醇醛摩尔比2∶3,进料位置为第9块塔板,回流比8。模拟得到了反应精馏塔的温度和浓度分布,对于甲缩醛的工业化生产有着重要的作用。     

Development of a new advanced process for manufacturing polyacetal resins. Part I. Development of a new process for manufacturing highly concentrated aqueous formaldehyde solution by methylal oxidation

A new technology for the production of highly concentrated aqueous formaldehyde was developed by oxidizing methylal. Whereas the oxidation of methanol yields 1 mol of water per 1 mol of formaldehyde, methylal oxidation produces only 1 mol of water for every 3 mol of formaldehyde. Thus, the output from methylal oxidation is more than 70% formaldehyde compared with 55% from methanol oxidation. For this purpose, basic research for methylal synthesis was tried and the world's first commercial production of methylal was accomplished. Using this methylal, the world's first technology of methylal oxidation for manufacturing highly concentrated aqueous formaldehyde was established by development of a new methylal oxidation catalyst composed of iron, molybdenum, and a third component. This highly concentrated aqueous formaldehyde is then fed to the acetal homopolymer and copolymer plant whose combined capacity is 35,000 tons/years. © 1993 John Wiley & Sons, Inc.     

连续催化合成甲缩醛工艺研究

以甲醇和甲醛为原料,在硫酸催化下反应精馏,一锅法合成了甲缩醛。稀酸酸经提浓后可套用。优化反应条件为:n(甲醇)∶n(甲醛)=2∶1,精馏回流比8~10∶1,催化剂加入量为甲醇质量的15%,产品含量≥98%,收率≥91%。     

甲缩醛合成催化剂的筛选和工艺条件

针对由甲醇、甲醛溶液合成甲缩醛反应。采用不同制备方法制备了四种不同组成的硅酸铝固体酸催化剂,在间歇操作方式下,通过改变催化剂用量、反应温度、原料甲醇和甲醛的摩尔配比以及反应原料中甲醛初浓度.考察了反应混合物中反应物和产物浓度随时间的变化关系以及反应的选择性和收率,得出了实验操作范围内适宜的催化剂组成、制备方法和反应工艺条件。     

催化精馏合成醋酸甲酯的研究

以强酸型阳离子交换树脂为催化剂,在直径为40 mm的填料塔内对催化精馏合成醋酸甲酯进行了研究。实验塔的三段填料高度分别为810、270、450 mm,填料段之间放置直径为60 mm、高度为175 mm的2节催化剂床层,并在塔釜放置催化剂。采用连续操作,着重考察了醇酸进料摩尔比、醋酸进料位置、甲醇进料位置和回流比对催化精馏合成醋酸甲酯的影响。在选定实验条件下,塔顶醋酸甲酯的质量分数可达到98.43%,醋酸的转化率达到99.13%。     

催化精馏过程制备碳酸二甲酯的研究

在自制的催化精馏实验装置中 ,以等体积浸渍法负载于碳分子筛上的 1 2 -磷钨酸为催化剂 ,将其捆束型的方式装填于精馏塔中 ,通过碳酸丙烯酯和甲醇之间简单的酯交换反应来进行碳酸二甲酯的制备。通过试验分别考察了原料配比、操作压力、回流比、处理量等工艺参数对催化精馏过程的影响 ,从而确定出适宜的工艺操作条件     

Heterogeneous extractive batch distillation of chloroform-methanol-water: Feasibility and experiments

A novel heterogeneous extractive distillation process is considered for separating the azeotropic mixture chloroform-methanol in a batch rectifying column, including for the first time an experimental validation of the process. Heterogeneous heavy entrainer water is selected inducing an unstable ternary heteroazeotrope and a saddle binary heteroazeotrope with chloroform (ternary diagram class 2.1-2b). Unlike the well-known heterogeneous azeotropic distillation process and thanks to continuous water feeding at the column top, the saddle binary heteroazeotrope chloroform-water is obtained at the column top, condensed and further split into the liquid-liquid decanter where the chloroform-rich phase is drawn as distillate. First, feasibility analysis is carried out by using a simplified differential model in the extractive section for determining the proper range of the entrainer flowrate and the reflux ratio. The operating conditions and reflux policy are validated by rigorous simulation with ProSim Batch Column^® where technical features of a bench scale distillation column have been described. Six reproducible experiments are run in the bench scale column matching the simulated operating conditions with two sequentially increasing reflux ratio values. Simulation and experiments agree well. With an average molar purity higher than 99%, more than 85% of recovery yield was obtained for chloroform and methanol.     

用新离子交换树脂催化剂优化连续催化精馏塔中乙基叔丁基醚的合成(英文)

Liquid phase synthesis of one of the important fuel oxygenate, ethyl tert-butyl ether （ETBE）, from etha-nol and tert-butyl alcohol （TBA） has been studied in catalytic distillation column （CDC） using ion exchange resin catalyst CT-145H. A packed CDC of 1.2 m height and 50 mm diameter with indigenously developed reactive sec-tion packing was used to generate experimental data. Effect of different key variables on product purity in distillate, was investigated to find the optimum operating conditions for ETBE synthesis. The optimum conditions for 0.2 kg·s-1 of ethanol feed were found：reboiler duty of 375 W, molar feed ratio of 1︰1.3 of reactants, and reflux ratio of 7. Concentration profiles for each component along each column section at optimum conditions were also drawn. Neither output nor input multiplicity was observed at experimental conditions.     

催化精馏制备乳酸乙酯

引言 乳酸乙酯具有无毒、溶解性好、不易挥发、可生物降解等特点,是一种极具开发价值和应用前景的"绿色溶剂"[1].     

乙酸甲酯与甲醇共沸物催化精馏水解工艺

以乙酸甲酯与甲醇共沸物为原料,采用阳离子交换树脂为催化剂,研究了乙酸甲酯催化精馏水解工艺。在实验中以捆扎包作为催化剂的装填方式,系统地研究了催化精馏段和提馏段的高度、进料位置、进料中含甲醇、水酯物质的量比、回流进料比和空速等对酯分解率的影响,获得了最佳的工艺条件。分析了传统的水解分离工艺,提出了可行的新工艺。在最佳工艺条件下,新工艺系统的能耗比传统的固定床工艺降低39.99%。     

酯交换法合成碳酸二甲酯的催化精馏过程研究

在催化精馏实验装置中 ,以等体积浸渍法负载于是碳分子筛上的 12 磷钨酸为催化剂 ,通过碳酸丙烯酯和甲醇之间的酯交换反应合成碳酸二甲酯。通过实验考察了原料配比、操作压力、回流比、处理量等工艺参数对催化精馏过程的影响。采用神经网络与遗传算法相结合的方法 ,用黑箱模型计算催化精馏过程 ,并进行了全局优化 ;以动力学模型为基础 ,借助ASPEN软件用平衡级模型进行了催化精馏过程的模拟与预测。     

Bifurcation analysis for MTBE synthesis in a suspension catalytic distillation column

A rigorous bifurcation study is presented of methyl tert-butyl ether synthesis by suspension catalytic distillation (SCD). SCD is a new development of catalytic distillation (CD) in which fine catalyst particles are suspended in liquid, not only inherits advantages of CD but overcomes transfer limitations in catalyst bed. A complete equilibrium stage model is developed. Analysis results show that this system is sensitive to the operating parameters: the reflux ratio, the bottom flowrate, the methanol feed, the n-butane feed and the operation pressure, and the characteristic parameter for SCD: the solid/liquid separator ratio. The bifurcation diagram displays very intricate and highly nonlinear steady-state behavior, which can results in as many as seven steady-state solutions for identical column specifications. Especially, the results reveal that the superior column performance can be reached under practical operating conditions because the upper bound of the multiplicity range for the solid/liquid separation ratio is very small.     

甲缩醛反应精馏过程模拟

通过实验取得了甲醛和甲醇合成甲缩醛的反应参数;建立了其连续生产工艺的数学模型,利用ASPEN PLUS软件对甲醛和甲醇缩合生成甲缩醛进行了模拟,结果表明反应精馏连续生产甲缩醛的工艺是可行的,转化率高达99%,并得到含甲缩醛99%的产物,同时确定了进料板和反应区.     

离子液体催化反应精馏合成乙酸乙酯工艺模拟

为研究离子液体在反应精馏中的作用,采用离子液体1-丁基-3-甲基咪唑硫酸氢盐（[BMIM]HSO₄）作为催化剂,对乙酸和乙醇合成乙酸乙酯的反应精馏流程进行了计算模拟。在确定了参数的酯化反应动力学的基础上,用Aspen Plus软件建立了反应精馏流程,研究了催化剂用量、精馏段理论板数、反应段理论板数、乙醇进料位置、进料摩尔比、持液量及回流比等参数对反应精馏过程的影响。研究结果表明,塔顶乙酸乙酯的质量分数随催化剂用量、精馏段理论板数、反应段理论板数和持液量增大而增大,工艺流程存在最佳回流比以及最佳进料酸醇摩尔比。得到的优化条件如下：离子液体与乙酸摩尔比为1：2.5,进料酸醇摩尔比为4：1,理论塔板数为21块,乙酸和催化剂在第7块理论塔板进料,乙醇在第19块理论塔板进料,塔板持液量0.1L,回流比为4,塔顶乙酸乙酯的质量分数可以达到98.73%。     

ASPEN模拟反应精馏生产醋酸甲酯及工业化探讨

采用Aspen Plus软件模拟催化反应精馏生产醋酸甲酯的工艺过程。考察操作压力、醋酸进料位置、回流比和醋酸/甲醇进料比对反应精馏塔塔顶醋酸甲酯纯度的影响。得出反应精馏塔优化操作条件为:操作压力1atm、醋酸在第5块板进料、回流比为1.9、酸醇比为1.6。在模拟计算的基础上,初步探讨工业化装置设计的技术关键点。     

2,2’-亚甲基双(6-环己基-4-甲基苯酚)的水相合成研究

本文以自制的2-环己基对甲酚为原料,在酸性催化剂条件下,以水为溶剂,与甲醛水溶液缩合反应合成了抗氧剂2,2’-亚甲基双(6-环己基-4-甲基苯酚)又称抗氧剂ZKF。本工艺采用廉价的甲醛水溶液代替国内外多数工艺中采用的甲缩醛或多聚甲醛,并以水为溶剂代替了有机溶剂,水溶液可循环使用5次,实现了清洁生产并降低了产品成本。产品收率为90.2%,产品纯度99.3%。