聚乙烯醇醇解母液回收技术进展

对近几年醇解母液回收技术进展进行评述.将乙酸甲酯水解为乙酸和甲醇,告别回收的传统工艺,在乙酸甲酯浓缩、高效催化精馏水解、甲醇双效精馏精制及乙酸精制等方面均取得了明显进步,同时也出现了将乙酸甲酯精制为产品的醇解母液回收新思路.目前已实现工业化的有加盐萃取精馏和变压精馏两种技术方案.从工业运行结果来看,加压精馏工艺具有流程短、能耗低、产品纯度高的特点,更具大规模推广应用前景.     

乙酸甲酯-甲醇-水的热集成萃取精馏工艺

首先在50 kPa下用水萃取精馏分离乙酸甲酯、甲醇和水的混合物,得到了高质量分数的乙酸甲酯,之后利用普通精馏分离甲醇和水。使用热集成技术改造该工艺流程,将甲醇单塔精馏改造为并流双效精馏,两塔压力分别为101.325、500.000k Pa。同时采用高温水对萃取精馏塔两股进料预热,以降低萃取精馏塔塔釜的能耗。在操作参数单因素灵敏度分析的基础上,以系统塔釜总能耗及乙酸甲酯质量分数为目标函数,采用响应面方法优化操作参数。结果表明,热集成工艺较之前工艺节能23.43%。     

PROⅡ对反应精馏系统的模拟分析

乙酸甲酯的制备是反应精馏在工业上的典型应用。采用美国SIMSCI公司开发的化工流程模拟软件PROII,模拟催化反应精馏法制备乙酸甲酯过程,分析了塔的操作压力、回流比、甲醇的进料位置以及甲醇过量程度等参数对反应精馏塔分离效果的影响。模拟结果表明,较低的操作压力有利于该反应的进行,反应精馏塔的最佳回流比为1.80~2.15,甲醇宜在反应区的底部进料,甲醇与乙酸的摩尔比宜为1.2∶1。     

1,4-丁二醇分离乙酸甲酯-甲醇二元恒沸物的研究

利用1,4-丁二醇与乙酸甲酯-甲醇二元恒沸物形成三元恒沸物,研究了乙酸甲酯与甲醇恒沸物的分离工艺。实验采用精馏、常压蒸馏、减压蒸馏及冷冻的方法,主要研究了各种方法对甲醇分离的影响,并获得了较佳的工艺条件。研究得出常压蒸馏法可行,乙酸甲酯纯度达到99.7%,收率98.1%,甲醇纯度96.1%,收率95.2%。     

催化精馏与固定床联合工艺用于乙酸甲酯水解

在原乙酸甲酯催化精馏水解技术工业化应用成功基础上,为进一步提高乙酸甲酯水解率,利用聚乙烯醇厂已具备的固定床设备,建立了乙酸甲酯水解催化精馏与固定床联合的工艺.通过系统的实验考察了进料位置、水酯比、回流进料比和空速对乙酸甲酯水解率和酸水比的影响,得出了满足厂家要求的适宜工艺条件,并与原催化精馏单塔工艺进行了比较.研究表明...     

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%。     

双溶剂协同萃取精馏分离乙酸甲酯-甲醇-水工艺模拟

针对乙酸甲酯-甲醇-水体系,在筛选萃取剂的基础上,提出了双溶剂四塔萃取精馏、单溶剂三塔萃取精馏及双溶剂协同萃取精馏3种分离工艺.用Aspen Plus软件模拟萃取精馏过程,并以能耗和年总费用作为评价指标,用SR-Polar方程计算各萃取精馏工艺合适的操作参数和设备参数.结果表明,水和乙二醇是分离该体系较合适的萃取剂,单溶剂三塔萃取精馏工艺较双溶剂四塔萃取精馏工艺优异,能耗减少约37.9%,年总费用降低约38.9%.双溶剂协同萃取精馏工艺比双溶剂四塔萃取精馏工艺和单溶剂三塔萃取精馏工艺能耗分别减少约45.6%和12.4%,年总费用分别降低约43.5%和11.6%.     

四氢呋喃-甲醇-乙酸甲酯-水热集成双溶剂萃取精馏工艺

针对四氢呋喃-甲醇-乙酸甲酯-水四元物系中存在多个二元共沸物的特点,本工作提出了常规双溶剂萃取和热集成双溶剂萃取两种精馏工艺。基于WILSON方程计算得到热力学数据,并对萃取剂进行了筛选。结果表明,对于四氢呋喃-甲醇和乙酸甲酯-甲醇共沸物系,选用水作为萃取剂最为合适;而对于四氢呋喃-水和乙酸甲酯-水共沸物系,则选用乙二醇作为萃取剂最为合适,且总溶剂比为0.65,乙二醇和水的比例为1.3。在此基础上,以能耗和年总费用(TAC)作为精馏工艺的评价指标,对提出的常规双溶剂萃取和热集成双溶剂萃取精馏工艺进行了模拟,并利用夹点分析技术对双溶剂萃取精馏系统的换热网络进行了优化。研究结果表明,优化后的换热网络其冷公用工程消耗降低44.12%,热公用工程消耗节约42.49%。与常规双溶剂萃取精馏工艺相比,热集成双溶剂萃取精馏工艺其能耗降低约43.29%,节省TAC约26.89%,热力学效率提高了3.25%。可见,热集成双溶剂萃取精馏工艺用于分离以上四元共沸物系,具有较好的技术经济优势。     

基于机械蒸汽再压缩和有机朗肯循环技术的双溶剂协同萃取精馏分离乙酸甲酯-甲醇-水节能工艺

针对双溶剂协同萃取精馏分离乙酸甲酯-甲醇-水三塔分离工艺特性及高能耗特点,把机械蒸汽再压缩(MVR)和有机朗肯循环(ORC)余热发电技术应用于该三塔的优化,提出了带中间再沸器的MVR热泵和ORC耦合MVR热泵两种节能精馏工艺。以年总费用(TAC)为精馏工艺评价指标,净输出功为ORC系统评价指标,采用Aspen Plus软件对提出的节能工艺进行模拟与优化。研究结果表明,就乙酸甲酯回收塔和甲醇回收塔而言,带中间再沸器的MVR热泵精馏工艺较常规双溶剂协同萃取精馏工艺能耗分别减少了57.38%和9.66%;TAC分别节省了31.34%和11.69%。而对于溶剂回收塔,带中间预分塔的ORC耦合MVR热泵精馏工艺较常规双溶剂协同萃取精馏工艺能耗减少了50.16%,TAC节省了36.13%。就整个萃取精馏系统而言,优化后的精馏工艺比原有双溶剂协同萃取精馏工艺能耗减少了45.48%,TAC节省了31.33%。     

[Emim]AC萃取精馏分离乙酸甲酯和甲醇工艺模拟

以离子液体1-乙基-3-甲基咪唑醋酸盐([Emim]AC)为萃取剂,萃取精馏分离乙酸甲酯和甲醇共沸体系。采用Aspen Plus流程模拟软件,对萃取精馏工艺进行了模拟和优化。考察了溶剂比、全塔理论塔板数、原料进料位置、萃取剂进料位置和回流比等工艺参数对分离效果的影响。萃取精馏塔的最佳工艺参数为:全塔理论板数30,原料和萃取剂进料位置分别为第23块和第2块理论板,回流比为1.0,溶剂比为0.7。闪蒸罐操作温度和压力分别为85℃和20 kPa。在最优工艺条件下,产品乙酸甲酯的质量分数达到99.95%,甲醇的质量分数达到99.54%,均满足分离要求。说明采用离子液体[Emim]AC作为萃取剂分离乙酸甲酯和甲醇共沸物具有工业应用前景。     

侧反应器反应精馏方法生产醋酸甲酯的模拟

采用强酸性阳离子交换树脂催化醋酸与甲醇反应精馏生成醋酸甲酯,可避免硫酸作为催化剂的不足。但该非均相催化反应受平衡限制,且达到平衡时间较长,采用传统反应精馏塔难以提供足够反应空间。文中设计侧反应器与精馏塔耦合新工艺,采用Aspen Plus软件模拟研究了侧反应器数量、位置,原料进料位置,回流比,醇酸比等对反应精馏过程的影响。结果表明,当装置具有7个侧反应器,反应器间隔4块板,在优化的操作条件下,醋酸甲酯质量分数可达99.1%。     

Methyl acetate–methanol mixture separation by extractive distillation: Economic aspects

Methyl acetate is considered low toxicity volatile solvent produced either as a by-product during methanol carbonylation or via acetic acid esterification with methanol. In both cases, pure methyl acetate has to be isolated from the reaction mixture. Simulation of methyl acetate separation from its mixture with methanol by extraction distillation was carried out in ASPEN + software. In total three case studies were assumed using two different extraction solvents and two solvent regeneration strategies. In case A, novel extraction solvent 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ionic liquid, was considered. Raw material separation was achieved in an extraction distillation column while the solvent regeneration was accomplished in a second distillation column in this case. In case study B, the same extraction solvent was used; however, its regeneration was carried out in a single-effect evaporator. Dimethyl sulfoxide was the second extraction solvent selected. Its use in methyl acetate-methanol separation is presented in case study C. As high purity of dimethyl sulfoxide was required for the methyl acetate-methanol azeotrope breaking, its regeneration was carried out in the second distillation column only. To simulate the ternary methyl acetate–methanol–extraction solvent mixtures separation, vapor–liquid equilibrium was predicted based on the NRTL equation. Further, unknown properties of the considered ionic liquid and variation of these properties with temperature were predicted and introduced into the ASPEN + components properties database. Based on these data, optimum operation parameters of the respective separation equipment were established. In all case studies, the same condition had to be fulfilled, namely minimum methyl acetate content in the distillate from the extraction distillation column of 99.5mol-%. Results of simulations using the respective optimum operation parameters were employed in the economic evaluation of the three separation unit designs studied. It was found that the least energy-demanding design corresponds to the case study B in terms of both capital as well as operation expenses.

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Investigation of enzymatic biodiesel production using ionic liquid as a co‐solvent

In this study, the lipase catalysed esterification reaction for biodiesel production was investigated in the presence of the ionic liquid [BMIM][PF₆]. Unlike regular organic solvents, many ionic liquids have no vapour pressure, and are therefore considered non‐volatile. When used in systems with enzyme catalysts, ionic liquids may enhance their activity, selectivity, and stability. The use of an enzyme (lipase) as a catalyst, and the ionic liquid as a solvent/immobilization agent also represents an environmentally friendly, “green” technology. Methyl acetate was used as the acyl acceptor as opposed to the more commonly used methanol due to the negative effects methanol and the glycerol by‐product has on lipase enzyme activity. The results of this research indicate that methyl oleate (i.e., biodiesel) was successfully produced, with an 80% overall biodiesel yield in the presence of ionic liquid, at a 1:1 ratio (v/v) to the amount of oil. This verified that the presence of an ionic liquid, at a specified amount, improved the activity of the lipase and the overall biodiesel yield. Results also indicate the addition of ionic liquid facilitated the separation of the methyl esters from the triacetylglycerol by‐product. The best conditions investigated was found to be: 14:1 molar ratio between oil and acyl acceptor; 20% (w immobilised lipase/w of oil; and a temperature in the range of 48–55°C. However, additional purification is required in order for the produced biodiesel to meet ASTM standards.     

New process for catalyst-free biodiesel production using subcritical acetic acid and supercritical methanol

The production of glycerol as a by-product is unavoidable in the current conventional biodiesel manufacturing processes. Since biodiesel production is expected to increase in the near future, effective utilization of glycerol will become an issue of interest. In this study, therefore, a process consisting of subcritical acetic acid treatment to convert rapeseed oil to fatty acids and triacetin followed by conversion of the obtained fatty acids to their fatty acid methyl esters in supercritical methanol treatment was investigated. The obtained results clearly revealed that this two-step reaction could proceed effectively at a high reaction rate, and that fatty acid methyl esters and triacetin could be obtained under milder reaction condition than the one-step process utilizing supercritical methyl acetate and supercritical methanol.     

猪板油直接萃取制备生物柴油的研究

研究了猪油原位萃取-酶法转化制生物柴油。考察了溶剂用量、萃取时间、萃取温度等对油脂得率的影响,探讨了以Novozyme 435酶为催化剂直接转化猪油生物柴油。结果表明,萃取猪油的较优参数为:乙酸甲酯为萃取剂,乙酸甲酯用量(mL)与猪板油质量(g)比为8∶1,萃取时间3 h,萃取温度50℃;以Novozyme 435脂肪酶转化猪油制备生物柴油,得率为95.12%,当Novozyme 435酶和Lipozyme TLIM酶混合比为1∶1时,生物柴油转化率最高,达97.12%。     

亚临界甲醇中麻疯树油制备生物柴油的研究

对麻疯树油在催化剂对甲苯磺酸作用下与亚临界甲醇反应制备脂肪酸甲酯(生物柴油)进行了研究。结果表明在反应温度170℃、醇油摩尔比40:1、催化剂用量占油重的0.75%和反应时间30 m in的条件下,反应产物中脂肪酸甲酯含量可达93%以上。制备的生物柴油,各项指标与柴油相似。主要性能指标,符合ASTMPS121-99(USA)和0#矿物柴油标准。     

Transesterification of palm oil with methanol in a reactive distillation column

The higher feedstock and processing costs for biodiesel production can be reduced by applying reactive distillation (RD) in transesterification process. The effects of reboiler temperature, amount of KOH catalyst, methanol to oil molar ratio and residence time on the methyl ester purity were determined by using a simple laboratory-scale RD packed column. The results indicated that from the empty column, the system reached the steady state in 8 h. Too high reboiler temperature and the amount of catalyst introduce more soap from saponification in the process. The optimal operating condition is at a reboiler temperature 90 °C, a methanol to oil molar ratio of 4.5:1.0, KOH of 1 wt.% respect to oil and 5 min of residence time in the column. This condition requires the fresh feed methanol 25% lower than in the conventional process and produces 92.27% methyl ester purity. Therefore this RD column can be applied in small or medium biodiesel enterprise.     

反应与催化精馏耦合提纯乳酸新工艺的研究

The purification of lactic acid based on the esterification of raw lactic acid from fermentation broth and then the catalytic distillation hydrolysis of methyl lactate simultaneously to achieve pure lactic acid is reported. The esterification kinetics of lactic acid with methanol catalyzed by strong-acid cation-exchange resins (Amberlyst-15,D001, D002, NKC, 002) was studied under the condition that simulates the real catalytic environment. Experimental results were correlated by a Langmuir-Hinselwood model and the nonideality of the solution was taken into account by using activities calculated by the universal quasichemical functional group activity coefficient (UNIFAC) method.A good agreement between the model and the experimental data was achieved. Continuous purification experiments were conducted to find the optimum column configuration and operation condition for the system. The effects of various parameters, e.g. the length of different section of the column, feed rate and ratio of reactants, packing material and catalyst type, were studied. This novel system shows good separation results in lab scale, and is potential for industrial application.