超临界流体对固定床甲醇合成反应促进作用的研究

为了阐明超临界流体对甲醇合成反应的促进作用,在固定床反应器中实验考察了超临界正己烷中合成气制甲醇反应。结果表明:忽略催化剂内扩散阻力时,氮气中甲醇合成反应的反应器出口甲醇浓度低于平衡值,而超临界正己烷介质中甲醇合成反应的反应器出口甲醇浓度远高于平衡值。此外,建立了固定床反应器内超临界正己烷中甲醇合成反应的浓度分布模型,模拟考察了甲醇四缔合体的存在对反应结果的影响,发现由于甲醇分子间的氢键缔合大大降低了催化剂表面单体甲醇浓度,促进平衡向着甲醇合成反应方向进行,使得固定床出口甲醇浓度大于平衡值。     

三相床甲醇合成新工艺

介绍三相床甲醇合成技术。作者通过冷态和热态试验，筛选出了ＴＰＭ－１甲醇合成催化剂及惰性液相热载体。实验室条件下，该催化剂使反应器出口气体甲醇含量达１１％～１２％。研究了淤浆床反应器的冷态特性，探讨了反应条件对三相床甲醇合成的影响。     

甲醇气相脱水制二甲醚多段原料气冷激反应器模拟与优化

针对百万吨级二甲醚生产的要求,建立了甲醇气相脱水制二甲醚的反应动力学模型以及多段原料气冷激的固定床反应器模型,并模拟计算得到甲醇制二甲醚过程中反应器浓度与温度的轴向分布.通过改变操作条件对反应器的参数敏感性进行分析,结果发现,甲醇原料气分为三段进入反应器较为合适,入口气量分配比例最好为7∶2∶1,此时反应器最高出口温度略高于360℃,各段出口温度大致相当,分布较合理;冷激气温度并非越低越有利,当二段入口温度低于催化剂起活温度就没有意义了,在入口甲醇原料温度为260℃、冷激气温度为140.0℃时,甲醇总转化率利二甲醚产量达到最大值.     

南京国昌化工科技有限公司

南京国昌化工科技有限公司是研究开发氨（甲醇）合成反应器及合成技术的专业企业，其研究开发的合成反应器（氨、甲醇）及合成技术已遍及全国并成功出口东南亚。     

超重力法脱除变换气中的CO2

用N2和CO2的混合气体模拟变换气,采用苯菲尔溶液为吸收液进行了超重力法脱除CO2的实验研究,考察了反应温度、系统压力、超重力水平、气液比对反应器出口CO2含量的影响。实验结果表明:随着温度的升高和超重力水平的增强,反应器出口CO2含量先降后升;随着压力的升高,反应器出口CO2含量逐渐降低;液体流量一定时,随着气液比的增大,反应器出口CO2含量逐渐升高。     

管壳外冷-绝热复合式甲醇合成反应器的应用

由煤制合成气经合成甲醇制燃料和化工产品的技术路线是煤洁净高效利用的方向之一.根据甲醇合成反应的特点,将管壳外冷-绝热复合式固定床催化反应器应用于甲醇生产中,单塔45万吨/年甲醇合成反应器已设计,单塔30～35万吨/年甲醇合成反应器已投入使用.双塔并联50万吨/年甲醇合成反应技术已经投入使用,工业生产情况表明:甲醇合成反应器结构合理,催化剂装卸方便,催化床温度调节简单,床层热点至出口温差小,回收高位热能、副产蒸汽.正在开展"十一五" 国家科技支撑计划课题180万吨/年甲醇合成反应器的研究.     

甲醇羰基合成醋酸装置

正本实用新型公开了一种甲醇羰基合成醋酸装置,该装置主要包括反应器、精制装置和涤气塔,还包括碘甲烷循环塔和蒸发器,所述反应器侧采出料出口连接碘甲烷循环塔,所述碘甲烷循环塔塔顶出口连接反应器,碘甲烷循环塔侧采出料出口连接蒸发器,蒸发器顶部的气体出口连接至精制装置,蒸发器底部的出口回连至反应器。本装置是通过由铑催化的羰基化反应生成醋酸,其通过在精馏装置前设置碘甲烷循环塔和蒸发器,使碘甲烷在反应系统循     

甲醇合成反应器催化剂使用周期与样品分析数据的关联性分析

在不同的操作条件下,甲醇合成反应器铜基催化剂的使用寿命有很大变化,催化剂自身的状况对分析数据也有很大的影响。本文对甲醇合成反应器催化剂的使用周期进行了统计,找到了催化剂工况与分析数据之间的关系。随着催化剂的性能下降,主反应的进行程度较浅,造成甲醇合成反应器循环气中的CO含量逐渐增大,同时催化剂性能的下降导致副反应增多,有机酸含量增大,造成粗甲醇的p H下降。     

甲醇制烯烃多级串联流化床反应器模拟

甲醇制烯烃(MTO)是现代煤化工发展的新技术,合理的甲醇制烯烃反应器操作模式可以有效提高催化剂的效率和低碳烯烃选择性。采用在工业SAPO34催化剂上实验得到的反应与失活动力学和流化床动态两相模型,结合颗粒停留时间分布模型,对MTO单一流化床反应器、二级串联及三级串联反应器进行了模拟,考察了催化剂停留时间、气固并流和气固逆流对甲醇制烯烃反应的影响。模拟结果表明:采用多级串联反应器有利于减小颗粒的返混,使出口积炭量分布更加均匀,催化剂寿命延长;二级气固逆流操作可以提高低碳烯烃选择性及出口催化剂积炭量,催化剂单位生产能力比单级反应器提高24.4%;三级串联、气固逆流反应器可以充分利用各级反应器的不同功能,使总的低碳烯烃选择性提高到79.36%(质量分数),比单级反应器提高1%,同时单位催化剂单程生产能力比单级提高31.1%。     

XNC-98催化剂甲醇合成本征动力学

在等温积分反应器中研究了XNC-98催化剂上甲醇合成反应本征动力学.实验压力为4~8MPa,空速7000~13000h-1,反应温度200~260℃.实验采用粒度为0.154~0.198mm的细颗粒催化剂.选取以各组分逸度表示的CO、CO2加氢合成甲醇的Langmuir-Hinshelwood本征动力学模型.采用正交实验设计,实验测定了25组数据,用全局通用算法结合马夸特算法确定动力学模型参数.残差分析和统计检验表明,动力学模型是适宜的.随温度升高,反应器出口甲醇浓度、CO和CO2转化率先增加后降低,在4~8MPa下,230~245℃为较佳反应温度范围:随着反应压力的提高,反应器出口甲醇浓度、CO和CO2转化率都有显著增加,提高反应压力能够有效提高反应器的生产能力.     

甲醇-乙醇双液系折光率-组成的模型研究

研究了在常压、温度303.15 K下,利用阿贝折光仪测定乙醇-水,甲醇-水以及甲醇-乙醇三个双液体系的折光率,并采用MATLAB建立了双液系折光率-组成关系模型。结果表明,折光率可快速鉴别甲醇和乙醇,而且利用拟合的关系模型可较精确地确定甲醇含量。     

Multivariate model for the prediction of total phenolic acids in crude extracts of polyphenols from canola and rapessed meals: A preliminary study

The feasibility of using UV spectrophotometry to develop multivariate models for prediction of total phenolic acids content in crude polyphenol extracts from defatted canola and rapeseed meals was investigated. The polyphenols were extracted from the meals with methanol/acetone/water (7∶7∶6, by vol). Partial least squares regression was used to correlate the spectral data of the crude polyphenols in methanol between 320 and 355 nm with the total phenolic acid content in canola and rapeseed meals. The Folin-Denis assay was used to provide reference data for creating the model. The predictive ability of the model is good, as indicated by the RPD value (the ratio of the SD of data to the standard error of calibration) of 3.84.     

液相法甲醇合成过程中机械搅拌反应器的模拟

本文对C301及C302两种不同催化剂条件下机械搅拌反应器内液相法甲醇过程进行了模拟,模拟中节气液之间的传质过程及催化剂气固相本征反应动力学,主要模拟条件：温度483K－528K,压力2．0MPa-6．0MPa,原料气中CO浓度0．06－0．45。模拟结果表明,在C301与C302催化剂条件,隆成总体速率的模拟计算与实测值相吻合,平均偏差分别为7．98％和11．92％,可以认为,气固相本征动力学模型应用于液相甲醇合成过程的工程设计与过程分析是适用和可靠的。     

腺苷蛋氨酸发酵液中甲醇含量测定方法研究

利用变色酸比色法和气相色谱法分别对甲醇诱导毕赤酵母基因工程菌发酵液中甲醇含量测定方法进行了研究。结果表明,变色酸比色法测定发酵液中甲醇浓度具有较好的精密度和准确度,与气相色谱法相比误差不大。因此,利用变色酸比色法测定腺苷蛋氨酸发酵液中甲醇浓度是一种简单、易行、准确的测定方法。     

Enhancing mass transport in direct methanol fuel cell by optimizing the microstructure of anode microporous layer

The microstructural characteristics of the anode microporous layer (MPL) can significantly affect the mass transport in direct methanol fuel cells by influencing the methanol delivery and CO₂ removal processes. The hydrophilic‐hydrophobic balance and pore structure of the flow path were established by optimizing the content of polytetrafluoroethylene (PTFE) in the anode MPL. An empirical model was developed to design and optimize the anode MPL to achieve better mass transport and cell performance. From the simulated and experimental results, increasing the content of PTFE enhanced the CO₂ removal ability in the anode MPL, thereby alleviating CO₂ blockage in the anode catalyst layer, whereas the narrowed flow path hindered methanol delivery in the anode MPL. A good balance between methanol delivery and CO₂ removal in terms of mass transport was achieved when the PTFE content was adjusted to 15 wt %, leading to the best cell performance. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3519–3528, 2018     

甲醇合成影响因素与粗甲醇中乙醇含量超标研究

操作条件、入塔气组成以及催化剂性能是影响甲醇合成反应的主要因素。文章对甲醇合成反应的影响因素进行分析,找出甲醇装置开车初期粗甲醇中乙醇含量超标的具体原因,并在此基础上进行优化操作,粗甲醇中乙醇含量达到或优于设计指标。     

Gasoline alkylation desulfurization over Amberlyst 35 resin: Influence of methanol and apparent reaction kinetics

Gasoline desulfurization is receiving attention worldwide due to the increasing stringent regulations on sulfur content for environmental protection purpose. As conventional hydrotreating technology leads to significant octane number loss and processing costs, the gasoline alkylation desulfurization process, which consists of weighing down the sulfuric compounds by catalytic alkylation with olefins present in the feed and distillation followed by, is a rather attractive way. In this paper, firstly alkylation of thiophenic compounds was researched over macroporous sulfonic resin Amberlyst 35 in methanol presence to increase the selectivity of catalyst, then kinetics of thiophenic sulfurs alkylation in FCC gasoline was researched without and with methanol. Results found that appropriate methanol (?2 wt.% methanol in model gasoline and ?1 wt.% methanol in FCC gasoline) could inhibit olefins oligomerization significantly without influence on the conversions of thiophenic compounds. The alkylation of thiophenic sulfurs could be described as pseudo first order reaction regardless of the existence of methanol. The introduction of methanol decreases the reaction rate constant and increases the activation energy of alkylation reactions.     

Analysis and modeling of synthesis gas conversion to methanol: New trends toward increasing methanol production profitability

Technologies for methanol production from synthesis gas are analyzed. Their main advantages and disadvantages are determined, and a new methanol synthesis technology without feed circulation is proposed, which, in particular, is also applicable at a significant nitrogen content of the synthesis gas feed. On the basis of the results of laboratory and bench tests of the new process, mathematical models of a catalyst grain and a catalytic reactor and a kinetic model of methanol synthesis are constructed and their parameters are estimated. It is shown that the models fit experimental data. A three-reactor methanol synthesis unit providing 75–80% conversion of the synthesis gas feed is calculated. The crude methanol obtained has a high content of the desired product of 94–99 wt %. It is demonstrated that this process is characterized by much lower feed and energy consumption.     

响应面法优化产低温脂肪酶工程菌Cl02的发酵条件

目的采用响应面法优化产低温脂肪酶工程菌Cl02的发酵条件。方法通过单因素试验考察培养基中酵母氮源含量、pH值、甘油含量和甲醇含量对酶活的影响,确定产酶的主要影响条件,在此基础上,根据Box-Benheken中心组合试验设计原理,采用三因素三水平的响应面分析法,综合考察各因子对低温脂肪酶酶活的影响,建立低温脂肪酶酶活的二次回归模型。结果培养基中酵母氮源含量、pH值和甲醇含量对酶活的影响显著。最适产低温脂肪酶条件为:酵母氮源含量7.3 g/L、pH 6.0、甲醇含量9.1 g/L,在此条件下,低温脂肪酶酶活可达42.25 IU/ml,比优化前(28.0 IU/ml)提高了50.9%。结论利用响应面法优化的发酵条件可显著提高工程菌的产酶能力,为规模化生产低温脂肪酶奠定了基础。     

Effects of temperature and feed composition on catalytic dehydration of methanol to dimethyl ether over γ-alumina

Catalytic dehydration of methanol to dimethyl ether (DME) is performed in an adiabatic fixed bed heterogeneous reactor by using acidic γ-alumina. By changing the mean average temperature of the catalyst bed (or operating temperature of the reactor) from 233 up to 303 °C, changes in methanol conversion were monitored. The results showed that the conversion of methanol strongly depended on the reactor operating temperature. Also, conversion of pure methanol and mixture of methanol and water versus time were studied and the effect of water on deactivation of the catalyst was investigated. The results revealed that when pure methanol was used as the process feed, the catalyst deactivation occurred very slowly. But, by adding water to the feed methanol, the deactivation of the γ-alumina was increased very rapidly; so much that, by increasing water content to 20 weight percent by weight, the catalyst lost its activity by about 12.5 folds more than in the process with pure methanol. Finally, a temperature dependent model developed to predict pure methanol conversion to DME correlates reasonably well with experimental data.