STUDY OF CHEMICAL EQUILIBRIA IN METHANOL SYNTHESIS I. Expertmental Measurement of Chemical Equilibrium Composition and Constant Kp

Abstract

The chemical equilibrium compositions and equilibrium constants of methanol synthesis reactions, starting from carbon monoxide, carbon dioxide and hydrogen, were studied experimentally at P=4.0-8. 6MP_a and t = 220～260°C. It was found that lower temperatures and higher pressures are favourable to chemical equilibria In the interested range of the synthesis reactions using low-pressure process, but the influence of temperature on K_p Is much larger than that of pressure.     

STUDY OF CHEMICAL EQUILIBRIA IN METHANOL SYNTHESIS II. Calculation of Equilibrium Constant Kp

Based on the experimental data of K_p measured In this paper, the thermodynamic calculation of K_p from K_r and equation of state was studied and it was found that the chemical equilibrium of methanol synthesis can be described well by using Cheredeichenko (1968)'s K_r, ₀₀ and Blssett (1977)' s K_r. _rs relationship and a modified SRK equation.

Meanwhile, the equilibrium constant K_r In methanol synthesis In literature since 1930_s were appraised. It was found that the obvious deviations of K_r values of different authors would be given because of different basic thermochemical data and the accumulations of the deviations.     

STUDY OF CHEMICAL EQUILIBRIA IN METHANOL SYNTHESIS II. Calculation of Equilibrium Constant Kp

Abstract

Based on the experimental data of K_p measured In this paper, the thermodynamic calculation of K_p from K_r and equation of state was studied and it was found that the chemical equilibrium of methanol synthesis can be described well by using Cheredeichenko (1968)'s K_r, ₀₀ and Blssett (1977)' s K_r. _rs relationship and a modified SRK equation.

Meanwhile, the equilibrium constant K_r In methanol synthesis In literature since 1930_s were appraised. It was found that the obvious deviations of K_r values of different authors would be given because of different basic thermochemical data and the accumulations of the deviations.     

二氧化碳加氢合成甲醇的 CuO-ZnO催化剂制备Ⅰ.制备方法

运用Ｘ射线衍射分析、程序升温度不原、热重分析,活性评价等手段,对二段化碳加氢合成甲醇ＣｕＯ－ＺｎＯ催化剂的不同制备方法进行了对比研究。试验结果表明,共沉淀法制备的催化剂的ＣｕＯ晶粒最细,催化性能最好;采用草酸共沉淀法制备催化剂时,溶剂地催化剂的活性有较大影响,乙醇作溶剂优于水作溶剂。     

汽油润滑性研究II.汽油化学组成的特点

化学组成是决定燃料润滑性的最重要的因素。研究汽油中存在哪些种类的化合物 ,包括烃和非烃 ,是研究汽油润滑性的关键。但是 ,汽油的组成在很大程度上取决于生产时进料的成分和加工的方法。近百年来 ,在汽车和汽油平行发展的过程中 ,汽油组成不断改变 ,而且各国情形也各不相同。直到 80年代末 ,完整的燃料组成数据还是很难得到。本研究中收集归纳了尽可能完整的系统的汽油组成数据 ,用于今后发展汽油润滑的模型及解释汽油润滑性的测定结果。这些数据包括烷烃、烯烃、芳烃、含硫化合物、含氮化合物、含氧化合物、染料和添加剂的结构和含量。     

润滑油基础油中硫、氮化合物的氧化性能研究I.硫、氮化合物在氧化过程中的作用机理

利用红外光谱和色谱 -质谱对含硫、氮模型化合物——甲基苄基硫醚、二苯并噻吩、喹啉和吲哚氧化前后的结构变化进行鉴定。结果表明 ,在氧化条件下 ,喹啉单独存在时具有较高的氧化稳定性 ,部分氧化后的产物为酮亚胺 ,与在白油中喹啉的氧化产物一致 ;吲哚的氧化活性比喹啉强 ,除了自身氧化生成酰胺外 ,极易发生缩合反应。从所推测的氧化历程来看 ,喹啉和吲哚在烃类氧化过程中起引发剂的作用 ,一个喹啉分子可以诱导产生 3个烃自由基 ;而吲哚只能诱导产生 2个烃自由基 ,且由于易缩合 ,故促进氧化的能力比喹啉弱 ;甲基苄基硫醚具有很高的氧化活性 ,氧化生成砜 ,砜分子中临近硫原子的 α-仲碳受 S=O基团的吸电子作用易氧化为酮 ;二苯并噻吩在有氧环境下 ,比甲基苄基硫醚要稳定得多 ,其氧化产物主要是砜。     

4-甲基联苯与甲醇择形甲基化合成4,4''''-二甲基联苯Ⅰ.氧化镁改性的与水热处理的HZSM-5催化剂的性能比较

以4-甲基联苯(4-MBP)与甲醇的烷基化为探针反应，在固定床反应器上考察了MgO改性与水热处理的HZSM-5的催化性能。结果表明，MgO改性和水热处理均可显著提高目的产物4．4’-二甲基联苯(4，4’-DMBP)的选择性，在MgO改性的HZSM-5上，4，4’-DMBP选择性可达80％；在水热处理的HZSM-5上，4，4’-DMBP选择性为70％；而在未改性的HZSM-5上仅为13％。水热处理HZSM-5再经HCl处理后，能改善其活性稳定性，反应1000min后4-MBP转化率仍有8％，而4，4’-DMBP选择性保持在65％。TPD数据表明，MgO改性和水热处理后，催化剂的酸性均有明显的下降；但氮气低温吸附数据表明，前者的微孔比表面积减小，而后者的中孔比表面积增加。4，4’-DMBP与甲醇在催化剂上的反应结果表明，MgO改性抑制了4，4’-DMBP的异构化、脱烷基化及进一步烷基化反应；而经水热处理后高的选择性是来源于4，4’-DMBP的异构化与脱烷基化反应受到抑制。     

超短接触催化裂解过程中的焦炭沉积规律I结焦过程的物理模型

采用一套微型反应器装置 ,在 6 5 0～ 80 0℃ ,0 .1～ 0 .2 5s高温超短接触条件下进行馏分油催化裂解实验 ,研究了催化剂上焦炭沉积的规律。在实验测定结焦速率基础上 ,分析了不同温度下焦炭沉积的机理 ,并通过理论计算证明了上述推测。以上规律对于进一步定量研究结焦规律 ,确定最优的操作条件 ,均具有指导意义。     

改性高岭土性能研究 Ⅰ.酸性和催化活性

利用２９Ｓｉ和２７ＡｌＭＡＳＮＭＲ、ＸＲＤ、ＮＨ３－ＴＰＤ、ＩＲ、ＭＡＴ等手段研究了高岭土酸改性过程和酸碱改性后的酸性、催化活性。结果表明,高岭土偏高岭土化过程中形成的四面体铝是偏高岭土具有酸反应活性的直接原因,在８５０℃左右活性达到最高。酸改性高岭土酸性的产生经历了一次脱羟基（铝的活化）、羟基化（酸反应）、二次脱羟基的过程,其中羟基化是酸性产生的关键步骤。碱改性高岭土的酸性中心数量少于酸改性高岭土,但是前者主要存在稳定的八面体Ａｌ—ＯＨ,是其酸性中心强度比后者高的原因,在磷含量小于０．８％时,磷改性处理可降低改性高岭土的酸强度。     

合成直链烷基苯的锆磷铝固体酸催化剂 I.催化剂合成及其影响因素

合成了一系列用于苯与直链烯烃烷基化反应的含有杂原子的磷铝分子筛固体酸催化剂 (MeZrAPO 5 ) ,同晶取代磷铝分子筛骨架中磷和铝的杂原子包括锆和至少一种选自硅、硼、镓、锗、铁、镁、锡等的元素。考察了晶化温度、晶化时间、杂原子种类、铝源等因素对催化剂合成的影响 ,探索了合成样品中模板剂脱除的最佳条件。结果表明 ,晶化温度高于 15 0℃、n(TEA) /n(Al2 O3 )≥ 1 5以及加入Zr原子都有利于直接生成MeZrAPO 5晶相 ;用小晶粒和高结晶度的铝源合成时 ,分子筛的结晶度高。     

加氢润滑油基础油结构组成与氧化安定性关系I.加氢润滑油基础油的物理性质和结构组成

 采用柱色谱、质谱法、1H NMR 、13C NMR和 DEPT 13C NMR等手段详细分析了6种不同基属原油生产的加氢润滑油基础油和1种聚α烯烃（PAO-6）的物理性质和烃类组成。结果表明,各种基础油的S、N含量很低,饱和烃含量很高,芳香烃含量很低;基础油碳类型含量的分布和基础油烃类结构组成影响其黏度指数。正构烷烃和亚甲基含量高的基础油的黏度指数高,而支链甲基和次甲基含量高的基础油黏度指数低;支化度与基础油黏温性能有负的相关性,支化度越大,黏温性能越差,黏度指数越低。不同基属原油生产的润滑油基础油烃类结构符合相应原油特性。     

Removal of Nickel and Vanadium from Crude Oil by Microwave-Chemical Method. I. Chemical Method

WY series demetalizers, some types of thiocarbamate, were synthesized by organic amine (diethylene triamine and triethylene tetramine), carbon disulfide, and sodium hydroxide and used to remove nickel and vanadium from crude oil. WY-1 demetallizer has excellent removal of nickel and vanadium efficiency for Shengli crude oil and Iran crude oil. The nickel and vanadium removal efficiency of Shengli crude oil reached 43.41 and 41.63% at the dosage of WY-1 500 mg/L, reaction time 30 min, and reaction temperature 70°C. With the dosage of WY-1 and increasing reaction time and reaction temperature, the nickel and vanadium removal efficiency of crude oil increased.     

重油加氢脱氮催化剂的研制 Ⅰ.载体氧化铝的pH摆动法制备

以铝钒土酸溶出的硫酸铝经脱铁后的溶液为铝源,与碱或碱金属盐交替加料中和沉淀（即ｐＨ摆动法）制备的氢氧化铝,具有典型的拟薄水铝石结构,可直接成型制成催化剂载体γ－Ａｌ２Ｏ３。该法原料价格低廉,制备方法简便。试验考察了原料匹配、溶液浓度、反应温度、摆动次数等条件对产品孔结构参数的影响,并对产品的晶型、形貌、表面酸性质等进行了测试。该法制备的氧化铝适宜作为加氢精制催化剂的载体,且特别适用于制备加工高含氮重油的加氢脱氮催化剂。     

汽油润滑性研究I.对欧洲汽油润滑性的初步考察

采用已建立的汽油磨损测试法对欧洲汽油的润滑性进行了初步考察,其目的是得到一些基本数据供进一步研究用。为了考察汽油润滑性问题内在的化学因素,对基础油、汽油组分、掺和剂、添加剂以及商品汽油进行了以下试验：（１）考察５种已知无铅基础汽油的磨损,并与瑞典环保柴油对比;（２）考察汽油各组分油的本体组成对汽油润滑性的影响;（３）对掺和剂ＭＴＢＥ加入汽油,考察其对润滑性的影响;）４）将清净剂加入汽油,考察其对润     

负载杂多酸催化剂的表征及催化合成乙酸正丁酯的研究Ⅰ.负载杂多酸催化剂制备及表征

采用浸渍法,以硅胶、中性氧化铝、超稳Y沸石和β沸石分子筛为载体,制备了一系列不同负载量的SiW12杂多酸催化剂,并采用IR和XRD等手段对催化剂的物化性质进行了表征.结果表明,在酸性载体(硅胶)、超稳Y沸石和8沸石上,可形成具有Keggin结构的SiW12杂多酸结晶,出现了明显的层状结构,酸性沸石原有的IR与XRD特征峰变得弥散或消失.在中性氧化铝上进行负载后,没有明显的Keggin结构特征峰.     

乙烯氧氯化反应技术的研究Ⅰ．催化剂表面的物理结构及化学状态

借助现代检测设备，对目前工业上使用的乙烯氧氯化反应ＣｕＣｌ＿２／Ａｌ＿２Ｏ＿３催化剂表面的结构和化学状态进行测试分析结果表明，在正常反应条件下，活性组份ＣｕＣｌ＿２的流失并不严重，反应过程中反应气氛的不同主要是通过改变催化剂表面的Ｃｌ／Ｃｕ原子比来影响催化剂的化学活性；吸附在催化剂表面上的水，在２００℃以上的反应温度下已基本被脱除。同时，在反应过程中，催化剂表面活性组份Ｃｕ上进行的是氧化－还原反应，而且表面孔径会变大，比表面减小，机械强度也随之降低。     

Study and Evaluation of Aging Performance of Petroleum Asphalts and Their Constituents During Oxygen Absorption. II. Chemical Group Composition and Structure Changes

Abstract

The changes of the chemical group compositions and the structures of Chinese Shanjiasi, Shengli, and Renqiu petroleum asphalts and their constituents during oxygen absorption were successfully studied based on the sample oxygen absorption behaviors. The research results show that every asphalt constituent after absorbing oxygen would change into the near heavier one with the exception of saturates, of which the greatest is the conversion rate of resin into asphaltene. The oxygen molecules absorbed by samples are mainly converted into the oxygen atoms in some oxygen-containing function groups, such as O-H, C=O, and S=O groups. The asphalt colloidal stabilities deteriorate clearly and the molecular weight distributions of asphalts and their constituents spread toward higher molecular weights. The molecular weights of all samples increase gradually after oxygen absorption. Resins and asphaltenes are the more unstable constituents in asphalts as shown by their evident changes after oxygen absorption. The changes of Shengli asphalt and its constituents absorbing more easily oxygen are clearly greater than those of Shanjiasi asphalt and its constituents.     

Study and Evaluation of Aging Performance of Petroleum Asphalts and Their Constituents During Oxygen Absorption. II. Chemical Group Composition and Structure Changes

The changes of the chemical group compositions and the structures of Chinese Shanjiasi, Shengli, and Renqiu petroleum asphalts and their constituents during oxygen absorption were successfully studied based on the sample oxygen absorption behaviors. The research results show that every asphalt constituent after absorbing oxygen would change into the near heavier one with the exception of saturates, of which the greatest is the conversion rate of resin into asphaltene. The oxygen molecules absorbed by samples are mainly converted into the oxygen atoms in some oxygen-containing function groups, such as O-H, C=O, and S=O groups. The asphalt colloidal stabilities deteriorate clearly and the molecular weight distributions of asphalts and their constituents spread toward higher molecular weights. The molecular weights of all samples increase gradually after oxygen absorption. Resins and asphaltenes are the more unstable constituents in asphalts as shown by their evident changes after oxygen absorption. The changes of Shengli asphalt and its constituents absorbing more easily oxygen are clearly greater than those of Shanjiasi asphalt and its constituents.     

Hydrotreating of Maya Crude Oil: I. Effect of Support Composition and Its Pore-diameter on Asphaltene Conversion

A systematic study for a concept governing support effect in heavy oil hydrotreating (HDT) catalysts is performed. Different Al₂O₃ and its mixed oxides supports were prepared and CoMo supported catalysts were tested for Maya heavy crude oil hydrotreating. Fresh and spent catalysts are characterized with N₂ adsorption-desorption, element analysis, and scanning electron microscopy-energy dispersion analysis by x-ray (SEM-EDAX), which confirms that coke and metals deposition on the surface of catalyst is most probably near the pore mouth. It is also demonstrated from these results that asphaltene conversion depends on the pore diameter of the catalyst, while other hydrotreating conversions (hydrodesulfurization (HDS), hydrodenitogenation (HDN), and in some extent hydrodemetallization (HDM)) are more likely affected by the nature of active metal distribution. The evaluation of alumina mixed oxide (TiO₂, ZrO₂, B₂O₃, and MgO) supported catalysts indicates that supports with basic nature have better stability than the acid ones.