Transesterification of Palm-based Methyl Palmitate into Esteramine Catalyzed by Calcium Oxide Catalyst

The technology for transesterification reactions between methyl esters and alcohols is well established by using classical homogeneous alkaline catalysts, which provide high conversion of methyl esters to specialty or nonindigenous esters. However, in certain products where the purity of the esters is of concern, the removal of homogeneous catalysts after the completion of the reaction is a challenge in terms of production cost and water footprint. Therefore, a study to investigate the potential of heterogeneous catalysts was conducted on reactions between methyl palmitate and triethanolamine. The degree of basicity and active surface area of calcium oxide (CaO), zinc oxide (ZnO), and magnesium oxide (MgO) were first characterized by using temperature-programmed desorption (TPD-CO₂) and Brunauere–Emmett–Teller (BET), respectively. Among the metal oxides investigated, the CaO catalyst showed the best catalytic activity toward the transesterification process as it gave the highest conversion of methyl palmitate and yielded fatty esteramine compositions similar to the conventional homogeneous catalyst. The optimum transesterification condition by using the CaO catalyst utilized a lower vacuum system of approximately 200 mbar, which could minimize a considerable amount of energy consumption. Furthermore, low CaO dosage of 0.1% was able to give a conversion of 94.5% methyl ester and formed esteramine at 170 °C for 2 h. Therefore, the production of esterquats from esteramine may become more economically feasible through the methyl ester route by using the CaO catalyst, which can be recycled three times.     

Effect of Different Cosolvents on Transesterification of Waste Cooking Oil in a Microreactor

Biodiesel was prepared from waste cooking oil combined with methanol. The process was performed via transesterification in a microreactor using kettle limescale as a heterogeneous catalyst and various cosolvents under different conditions. n‐Hexane and tetrahydrofuran were selected as cosolvents to investigate fatty acid methyl esters (FAMEs). To optimize the reaction conditions, the main parameters affecting FAME% including reaction temperature, catalyst concentration, oil‐to‐methanol volumetric ratio, and cosolvent‐to‐methanol volumetric ratio were studied via response surface methodology. Under optimal reaction conditions and in the presence of the cosolvents n‐hexane and tetrahydrofuran, high FAME purities were achieved. Considering the experimental results, the limescale catalyst is a unique material, and the cosolvent method can reduce significantly the reaction time and biodiesel production cost.     

1,5-己二烯交联烯烃聚合物的合成及其抗剪切稳定性

以金属配合物为催化剂、1,5-己二烯为交联剂,采用本体聚合法合成了交联超高相对分子质量烯烃类聚合物(简称交联聚合物)。用傅里叶变换红外光谱、核磁共振、凝胶渗透色潜表征交联聚合物的结构和相对分子质量。用旋转黏度计和超声波仪研究了1,5-己二烯用量对交联聚合物溶液表观黏度的影响及交联聚合物的相对分子质量对交联聚合物溶液抗剪切稳定性的影响。实验结果表明,在最佳聚合条件(单体80mL、助催化剂0．4mL、CS-1催化剂0．090g、1,5-己二烯0．40mL、0℃、24 b)下所合成的交联聚合物的重均相对分子质量为7．7×106,数均相对分子质量3．6×106。加入少量1,5-己二烯能提高交联聚合物的抗剪切能力,同时也能提高交联聚合物的相对分子质量。交联聚合物的相对分子质量越大,抗剪切稳定性越好。1,5-己二烯用量约为0．1 mL时(单体40 mL),交联聚合物溶液的表观黏度达到最大值(16．8 mPa·s)。     

聚烯烃催化剂硅胶载体的制备和表征

采用并流共沉淀法制备了适用于聚烯烃催化剂的硅胶载体,为减少颗粒的聚集,在制备过程中添加一种表面活性剂。利用透射电子显微镜(TEM)、比表面积测定(BET)和X射线粉末衍射(XRD)法对制备的硅胶载体进行了表征;考察了在制备硅胶载体过程中原料硅酸钠溶液的浓度、溶液pH以及焙烧温度对产物硅胶载体的物理性能的影响。实验结果表明,硅酸钠溶液的浓度影响硅胶的初始粒子的大小,溶液pH直接影响硅酸钠的水解速率,焙烧温度影响硅胶的孔结构和比表面积。当硅酸钠溶液的浓度为0．2mol／L、溶液pH为8-9、反应温度为70℃、焙烧温度为700℃时,硅胶载体的BET比表面积为242．22m2／g、最可几孔径为16．45 nm、堆密度为0．492 1g/mL,与进口硅胶(Silica Gel 955)的物理性能相近。     

Study on Hydrocracking of VGO Derived from Kazakhstan-Russian Mixed Crude

1 Introduction With the successful completion of the construction of the China-Kazakhstan oil pipeline the refinery at Dushanzi Pet- rochemical Company will process the Kazakhstan-Russian mixed crude at full steam starting 2007. The high sulfur, nitro- gen and heavy metals contents in the Kazakhstan-Russian mixed crude would have a serious impact on the secondary processing units of the Dushanzi refinery, in particular on the distillate hydrocracking unit, which mainly operates on vacuum g…     

SO4^2-／ZrO2固体超强酸的制备及其催化合成ETBE的研究

采用沉淀一浸渍法制备了负载型SO4^2-／ZrO2固体超强酸催化剂，运用IR、XRD等方法表征所制备催化剂的物化性质。结果表明，所制备的催化剂具有固体超强酸催化剂的特征，酸性与焙烧温度有关，适当提高焙烧温度有利于样品酸强度的提高，但焙烧温度过高会导致脱硫；浸渍液H2SO4浓度高有利于提高催化剂的硫含量，但是浓度过高，会在催化剂上形成硫酸盐，从而降低催化剂的比表面积和酸性。采用制备的催化剂气相催化乙醇与叔丁醇合成乙基叔丁基醚反应，乙基叔丁基醚的选择性为54．71％。     

渣油胶质和沥青质在分散型催化剂作用下的临氢热反应行为

采用四组分法从辽河减压渣油中分离出胶质、沥青质，分别考察了它们在分散型催化剂作用下的临氢热反应行为。结果表明，胶质、沥青质一方面要裂化生成较轻的产物；另一方面也要发生缩合反应生成较重的反应产物以及甲苯不溶物。渣油在临氢热反应过程中，沥青质是生焦的主要来源，其次才是胶质。比较了热反应生成的沥青质与原生沥青质之间以及热反应生成的胶质与原生胶质之间化学组成的区别，结果表明，反应生成的沥青质和胶质较原生的沥青质和胶质分子结构缩合程度高，并且反应苛刻度越高，缩合程度也越高。     

基于中压加氢改质方案的炼油流程协同优化

中国石化北京燕山分公司(简称燕山分公司）为增产高附加值产品、提升效益，对炼油系统进行了流程协同优化。中压加氢裂化装置掺炼催化裂化柴油，由加氢裂化方案改为加氢改质方案运行，将改质柴油送入三号催化裂化装置（简称三催化装置）的提升管进行回炼；同时，将焦化蜡油改入加氢裂化装置进行加工，而蜡油加氢装置不再加工焦化蜡油以改善催化裂化原料。协同优化后，中压加氢改质装置的柴油产品十六烷值提高7个单位；三催化装置的液化气收率提高1.96百分点，汽油收率增加0.88百分点，总液体收率增加2.28百分点；高压加氢裂化装置喷气燃料产品的密度（20 ℃）降低至806 kg/m3，烟点为23.8 mm，尾油BMCI由11.8降低至10.8；蜡油加氢装置精制蜡油的饱和分质量分数提高4.68百分点，芳香分质量分数降低5.96百分点，氮质量分数降低0.06百分点，使催化裂化原料性质得以改善。通过将中压加氢改质装置的喷气燃料馏分抽出送催化裂化装置回炼，与回炼改质柴油相比，催化裂化汽油的研究法辛烷值（RON）增加1.0个单位，改质柴油十六烷值提高4.8个单位。通过全炼油板块系统性优化，燕山分公司车用柴油产品的十六烷值由53.5降低至51.5，解决了质量过剩问题。     

溶胶-凝胶法制备Na_2WO_4~-Mn/SiO_2催化剂及其甲烷氧化偶联反应性能的研究

采用溶胶-凝胶法制备了一系列5%Na2WO4-2%Mn/SiO2催化剂;用XRD、XPS、BET、O2-TPD和CO2-TPD等方法对催化剂进行了表征,并考察了对甲烷氧化偶联反应的催化性能。结果表明,与常规浸渍法相比,采用溶胶-凝胶法制备的Na2WO4-Mn/SiO2催化剂中W和Mn的原子浓度在催化剂表面和体相分布较为接近,而且两种制备方法所得的催化剂具有相似的催化性能,Na2WO4与α-方石英之间的相互作用,催化剂释放晶格氧的能力,碱性强弱是影响甲烷氧化偶联活性的关键因素。     

二氧化碳加氢直接合成二甲醚催化剂的研究——沉淀次序对复合催化剂结构和性能的影响

以草酸乙醇溶液为沉淀剂,采用不同的沉淀次序(并流、反加和正加)制备了CuO-ZnO-Al2O3/HZSM-5复合型催化剂,对CO2加氢直接合成二甲醚反应的催化活性顺序为:并流法催化剂>反加法催化剂>正加法催化剂。3种复合催化剂的还原温度由低到高的顺序为:并流法催化剂<反加法催化剂<正加法催化剂。在沉淀过程中,反加法和正加法均形成类胶体沉淀,相应催化剂的比表面积也较大。IR研究发现,催化剂在1101cm-1处表现Cu/Zn/Al氧化物与HZSM-5分子筛之间相互作用的IR吸收峰强度与其催化活性间存在对应关系。XRD结果表明,并流法得到的催化剂前驱体中有铜锌同形取代现象,有利于催化剂活性的发挥。