Mild and Highly Selective Preparation of Alkylate Gasoline Promoted by Using Polyetheramine-Based Acidic Ionic Liquid

A polyetheramine(PEA)-based Br?nsted-acidic ionic liquid(IL) was firstly prepared and used to promote the alkylation of isobutane with isobutene catalyzed by trifluoromethanesulfonic acid(TfOH). PEA-IL not only can resolve the persistent problem of poor solubility of the volatile and refractory reactants, but also can satisfactorily exhibit the separation of the catalyst from product oil for reuse. The PEA-IL/TfOH catalytic system with an adjustable acidity ensures a high alkylate selectivity. Under the conditions covering a VIL/VTfOH ratio of 10:3, a temperature of 25 °C, and a reaction time of 25 min, the C_8-product selectivity reaches 86.63%. The PEA-IL/TfOH catalyst can be reused 13 times without a decrease in the catalytic performance. After many operating cycles, the hydrophobic PEA-IL can be easily regenerated by simply adding water. This study provides a green, economic, and highly efficient method for producing high-octane alkylate gasoline.     

Vapour Phase Alkylation of Naphthalene over Lanthana Modified Zeolites

Lanthanum oxide impregnated large-pore zeolite catalysts were prepared. The catalysts were characterized by XRD （X-ray diffraction）, PSA （particle size analysis）, TPD （temperature programmed desorption） and SEM （scanning electron microscope）. The performances of the catalysts were investigated using the alkylation reaction of naphthalene with methanol. Under comparable conditions, the La-impregnated β-zeolite catalyst showed the highest catalytic activity among all the catalysts tested. The lower reaction temperature is favorable for the formation of 2,6-dimethyl naphthalene.     

Molecular Simulation of Transesterification of Ethylene Carbonate and Methanol Catalyzed by Ionic Liquids

Four ionic liquids [BMIM]OH, [BMIM]IM, [BMIM]Br, and [BMIM]PF6 were synthesized and characterized by infrared spectroscopy. Then the effects of ionic liquids(ILs), cocatalysts, and reaction temperature on the catalytic performance for transesterification of ethylene carbonate and methanol were investigated with orthogonal experiments. The influence of cations and anions of ILs on catalytic activity was revealed by the density functional theory(DFT). The reaction mechanism was proposed based on the experimental results and DFT. The results demonstrated that the optimal catalyst was [Bmim]PF_6/CaO, which exhibited the advantages of high activity, excellent stability, and easy recycling. Under the optimized conditions covering a catalytic temperature of 130 °C, an ionic liquid/cocatalyst mass ratio of 5:1, and a catalyst dosage of 4.0%, the conversion rate could reach 65.23% with a dimethyl carbonate selectivity of 98.95%. No significant loss of catalyst activity was detected after 7 recycle times.     

回炼油催化裂化及PSO-RBF神经网络模型

Catalytic cracking experiments of FCC cycle oil were carried out in a fixed fluidized bed reactor. Effects of reac- tion conditions, such as temperature, catalyst to oil ratio and weight hourly space velocity, were investigated. Hydrocarbon composition of gasoline was analyzed by gas chromatograph. Experimental results showed that conversion of cycle oil was low on account of its poor crackability performance, and the effect of reaction conditions on gasoline yield was obvi- ous. The paraffin content was very high in gasoline. Based on the experimental yields under different reaction conditions, a model for prediction of gasoline and diesel yields was established by radial basis function neural network （RBFNN）. In the model, the product yield was viewed as function of reaction conditions. Particle swarm optimization （PSO） algorithm with global search capability was used to obtain optimal conditions for a highest yield of light oil. The results showed that the yield of gasoline and diesel predicted by RBF neural network agreed well with the experimental values. The optimized reac- tion conditions were obtained at a reaction temperature of around 520 ~C, a catalyst to oil ratio of 7.4 and a space velocity of 8 h~. The predicted total yield of gasoline and diesel reached 42.2% under optimized conditions.     

三乙胺氯铝酸离子液体催化合成2-异丙基萘

In this paper, 2-isopropyl naphthalene has been synthesized by the reaction of naphthalene and isopropyl bromide, using triethylamine hydrochloride-aluminum chloride ionic liquid as the catalyst. The effect of the catalyst composition, the reaction time, the reaction temperature, the ionic liquid dosage, as well as the molar ratio of the reagents on the 2-isopropyl naphthalene yield was systematically investigated. The optimal reaction conditions cover: an AlCl3 to Et3NHCl ratio of 2.0, a reaction time of 3 h, a reaction temperature of 15.0 ℃, a volume fraction of ionic liquid to the mixture(isopropyl bromide, n-dodecane and n-hexane) of 9%, and a naphthalene/isopropyl bromide molar ratio of 4.0. Under the optimal reaction conditions, the conversion of isopropyl bromide reached 98% and the selectivity of 2-isopropyl naphthalene was equal to 80%. The test results verified good catalytic activity upon using Et3NHCl-AlCl3 ionic liquid as the catalyst for alkylation of naphthalene with isopropyl bromide. The activity of the ionic liquid remains unchanged after it has been recycled for 4 times.     

Development of Novel Resid Hydrometallization Catalyst RDM-3

Based on the reaction mechanism of resid hydrodemetallization, a new catalyst carrier was designed and prepared. As compared with the similar type of catalyst carrier, the said new carrier featured a higher pore volume, a larger pore diameter and a weaker surface acidity, which could improve the diffusion performance and stable reaction performance of the catalyst. The active metal components were loaded on the said carrier by a new technique for better metal dispersion, thus the impurity removal rate of the new catalyst, RDM-3, was improved significantly. The commercial test of the RDM-3 catalyst showed that the process of catalyst preparation was stable, the catalyst performance was slightly better than the catalyst prepared in the lab, therefore, the catalyst could be manufactured in commercial scale.     

盐酸三乙胺-三氯化铝离子液体催化甲苯与氯代叔丁烷烷基化反应

Alkylation of toluene with 2-chloro-2-methylpropane (t-Bu-Cl) to synthesize para-tert-butyltoluene (PTBT) was carried out in the presence of triethylamine hydrochloride-aluminum chloride ionic liquids used as the catalyst. The ionic liquids were prepared with different molar ratios of Et3NHCl to AlCl3 , and the effect of the molar ratio between AlCl 3 and Et3NHCl, the reaction time, the reaction temperature, the ionic liquid dosage, as well as the molar ratio of toluene to chloro-2-methylpropane on the alkylation reaction of toluene with chloro-2-methyl-propane was investigated. The test results showed that the acidic ionic liquids prepared with Et3NHCl and AlCl3 had good activity and selectivity for the alkylation reaction of toluene with alkyl chloride to produce PTBT. The optimal reaction conditions were specified at anAlCl3 to Et3NHCl ratio of 1.6, a reaction temperature of 20℃, a mass fraction of toluene to ionic liquid of 10%, and a chloro-2-methylpropane to toluene molar ratio of 0.5. Under the suitable reaction conditions, a 98% conversion of chloro-2-methylpropane and an 82.5% selectivity of PTBT were obtained. Ionic liquids could be reused 5 times with its catalytic activity unchanged, and the regenerated ionic liquids can be recycled.     

Residue Upgrading in Slurry Phase over Ultra-fine NiMo/γ-Al_2O_3 Catalyst

In this article, residual oil hydroconversion was studied in slurry phase in the presence of fine solid Ni Mo/γ-Al2O3 catalyst and the effects of operating conditions were carefully studied. The results showed that residue conversion was only affected by the reaction temperature and reaction time. The coke yield increased with a higher reaction temperature, a bigger catalyst particle size, a longer reaction time, a lower initial hydrogen pressure and a lower catalyst concentration. Heteroatoms removal rate increased with a higher reaction temperature, a longer reaction time, a higher initial hydrogen pressure, a higher catalyst concentration, and a smaller catalyst particle size. The role of catalyst in the slurry bed technology was discussed and its function could be stated as follows: the metal was applied to activate the hydrogen atoms for removing heteroatoms and saturating aromatics, while the support of the catalyst was used to prevent the mesophase coalescence for reducing coke formation.     

Study on Removing Trace Olefins in Aromatic Hydrocarbons with HPMo-loaded Y Zeolites

HPMo-loaded Y-zeolites were prepared for the removal of trace olefins from aromatic hydrocarbons. The temperature of calcination and the proportion of phospho-molybdic acid in the catalyst were studied. The catalytic activity for olefins removal and the service life of the catalyst were tested in a fixed bed microreactor. The results showed that the catalyst containing 3% phospho-molybdic acid, which was calcined at 550℃, demonstrated the best activity for olefins removal. The catalyst could be regenerated and could perform still very well. Catalyst characterization was performed by XRD and measured by pyridine-FTIR spectrometry. The test results indicated that the activity of the catalyst was related with the effect of acid concentration and acid strength. Besides, the deactivation of the catalyst was associated with the formation of coke deposits and the deactivated catalyst could recover its activity by oxidation with air under a proper temperature.     

磷化钼作为同时加氢脱氮、脱硫和降烯烃催化剂的研究

Transition-metal molybdenum phosphides were prepared by direct reduction of an amorphous phosphate precursor in hydrogen at relatively low temperature(650℃).XRD(X-ray diffraction analysis)measurements showed that pure molybdenum phosphide formed after the reduction with H2.The reactivity was determined in a continuous-flow microreactor at a H2 pressure of 3.0 MPa.A sample of prepared molybdenum phosphide catalyst diluted with γ-Al2O3(20% phosphate precursor)was used for simultaneuous HDN(Hydrodenitrogenation),HDS (Hydrodesulfurization and HDY)Hydrogenation of aromatics).The influences of space velocity,flow rate of hydrogen,reaction time and temperature on hydrotreating performance were studied.Pyridine,thiophene and cyclohexene were used as model compunds,their contents were respectively 5%,5% and 20%,Cyclohexane was used as the solvent.     

大孔磺酸树脂CT175催化噻吩与异丁烯烷基化硫转移反应的研究

以CT175树脂为催化剂,考察了噻吩与异丁烯烷基化的反应性能。研究结果表明,CT175树脂催化剂在常压、80℃、气体(异丁烯与氮气摩尔比为1/1)流量7.5 ml/min、反应液体原料(含4 g/L噻吩的苯溶液)质量空速2.64h-1的条件下,噻吩烷基化转化率高达99％以上。并用不同原料对CT175树脂催化噻吩与异丁烯烷基化反应中的失活行为及再生性能进行了考察,研究发现,原料中的二烯烃是导致催化剂失活的主要原因,失活后的催化荆的再生实验表明此催化剂有良好的再生性能。     

延迟焦化低硅消泡剂的研制

研制了一种用于延迟焦化过程的低硅消泡剂,该消泡剂是以聚醚改性聚硅氧烷为主体复配而成。以含氢硅油与聚醚为原料,催化合成了聚醚改性聚硅氧烷;考察了反应时间、反应温度、物料配比、催化剂用量对反应的影响,确定了最佳合成条件,即含氢硅油中的Si-H与聚醚中的-OH的摩尔比为1:(1.4~1.6)、催化剂FA-2的质量分数为0.4 %、反应温度为110 ℃、反应时间为8 h。评价结果表明,所制备的聚醚改性聚硅氧烷及其复配物的消泡及抑泡性能良好。     

H-ZSM-5/ZrO2/SO42-固体酸复合催化剂的表征及烷基化反应性能

将H-ZSM-5分子筛与Zr基氧化物进行复合,经过硫酸处理后,合成H-ZSM-5/wZrO₂/SO^2-₄(w分别为40%、50%、60%)固体酸复合催化剂。采用X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)及NH₃程序升温吸附-脱附(NH₃-TPD)等分析手段对催化剂进行表征,并在固定床反应装置上考察了不同催化剂催化异丁烯-异丁烷烷基化反应性能。结果表明：经过硫酸处理后,催化剂中单斜晶相m-ZrO₂转化为对烷基化反应有利的四方晶相t-ZrO₂;H-ZSM-5/50%ZrO₂/ SO^2-₄固体酸复合催化剂具有最高的总酸量和中强酸酸量,中强酸是催化异丁烯 异丁烷烷基化反应的控制因素;同时也证实了H-ZSM-5和ZrO₂ 2种组分在复合催化剂中具有协同作用。在压力为1.4 MPa、温度为80 ℃、原料进料体积流速为2.0 mL/h、载气体积流速为1200 mL/h、反应时间为120 min的条件下,H-ZSM-5/50% ZrO₂/SO^2-₄复合催化剂作用下产物C8选择性最高为83.0%,异丁烯最高转化率为94.1%,反应稳定后异丁烯转化率保持在55.2%,收率保持在45.8%,说明H-ZSM-5/50% ZrO₂/SO^2-₄固体酸复合催化剂具有良好的催化反应性能。     

烷基甲苯氯化法合成2,6-二氯甲苯

实验以氯气,异丁烯,甲苯为原料,经烷基化,氯化,脱烷基反应制备了2,6-二氯甲苯.其中烷基化温度30℃,n(甲苯):n(叔丁基氯)=1:2,收率为73%.氯化反应采用5 g m(FeCl<,3>):m(AlCl<,3>)=1:2的复合催化剂,温度50℃,收率可达82%;脱烷基过程温度50℃,反应时间8 h,产生的异丁烯...     

C4烷基化反应机理的分子模拟

采用基于密度泛函理论的量子化学方法计算了异丁烷/丁烯烷基化基元反应的反应能垒。结果表明,反应能垒最高的异丁烷氢负离子转移反应是烷基化反应的速率控制步骤。tert C+4与丁烯反应主要得到目标产物三甲基戊烷, tert C+4可由异丁烯质子化生成,或由sec C+4骨架异构化生成,也可由正丁烯先异构化生成异丁烯,异丁烯进一步质子化生成,还可由异丁烷氢负离子转移反应生成。通过对反应过程中与C4烷基化目标产物C+8相关的异构化基元反应能垒的计算,得到C4烷基化反应中目标产物C8产物的生成路线,分子模拟所得的结果与实验所得的产物选择性结果相一致。     

对叔丁基苯酚的杂多酸催化合成

采用高选择性的杂多酸H_4GeW_(12)O_(40)·xH_2O作催化剂,苯酚与异丁烯烷基化合成了对叔丁基苯酚。通过正交试验和条件试验,考察了反应温度、反应时间、原料配比、催化剂用量等因素对对叔丁基苯酚收率的影响,确定的最佳工艺条件是:反应温度110℃,反应时间4.5 h,苯酚与异丁烯的摩尔比1:2,催化剂用量为苯酚质量的3％。在此条件下,产品的收率达85％,与硫酸催化剂相比,提高收率20％以上。     

聚醚脂肪酸酯的合成及应用

以对甲苯磺酸为催化剂、石油醚为携水剂,合成了性能优良的聚醚脂肪酸酯。考察了聚醚相对分子质量、反应温度、反应时间、催化剂用量及原料摩尔比等工艺条件对脂肪酸转化率的影响。结果表明,在聚醚相对分子质量1300,反应温度180qC、反应时N4h、催化剂用量占反应物总量0．5％、原料聚醚与脂肪酸摩尔比1．1：1的优化条件下,合成的聚醚脂肪酸酯作为单体之一,用于高速纺化纤油剂中,具有良好的耐热性、平滑性、集束性与牵伸性。     

氯铝酸离子液体催化苯与氯乙烷合成乙苯

以氯铝酸离子液体([Et3NH]Cl-AlCl3)为催化剂,催化苯与氯乙烷烷基化反应合成乙苯,考察了反应投料方式、原料配比、反应温度、反应时间和[Et3NH]Cl-AlCl3用量对烷基化反应的影响,并对比了[Et3NH]Cl-AlCl3和AlCl3的催化效果。实验结果表明,在间歇式和半间歇式两种投料方式下,最佳反应条件均为:反应温度70℃,n(苯)∶n(氯乙烷)=(8.0～10.0)∶1,催化剂用量为原料总质量的10%,反应时间20～30 min;半间歇式反应的苯转化率和乙苯选择性均高于间歇式反应,半间歇式反应的苯转化率可达到9.48%,乙苯选择性为93.65%;[Et3NH]Cl-AlCl3的催化活性明显高于AlCl3。     

正癸烷在不同酸性Y型分子筛催化剂上催化裂化生成C4烃的规律研究

采用USY,REHY,REY分子筛作为活性组分,经喷雾干燥制备了USY,REHY,REY分子筛催化剂;以正癸烷为模型化合物,在小型流化床装置上考察反应温度、剂油比、催化剂酸量对C4烃产物选择性的影响。结果表明：3种催化剂作用下,在剂油质量比为6、反应时间为75 s的条件下,随着反应温度从460 ℃升高到540 ℃,异丁烷选择性下降2百分点左右,正丁烷和异丁烯选择性上升1百分点左右,正丁烯选择性增加2?3百分点;在反应温度为500 ℃,反应时间分别为150 s（剂油质量比3）,75 s（剂油质量比6）,50 s（剂油质量比9）的条件下,随着剂油质量比从3增大到9,C4烃产物选择性基本不变;相同条件下,增加催化剂酸量有利于增加正丁烷和异丁烷选择性,降低正丁烯和异丁烯选择性。     

苯酚-甲醇气相烷基化合成邻甲酚

采用共沉淀法制备了一种新型Fe-Mg-O催化剂,考察了该催化剂对苯酚-甲醇气相烷基化合成邻甲酚反应的催化性能。实验结果表明,Fe-Mg-O催化剂具有良好的低温活性和稳定性,是一种邻甲酚选择性高的苯酚邻位甲基化催化剂。在反应温度360℃、液态空速1.0h~(-1)、常压、苯酚与甲醇的摩尔比1:4的反应条件下,苯酚单程转化率达47.3%,邻甲酚选择性达90%以上。催化剂制备的重复性好、再生容易,在反应温度350～380℃的范围内,催化剂连续运转800h后仍具有较高的催化活性。