Improving Stability of FCC Gasoline Using Ionic Liquids Catalyst After Treating

The ionic liquids used herein were alkyl-containing ammonium-aluminum chloride ionic liquids system, which were made by the reaction of short-chain alkyl ammonium salts and aluminum chloride. The factors influencing stability of gasoline and the importance of improving it were described in this article, so was the characteristic of ionic liquids. A novel way to improve the stability of gasoline using ionic liquids was studied herein, as well as the study of decreasing the basic nitrogen content and the sulfur content of mercaptan, treating the gasoline and decreasing the olefin content of gasoline with supported ionic liquids catalyst on a small scale. After treating, the sulfur content of gasoline decreased to 0 nearly, and the basic nitrogen content decreased greatly too, whereas the octane number (RON) of gasoline increased a little. To improve the catalysis of ionic liquids and prolong the using life of ionic liquids, a buffering agent was added into ionic liquids. Ionic liquids catalyst, as a green catalyst friendly to environment, can displace many other alkylation catalysts, decrease the olefin content of gasoline, and show their notable advantages: mild conditions, short reaction time, simple operation, easy separation of the products and the catalyst.     

Improving Stability of FCC Gasoline Using Ionic Liquids Catalyst After Treating

Abstract

The ionic liquids used herein were alkyl-containing ammonium-aluminum chloride ionic liquids system, which were made by the reaction of short-chain alkyl ammonium salts and aluminum chloride. The factors influencing stability of gasoline and the importance of improving it were described in this article, so was the characteristic of ionic liquids. A novel way to improve the stability of gasoline using ionic liquids was studied herein, as well as the study of decreasing the basic nitrogen content and the sulfur content of mercaptan, treating the gasoline and decreasing the olefin content of gasoline with supported ionic liquids catalyst on a small scale. After treating, the sulfur content of gasoline decreased to 0 nearly, and the basic nitrogen content decreased greatly too, whereas the octane number (RON) of gasoline increased a little. To improve the catalysis of ionic liquids and prolong the using life of ionic liquids, a buffering agent was added into ionic liquids. Ionic liquids catalyst, as a green catalyst friendly to environment, can displace many other alkylation catalysts, decrease the olefin content of gasoline, and show their notable advantages: mild conditions, short reaction time, simple operation, easy separation of the products and the catalyst.     

Application of High Shear Agitation for Desulfurization of Gasoline Using Ionic Liquids

The high shear agitation device was first adopted for gasoline desulfurization by ionic liquids. The effect of benzylimidazol fluoborate in desulfurization of gasoline and the influence of moisture on deuslfurization rate were investigated. The experimental results showed that the ionic liquid could effectively decrease the sulfur content of gasoline and the optimal conditions were as follows: The reaction could be carried out at room temperature, a volumetric ratio between oil and the liquid of 2∶1, a volumetric ratio between water and ionic liquid of 0.04∶1, a rotational speed of 5 krad/s, and a reaction time of 1 minute. The desulfurization rate of gasoline reached 53.6%, and the gasoline yield was up to 97.3%. The ionic liquid could be recycled for repeated use, and the use of high shear agitation for gasoline would have good prospects.     

Imidazolium-based Alkylsulfate Ionic Liquids and Removal of Sulfur Content From Model of Gasoline

Two ionic liquids, butyl-methyl-imidazolium octylsulfate, [BMIM][OCSO₄], and ethyl-methyl-imidazolium ethylsulfate, [EMIM][EtSO₄], were demonstrated to be effective for the removal of aromatic sulfur compounds such as benzothiophene and thiophene from model of gasoline. Organic compounds with higher aromatic π-electron density were favorably adsorbed by using ionic liquids. It was shown that the extractive ability of the alkylsulfate IL_s was dominated by the structure and size of cation and anion. The cation and anion structure and size of ionic liquids are important factors affecting the absorption capacity for aromatic compounds. It is found that [BMIM][OCSO₄] has the best effect on the selective removal of sulfur compounds from gasoline. Sulfur extractive selectivity for specified IL followed the order BT>T>3-MT>2-MT.     

Extractive Desulfurization of Gasoline Using Ionic Liquid Based on CuCl

Abstract

CuCl-based ionic liquid ([HMim]Cl/CuCl) was synthesized by mixing 1-hydracid-3-methylimidazolium chloride ([HMim]Cl) with CuCl. Ionic liquid ([HMim]Cl/CuCl) was employed as an extractant remove sulfur from gasoline. It was found that [HMim]Cl/CuCl can remove sulfur-containing compounds from gasoline at room temperature. The extractive desulfurization mechanism of ionic liquid was proposed. The effects of extractive conditions on desulfurization of gasoline was investigated. The used ionic liquids can be regenerated by re-extraction using tetrachloromethane and reused five times.     

FCC汽油在ZSM-5分子筛上的芳构化反应

考察了全馏分催化裂化（FCC）汽油的芳构化改质反应，结果表明，在三种不同硅铝比的分子筛中，以硅铝比为50的分子筛为载体所制备的催化剂性能较好。对Ni、Mo、Zn、Co4种金属活性组分的选择考察，以Zn为活性组分的催化剂芳构化性能最好，以Ni为活性组分的催化剂液收最高。分析了FCC汽油中不同烃类的芳构化反应历程．得出金属组分应有适宜的含量。     

操作参数对FCC汽油烯烃度的影响

在XTL-5小型提升管催化裂化试验装置上,考察了操作条件对汽油烯烃度的影响。在此基础上,分别构造了两个表示烯烃含量大小和氢转移反应强弱的参数——烯烃度和氢转移指数。还探讨了反应温度和剂油比等操作条件对FCC汽油烯烃度的影响规律及机理。     

Study on Disproportionation Reaction of FCC Gasoline on Acid Catalyst

Based on the experimental data relating to the reaction of FCC gasoline on acid catalyst the analysis of product distribution, and composition of gasoline and diesel fractions have been analyzed. The occurrence of disproportionation reaction of FCC gasoline on acid catalyst and the network of disproportionation reaction have been identified. Study has also shown that different reaction temperatures can result in different pathways of disproportionation reactions on acid catalyst.     

FCC汽油加氢改质催化剂研究开发进展

综述了FCC汽油加氢改质催化剂的研究开发进展,分析比较了各种催化剂的特点,讨论了其适用范围,指出了目前汽油改质催化剂研究开发存在的问题,认为具有高度加氢异构-适度芳构化双功能和长期稳定性的新型催化剂将是FCC汽油改质催化剂今后发展的趋势。     

金属络合类离子液体用于汽油萃取脱硫的研究

本文由原料[Et₃NH]Cl、无水FeCl₃和无水CuCl合成了离子液体[Et₃NH]Cl-FeCl₃/CuCl,考察了其萃取脱硫性能。结果表明：在对模拟汽油（噻吩溶于正辛烷）和FCC汽油脱硫时,离子液体[Et₃NH]Cl-FeCl₃/CuCl均表现出了较好的脱硫性能。当离子液体和模拟汽油的体积比V(IL):V(oil)=0.08,时间t=50min,温度T=50℃时,模拟汽油中噻吩的脱除率能够达到 93.9%。在相同的温度和时间条件下,当离子液体和FCC汽油的体积比V(IL):V(oil)=0.1时,经过三次萃取,能够获得低硫（硫含量小于10μg/g）FCC汽油,FCC汽油的收率为94.3%。离子液体具有较好的循环使用能力,循环使用5次后,汽油中噻吩的脱除率没有明显降低。     

提高汽油质量的措施

针对汽油中硫及烯烃含量高、调和组分单一的现状，以欧洲Ⅲ汽油标准为指导原则，根据实际生产情况，优化催化裂化装置原料，使用降硫助剂和降烯烃催化剂，采用新技术新工艺，增加高标号调和组分．增建汽油加氢改质装置和吸附脱硫装置等一系列技术措施，使汽油产品质量指标满足GB17930—1999要求。     

Development and Commercial Application of RFCC Catalyst for Reducing Sulfur Content in Gasoline

The sulfur-reducing functional component the Lewis acid-base pair compound and associated active zeolite component were developed to prepare the RFCC catalyst DOS for reducing sulfur content in gasoline. The results of catalyst evaluation have revealed that the Lewis acid-base pair compound developed hereby could enhance the conversion of macromolecular sulfur compounds by the catalyst to promote the proceeding of desulfurization reactions, and the synergetic action of the selected zeolite and the Lewis acid-base pair compound could definitely reduce the olefins and sulfur contents in gasoline. The heavy oil conversion capability of the catalyst DOS thus developed was higher coupled with an enhanced resistance to heavy metals contamination to reduce the sulfur content in gasoline by over 20%. The commercial application of this catalyst at the SINOPEC Jiujiang Branch Company has revealed that compared to the GRV-C catalyst the oil slurry yield obtained by the catalyst DOS was reduced along with an improved coke selectivity, an increased total liquid yield, and a decreased olefin content in gasoline. The ratio of sulfur in gasoline/sulfur in feed oil could be reduced by 20.3 m%.     

Effects of Chemical Components on Stability of FCC Gasoline

The effects of the mercaptan sulfur, nitrogen compounds, phenolic compounds, and conjugated dienes on the stability of FCC naphtha were investigated by means of chemical treatment and addition of model compounds. Experimental results indicated that conjugated dienes in spite of its very small content in naphtha played the most important effect on the stability of naphtha. After the conjugated dienes have been removed, the stability would increase significantly. A high amount of mono-olefins is another important reason for naphtha oxidation although its effect is less than that of dienes. A certain amount of phenolic compounds should be retained during the naphtha refining. Nitrogen compounds and sulfur compounds cause poor effects on the stability of naphtha, but their effects are minimal because of the small quantity in the naphtha.     

制备因素对催化裂化汽油加氢脱硫催化剂性能的影响

针对催化裂化汽油脱硫技术要求,介绍了一种以共沉淀法制备的载体负载Co、Mo活性金属组分的催化汽油加氢脱硫催化剂,考察了载体Mg／Al原子比、焙烧温度、活性金属含量对催化剂活性及选择性的影响,并对本研究的催化剂进行了1000h的稳定性试验。实验结果表明,采用Mg／Al=X 0、5、焙烧温度(y 200)℃所制备的载体,在其活性金属MoO3含量8％、CoO含量2.0％时,催化剂具有适宜的酸性中心数和最佳的脱硫选择性;本研究催化剂在1000h的试验运转过程中,具有较高的脱硫率和较低的烯烃饱和率,其活性稳定性良好。     

FCC Gasoline Sulfur Reduction by Additives: A Review

This review covers publications in the open literature and patents issued during the last 10 years on issues related to fluid catalytic cracking (FCC) gasoline sulfur reduction. Emphasis was placed on FCC additives, their composition and performance. An attempt was made to elucidate the mechanism for sulfur reduction at FCC cracking conditions. Fluid catalytic cracking technology advances, both process and catalyst, have historically worked together to achieve significant improvements in FCC performance. There is every reason to expect that this will continue to be the case in the future. These advances will have an impact on the volume and quality of the FCC gasoline produced and will offer additional operating flexibility.     

FCC Gasoline Sulfur Reduction by Additives: A Review

Abstract

This review covers publications in the open literature and patents issued during the last 10 years on issues related to fluid catalytic cracking (FCC) gasoline sulfur reduction. Emphasis was placed on FCC additives, their composition and performance. An attempt was made to elucidate the mechanism for sulfur reduction at FCC cracking conditions. Fluid catalytic cracking technology advances, both process and catalyst, have historically worked together to achieve significant improvements in FCC performance. There is every reason to expect that this will continue to be the case in the future. These advances will have an impact on the volume and quality of the FCC gasoline produced and will offer additional operating flexibility.     

催化裂化汽油的下行床催化转化

以循环下行床为反应器,催化裂化汽油为原料,在工业催化裂化(FCC)催化剂和催化裂解(DCC)催化剂作用下,研究了催化裂化汽油的催化转化过程。实验结果表明,在下行床反应器中,催化裂化汽油中的烯烃能显著降低,主要转化为低碳烯烃产品,同时得到富含芳烃的液体产品,副产干气和焦炭量很低。催化裂化汽油在FCC催化剂和DCC催化剂上表现出不同的反应机理。FCC催化剂孔道大,可以发生双分子裂化反应和单分子裂化反应,而DCC催化剂孔道小,以单分子裂化反应机理为主,同时DCC催化剂低碳烯烃选择性更高。     

催化裂化汽油烷基化脱硫技术研究及进展

介绍了催化裂化汽油烷基化脱硫的特点及原理,综述了近年来国内外烷基化脱硫的工艺现状及脱硫催化剂的研究发展情况。认为烷基化脱硫具备了脱硫效率高、可降低油品烯烃含量且辛烷值损失小、操作费用低、投资设备少等优点,适合大力开展研究。     

催化裂化汽油腐蚀不合格的处理方法

针对广州石油化工总厂催化裂化汽油腐蚀不合格原因，进行了一些处理方法的研究，并开发出ＣＩ－１汽油抗腐蚀添加剂，解决了催化裂化汽油腐蚀不合格的问题。该剂使用简单易行、成本低、效果好。     

连续式离子液体催化芳烃烷基化

以离子液体为催化剂,采用间歇式和连续式烷基化装置,研究了C20~C28长链α烯烃和芳烃烷基化制备长链烷基苯和长链烷基甲苯的工艺。得出连续式离子液体催化烷基化的最佳反应条件:原料水含量为30μg/g、反应温度为80℃、苯与烯烃摩尔比为12∶1(甲苯与烯烃摩尔比为6∶1)、离子液体与烯烃质量比为0.004;在此条件下,烯烃转化率均大于99.9%,单烷基苯和单烷基甲苯选择性分别大于85%和90%。连续式烷基化的最佳催化剂用量仅为间歇式烷基化催化剂用量的一半。