Synthesis of Chloroaluminate Ionic Liquids and Use for Olefin Reduction in FCC Gasoline

Room temperature ionic liquids (RTILs) are mainly referred to melting salt systems composed by organic cations and organic or inorganic anions that exhibit liquid-like behavior at or around room temperature. Chloroaluminate room temperature ionic liquid (chloroaluminate RTILs) is one kind of RTIL synthesized by chloride quaternary ammonium salts and anhydrous AlCl₃. Three kinds of chloroaluminate RTILs were synthesized using trimethylamine hydrochloride (TA), 1-butylpyrinium chloride (BPyC), or 1-methyl-3-alkylimidazolium (BMIC), respectively, with anhydrous AlCl₃ and their application in reducing the content of olefin in FCC gasoline from the Jinzhou Petrochemical Corporation was studied. The effects of chloroaluminate RTIL component and operation conditions on olefin reduction were investigated as well as the repeatability of chloroaluminate RTILs. The results show that at room temperature, when the ratio of anhydrous AlCl₃ to quaternary ammonium (mole/mole), the solvent-oil ratio (g/g), and the reaction time were 2/1, 20/100, and 1/2 h, respectively, the content of olefin in FCC gasoline was deduced more than 30%. The chloroaluminate RTILs could be used at least four times on the basis of keeping their activity.     

Remove Olefin from Diesel Oil with Chloroaluminate(III) Ionic Liquids

Abstract

Ionic liquids are low-melting-point salts that represent an exciting new class of reaction solvents. In this article, the author mainly refers to the effects of the olefin removal in the diesel oil using [bmim]Br-AlCl₃ (where [bmim] is 1-butyl-3-methylimidazolium cation) ionic liquid. The result shows the better performance in the olefin removal. Therefore, an environmental friendly approach for olefin removal from diesel is provided.     

降低汽油烯烃含量用RFG-NJ催化剂的工业试验

在 1.0Mt/a重油催化裂化装置上进行了降低汽油烯烃含量用RFG -NJ催化剂的工业试验 ,并进行了标定。标定结果和日常统计数据分析表明 ,RFG -NJ催化剂具有显著降低汽油烯烃含量的性能。在装置掺渣率为 2 5 %左右、反应温度下降 6℃的情况下 ,汽油烯烃含量由48.6%下降至 3 6.5 % ,下降了 12 .1个百分点 ,汽油的诱导期延长 ,安定性得到改善 ,但汽油辛烷值略有下降 ,装置的总轻烃收率变化不大 ,丙烯收率下降了 0 .13个百分点     

催化裂化汽油脱硫降烯烃助剂的研制

本研究旨在开发一种能同时降低FCC汽油中硫和烯烃含量的助剂,该助剂配方含强度和含量适中的L酸、B酸组分,有较高的噻吩饱和能力和氢转移能力,对FCC催化剂活性和选择性以及汽油性质不会产生明显不利影响。研究中将助剂按一定比例与FCC平衡剂混合装入固体流化床反应器（FFB）进行催化裂化反应,评价了几种金属组分和载体的脱硫和降烯烃性能及对FCC产品分布的影响。不但筛选了合适的金属和载体组分,而且作了必要的改性研究,多个样品小试结果表明,该助剂脱硫和降烯烃均超过30％,产品分布基本没有恶化,汽油辛烷值不下降。     

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.     

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.     

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。     

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。     

降低催化裂化汽油烯烃含量的后加工技术

随着环保意识的加强，对汽油中的烯烃含量限制越来越严格。针对近期研究动态，从芳构化、选择加氢精制及醚化技术方面介绍了降低催化裂化汽油烯烃含量的后加工技术进展。重点介绍已工业应用的3种芳构化技术，即Cyclar工艺、M-2 Forming工艺和Aroforming工艺，用于芳构化工艺的沸石催化剂；2种选择性加氧技术，即SCANfining工艺和ISAL工艺，用于选择性加氢精制催化剂；催化蒸馏合成醚类产物，用于烯烃醚化反应的催化剂。     

Analysis of Factors Affecting Olefin Content in FCC Gasoline

In order to meet the urgent need for reducing olefin content in cracked naphtha,the influence of feedstock characteristics on the olefin content was discussed.The different types and perfomance of catalysts developed by RIPP were introduced,Moreover,some effective operation approaches in commercial units presented to serve as a reference to the refiners for catalyst selection.     

第二代降低FCC汽油烯烃助剂的研制

LAP-1助剂可有效降低FCC汽油烯烃含量,但影响FCC产品分布。新开发的LAP-2助剂在LAP-1的基础上对催化剂的活性组分和载体进行了改进,提高了助剂水热稳定性、氢转移活性和异构化能力,协调芳构化与氢转移反应,提高了降烯烃能力,改善了FCC产品分布。     

工艺条件对降低催化汽油烯烃过程中汽油烯烃分布的影响

着重考察了在使用降烯烃催化剂GOR-Q和常规催化剂MLC-500时工艺条件对催化汽油烯烃分布的影响。结果表明：GOR-Q催化剂具有明显降低催化汽油各类烯烃的效果。从碳数分布看,催化汽油中的烯烃主要集中在C5～C7之间。从类型看,单烯烃是催化汽油烯烃的主要存在形式,其中又以正构烯烃和单支链烯烃为主。降低催化汽油烯烃主要是通过小分子烯烃或单烯烃、正构烯烃、单支链烯烃的降低来实现。低温、低空速、高剂油比有利于降低催化汽油中单烯烃、正构烯烃、单支链烯烃和二烯烃含量,但为了减少辛烷值的损失,在降低催化汽油烯烃时首先应采用提高剂油比的方式。     

清洁汽油的研究与生产技术 Ⅰ．催化裂化汽油降烯烃及加氢脱硫技术进展

综述了国内外催化裂化汽油降烯烃及加氢脱硫技术进展。通过优化操作条件及采用新工艺，对裂化反应、氢转移反应和异构化反应等进行控制与选择，可以明显降低汽油烯烃含量；加氢脱硫技术能够有效降低汽油硫含量，减少辛烷值损失。针对国内汽油质量现状，提出了优化技术方案，降低生产成本的建议。     

清洁汽油的研究与生产技术Ⅰ.催化裂化汽油降烯烃及加氢脱硫技术进展

综述了国内外催化裂化汽油降烯烃及加氢脱硫技术进展.通过优化操作条件及采用新工艺,对裂化反应、氢转移反应和异构化反应等进行控制与选择,可以明显降低汽油烯烃含量;加氢脱硫技术能够有效降低汽油硫含量,减少辛烷值损失.针对国内汽油质量现状,提出了优化技术方案,降低生产成本的建议.     

Study on Olefin Decrement Reformulation and Increasing Light Olefins of FCC Gasoline by Catalytic Cracking

Abstract

Catalytic upgrading of fluid catalytic cracked (FCC) gasoline obtained from Huabei Petrochemical Company, PetroChina (Renqiu, Hebei, China), was investigated using a microreactor and gas chromatograph integrated unit in order to decrease the content of olefins in gasoline and increase the light olefins (ethylene, propylene, and butylene) content. The experimental results showed that the olefin content in upgraded gasoline can be decreased from 42.6% in raw material to nearly 10%, meeting the requirements of the new gasoline standard, whereas iso-alkane and aromatics contents were markedly increased, from 28.4 and 18.2% to 47 and 36.1%, respectively, so the octane number of gasoline should not be reduced. In addition, higher yields of light olefins were obtained after FCC gasoline was reformulated under laboratory conditions. Higher reaction temperature, longer reaction time, higher weight ratio of catalyst to oil, and higher catalyst activity were beneficial to decrease the olefin content of FCC gasoline and increase the yields of light olefins.     

Investigation of ZSM-5/MCM-41 Composite Molecular Sieve for Reducing Olefin Content of FCC Gasoline

ZSM-5/MCM-41 composite molecular sieve was prepared by the nano-assembling method.The ZSM-5 molecular sieve,the MCM-41 molecular sieve,the ZSM-5/MCM-41 mechanical mixture and the ZSM-5/MCM-41 composite molecular sieve were characterized by X-ray powder diffractometry,N2 adsorption isotherms,temperature programmed desorption of ammonia and scanning electron microscopy and their properties were analyzed.Using FCC gasoline as the feed,activities of different molecular sieves for reducing olefin content were investigated in a continuous high-pressure micro-reactor unit under the following conditions:a reaction temperature of 400℃,a reaction time of 2 h,a weight hourly space velocity of 3 h-1,and a reaction pressure of 2.0 MPa.The results showed that the HMCM-41 molecular sieve had low reaction performance,and the HZSM-5 molecular sieve demonstrated high aromatization activity,while the ZSM-5/MCM-41 composite molecular sieve exhibited a best olefin-reducing performance because of its high isomerization activity and moderate aromatization activity.With a largest olefin-reducing capability and a reasonable distribution of products,the composite molecular sieve was more suitable for FCC gasoline upgrading compared to other three catalysts.     

Olefin Reduction of FCC Naphtha Using β-zeolite Catalyst in the Absence of Hydrogen

In order to fulfill the requirement of environmental protection, experimentation of reducing FCC gasoline olefin content and optimization of the process operating conditions were studied in a small fixed vector. Under the action of a macroporous molecular sieve catalyst, which consists of active composition of Ni and Mo metal in β-zeolite supporter, when the reaction temperature was 140°C, reaction pressure was 2.0 MPa, and space velocity was 1.0 h^-1-2.0 h^-1, aromatization reactions, isomerization reactions, and hydrogen transfer reactions happened, so that the olefin, benzene, and arene in product gasoline were no more than 35%, 2.5%, and 40%, respectively. The octane number of petroleum is slightly increased. And it overcomes the disadvantage of losing octane by hydrogenation process. The catalyst could be regenerated using a multi-cycle with an average running cycle of about 96 hr. The results show that the process reaction condition is relaxation, process is non-hydrogenation, process flow is simple, technical and economic target is advanced, benefit is high, and cost is low.     

RFCC汽油降烯烃前后氢平衡计算与分析

通过对中国石油化工股份有限公司北京燕山分公司三催化装置使用GOR－DQ降烯烃催化剂前后氢平衡及氢分布的计算与分析，验证了该装置物料平衡的准确性，并发现使用该催化剂在明显降低汽油烯烃的同时，使氢分布趋于合理。     

汽油加氢脱硫异构降烯烃工艺的工业应用

阐述了220kt／a催化裂化汽油加氢脱硫异构降烯烃装置的运行和标定情况。该装置产品汽油烯烃含量小于20％(V)，抗爆指数下降小于2个单位，硫含量等指标大幅度改善，汽油收率大于89％(m)，表明该技术已经作为汽油清洁化的重要手段之一；同时指出由于该装置是在原有装置基础上改造而成，反应温度控制难度大，换热方案有优化的必要；液化气中C2含量高，适合作乙烯裂解原料。     

Analysis of Measures and Effect on Reducing Olefin Content in Gasoline

This article refers to major measures for reducing olefin content of automotive gasoline and the effect after adoption of these measures. The key for reducing olefin content in China＇s automotive gasoline pool is to reduce the olefin content of FCC naphtha. The domestic refiners apply the olefinreducing catalyst to decrease the olefin content of FCC gasoline as a convenient and cheap means to meet the national standard for automotive gasoline at the present phase. Furthermore, the novel domestic FCC reaction processes, such as the MIP, MGD, FDFCC and other processes can also apparently reduce olefin content in FCC gasoline. In order to further reduce the olefin content in gasoline to meet more stringent standard for automotive gasoline, Chinese refiners should optimize the processing scheme while aggressively disseminating hydrogenation process along with development of catalytic reforming, alkylation, etherification and other processes to completely change the simplistic composition of domestic gasoline pool.