催化裂化汽油加氢脱硫技术研究概述

世界上的车用汽油质量标准正朝着超低硫、低烯烃、低芳烃的清洁化方向发展。本文概述了催化裂化汽油加氢脱硫的反应原理和国内外典型的加氢脱硫工艺,并对比了各工艺之间的特点,以期为后续的相关研究提供有价值的参考信息,并希望后续的研究能在汽油深度脱硫工艺流程与操作条件优化、新型催化剂开发与性能改进以及组合工艺的设计与开发等方面做出努力。     

一种高硫、高烯烃催化汽油的选择性加氢脱硫方法

一种高硫、高烯烃催化裂化汽油清洁化生产的方法,它是将全馏分催化裂化汽油进入选择性加氢,采用汽油加氢预处理催化剂进行加氢,通过加氢脱出小分子硫醇、硫醚、二硫化合物等活性硫化物,选择性加氢工艺条件为:氢分压     

催化裂化汽油脱硫精制技术研究进展

催化裂化汽油是我国车用汽油的主要调和来源,但是硫含量远高于车用汽油质量标准的要求值;因此如何高效降低硫含量是催化裂化汽油精制处理的关键。本文综述了国内外催化裂化汽油脱硫精制生产技术。从选择性加氢脱硫技术（Prime-G⁺技术、SCANfining技术、CD Tech技术、RSDS技术、OCT-M技术和DSO技术）,选择性加氢脱硫耦合辛烷值恢复技术（RIDOS技术和GARDES技术）以及吸附脱硫技术（S-Zorb技术）三方面来阐述国内外催化裂化汽油清洁化技术的原理、特点及其应用。指出深度脱硫和辛烷值保持、烯烃饱和率之间的矛盾,后续研究者仍需在工艺流程改进、工艺条件优化以及新型催化剂开发等方面做出巨大努力。     

汽油选择性加氢催化剂获专利奖

由中国石化抚顺石油化工研究院发明创造的“汽油选择性加氢催化剂及工艺”，日前在第十届中国专利奖评选中获得中国专利优秀奖。该发明是一种用于催化裂化汽油等劣质原料生产高质量清洁汽油的催化剂及工艺方法。采用该催化剂及配套工艺，可以实现劣质的催化裂化等汽油原料的深度加氢脱硫和适宜的烯烃加氢饱和，在产品中保留适宜和适量的烯烃，进而实现在脱硫和脱烯烃的同时，使产品的辛烷值损失达到最少，获得硫含量、     

高硫FCC汽油加氢脱硫降烯烃DSRA技术开发

在分析催化裂化汽油硫和烯烃分布不均匀的基础上,对催化裂化汽油进行轻、重组分分馏,开发了活性高和稳定性好的重馏分辛烷值恢复催化剂及FCC汽油加氢脱硫降烯烃DSRA技术。采用DSRA技术对高硫格尔木催化裂化汽油进行轻馏分脱硫醇、重馏分加氢脱硫和辛烷值恢复等改质处理,总脱硫率为94.1%,烯烃降至20%,辛烷值不损失,汽油收率97.83%,化学氢耗0.88%,可生产符合欧Ⅲ规范的清洁汽油。     

FCC汽油加氢脱硫/降烯烃工艺技术的研究

在分析催化裂化汽油硫和烯烃分布不均匀的基础上,对催化裂化汽油进行分馏,开发出了活性高和稳定性好的重馏分辛烷值改进催化剂和选择性加氢脱硫催化剂及其工艺技术。采用该工艺技术对RFCC汽油进行轻馏分碱洗抽提脱硫醇,重馏分辛烷值改进/选择性加氢脱硫等改质处理,再按分馏比例回调,产品汽油烯烃含量为24.2v%,较原料油降低了16.0v%,芳烃含量为19.2v%,较原料油提高了4.1v%,硫含量为41.5ppm,总脱硫率为85.46%,RON为87.8,较原料油提高0.4个单位,液收99.1%,可生产符合国Ⅳ规范的清洁汽油。     

催化裂化生产清洁燃料

介绍了当前轻质油品脱硫的一些方法,包括传统的加氧脱硫和吸附脱硫等工艺过程。21 世纪的炼油企业将围绕炼油厂清洁化生产和生产更加清洁的燃料方向发展,重点发展各种汽油加氢技术并开发非加氢技术、发展轻烯烃改质以及催化汽油降烯烃技术。     

催化裂化汽油加氢及反应吸附脱硫进展

介绍了具有代表性的选择性和结合辛烷值恢复的催化裂化（FCC）汽油精制脱硫加氢工艺。而加氢工艺中的结合辛烷值恢复的加氢工艺更适合我国国情,并提出以辛烷值恢复技术中的异构化和芳构化为主线．研制脱硫能力强和辛烷值保持能力高的脱硫催化剂．适度增强催化剂的酸位疏通孔道,提高其芳构化活性及稳定性。针对反应吸附脱硫工艺,通过寻找硫容量高、吸附性能强的新材料、深度研究脱硫反应机理、简化工艺流程来开展脱硫效果更好、汽油辛烷值维持高的反应吸附脱硫工艺。     

TS-1催化剂选择性加氢脱硫性能的研究

通过负载Co -Mo活性组分及乙二胺四乙酸(EDTA)对TS-1催化剂进行改性,以全馏分FCC汽油为探针原料,考察其选择性加氢脱硫性能并考察了反应条件的影响.采用XRD、XRF、FT-IR、BET及UV -Vis对催化剂进行了表征.反应结果表明,TS-1具有良好的选择性加氢脱硫性能,其脱硫活性对温度和空速敏感,烯烃加氢活性对温度和空速的变化不敏感;负载Co -Mo后的TS-1在高温下表现出很好的保烯烃性能和较好的脱硫能力;再加入第3组分EDTA改性后的TS-1催化剂脱硫活性和烯烃加氢活性均大幅提高并对反应温度敏感,低温下具有高脱硫活性和高加氢选择性.     

催化裂化汽油加氢改质催化剂的改进

针对催化裂化汽油加氢脱硫降烯烃组合工艺技术中，芳构化降烯烃改质催化剂M应用于重馏分汽油加氢时，存在因反应温度高而影响催化剂长周期运行及液体总收率等问题，对催化剂进行优化升级改进研究。结果表明，在M催化剂基础上，通过对HZSM-5分子筛原料改进及调变活性金属组分，研制出活性高和稳定性好的催化裂化重汽油芳构化降烯烃改质催化剂M-Ⅱ，与M催化剂相比，烯烃降低幅度相当时，芳烃增加1.5个百分点，研究法辛烷值提高0.8个单位。     

清洁油品升级背景下加氢脱硫技术研究进展

为满足“史上最严”的国Ⅵ汽油质量标准,发展“低硫、控烯、保辛烷值”的清洁汽油生产新技术成为当前研究热点。当前清洁汽油生产的主流技术是选择性催化加氢脱硫技术,本文首先从催化裂化（FCC）汽油中汽油辛烷值损失与汽油中不同碳数和结构烯烃加氢饱和规律的研究开始,详细分析了当前国Ⅵ升级背景下的加氢脱硫技术发展现状,特别针对提高加氢脱硫催化剂脱硫选择性及辛烷值恢复性能的研究进展进行了综述。基于现有的炼油发展现状及难题,建议了未来清洁油品的发展方向：秉承“分子炼油”理念,进一步完善分子层次的汽油组成认知,不断实现汽油组成中各类烃的精准分离和高效转化,可满足清洁油品的升级需求,还可应对未来油品结构调整。     

A process for producing ultraclean gasoline by coupling efficient hydrodesulfurization and directional olefin conversion

To solve the contradiction between ultradeep hydrodesulfurization (HDS) and octane recovery in clean gasoline production, this article proposes a novel two‐stage fluid catalytic cracking (FCC) gasoline hydro‐upgrading process with the selective HDS catalyst in the first reactor and the complemental HDS and octane recovery catalyst in the second reactor. The process achieved the relayed removal of sulfur‐containing compounds with different natures, providing itself with excellent HDS performance, and the hydroisomerization and aromatization of olefins in the second stage endowed the process with superior octane recovery ability and high product yield while remarkably reducing the olefin content of FCC gasoline. The process was also featured by low hydrogen consumption due to the low first‐stage olefin saturation and the balanced second‐stage hydrogenation and dehydrogenation. The two‐stage process developed here sheds a light for efficiently producing ultralow sulfur gasoline from the poor‐quality FCC gasoline of high olefin and sulfur contents. © 2012 American Institute of Chemical Engineers AIChE J, 59: 571–581, 2013     

汽油精制过程中二次硫化物的生成研究进展

在汽油加氢过程中,原料中存在的烯烃和加氢脱硫生成的硫化氢会发生反应生成硫醇和其他硫化物等二次硫化物,使加氢脱硫后油品中硫醇硫及总硫含量升高,这对生产清洁汽油是一个严重的障碍。综述了汽油加氢精制过程中生成二次硫化物的国内外研究进展,并对研究该反应的重要性及未来趋势进行了展望。     

Reactivity of olefins in the hydrodesulfurization of FCC gasoline over CoMo sulfide catalyst

To achieve selective hydrodesulfurization (HDS) of fluid catalytic-cracked (FCC) gasoline for producing sulfur-free gasoline (S < 10 ppm), the reactivity of various olefins contained in FCC gasoline on CoMoP/Al₂O₃ sulfide catalysts was investigated. Isomerization of the CC double bond from the terminal position to an internal position was observed. The steric hindrance around the CC double bond suppresses the reactivity of olefin hydrogenation. The sulfidation temperature of the catalyst has a major influence on olefin hydrogenation active sites. Addition of the appropriate amount of cobalt (Co/Mo ratio approximately 0.6) contributes to the suppression of olefin hydrogenation at high reaction temperature (260 °C). From the comparison of catalytic performance and characterization of our CoMoP/Al₂O₃ catalyst with an analogous commercial catalyst, it is suggested that the hydrogenation of olefins depends not only on the state of the Mo CUS but also on the steric effects of both olefin structure and MoS₂ crystalline structure.     

催化裂化汽油加氢脱硫技术的研究

在分析催化裂化汽油硫和烯烃分布不均匀的基础上,对全馏分催化裂化汽油选择性预加氢后再分馏,开发出活性高和稳定性好的催化裂化汽油加氢脱硫催化剂及工艺技术。结果表明,产品汽油硫含量由196.2×10^-6降至39.2×10^-6,加氢脱硫率80.1%,硫醇由33.8×10^-6降至5.95×10^-6,烯烃体积分数较原料油降低了2.1个百分点, 研究法辛烷值损失0.5个单位,收率99.24%,可生产满足国Ⅳ清洁标准的汽油调和组分。     

High efficient separation of olefin from fluid catalytic cracking naphtha: Separation mechanism and universal simulation method

The fluid catalytic cracking (FCC) naphtha critical component-oriented separation process is an efficient method to produce ultra-low-sulfur (<10 μg/g) gasoline with minimal loss of octane number (<1 RON). However, the product quality is highly dependent on the structure of the components of FCC naphtha. Aromatics and thiophene sulfides without a methyl side chain favor the separation of olefin. The major impulse of olefin separation is the solvent-induced dipole of aromatics or thiophene sulfides, leading to a “Plane-to-Plane” combination between the solvent and aromatics or thiophene sulfides, accompanied by a steric hindrance due to their side chains. This condition resulted in 2–3 times greater θ of benzene and thiophene compared with that of toluene and 3-methylthiophene. In addition, an improved non-random two-liquid model was proposed based on the above results, and a simulation method for FCC naphtha solvent extraction process was established. The calculation results accorded well with industry data.     

The Crystal Size Effect of Nano-Sized ZSM-5 in the Catalytic Performance of Petrochemical Processes: A Review

The ZSM-5 catalyst has received significant attention in recent years due to its significant properties such as strong acidity and high surface area. Crystal size of the catalyst has been recognized as an important factor in its performance. This review investigates the effects of the crystal size of ZSM-5 on its catalytic performance—selectivity; conversion; lifetime, product distribution; and coke formation during methanol to hydrocarbons (MTH), methanol to dimethyl ether, ethanol to gasoline (ETG), ethylene to gasoline (ETG), acetone to gasoline (ATG), acetone to olefin (ATO), naphtha cracking, and and n-dodecane cracking processes. This study demonstrates that the reduction of crystal size leads to higher levels of activity, conversion, and stability in these various processes.     

FCC汽油脱硫工艺及发展现状

国内、外对车用汽油硫含量的限制日趋严格,采用有效的技术手段降低催化裂化汽油硫含量是关键。针对FCC汽油中含硫化合物的特点,本文综述了国内外开发的一系列FCC汽油加氢脱硫、吸附脱硫以及一些其他脱硫技术特点和发展现状,并对今后脱硫方法的发展方向加以预测。     

催化裂化汽油临氢异构化/芳构化改质过程的反应特性

采用工业Ni-Mo/Al₂O₃-HZSM-5催化剂在小型固定床加氢微反装置上对催化裂化（FCC）汽油临氢改质过程的反应特性进行了研究,通过考察反应温度、压力、空速和氢油体积比对改质后的FCC汽油烃类组成的影响,分析了汽油中不同烃类的转化性能。结果表明,氢油比对产物组成影响不大,高温、低压、低空速有利于增加芳烃的选择性,低温、高压、高空速则有利于增加异构烷烃的选择性;临氢改质后,FCC汽油的烯烃含量明显降低,芳烃和异构烷烃含量增加,因而产品汽油的辛烷值基本保持不变;全馏分、轻馏分和重馏分FCC汽油临氢改质实验结果表明,烯烃含量较高的轻馏分具有更高的转化活性;在FCC汽油临氢改质过程中,同碳数的端烯烃反应活性高于内烯烃,直链烯烃的反应活性高于支链烯烃。