Study on Commercial Application of FCC with Auxiliary Gasoline Reactor for Improving FCC Naphtha Quality

This article introduces the commercial application of FCC technology equipped with a gasoline auxiliary reactor in the RFCC unit at PetroChina Harbin Petrochemical Branch Company. Test results have shown the excellent outcome for commercial application of the gasoline upgrading in the auxiliary reactor to reduce the olefin content in FCC naphtha. Application of this technology can reduce the olefin content in FCC naphtha to less than 35 v%. Adjustment of the FCC operation towards more severe conditions can further reduce the olefin content in FCC naphtha to less than 20 v%, so that the FCC naphtha can meet the current standard or meet more stringent specification requirements in the future to achieve compelling economic and social benefits.     

国内催化裂化装置降低汽油烯烃技术进展

介绍了国内催化裂化装置降低汽油烯烃含量的新丁艺及催化剂,包括辅助反应器改质降烯烃技术、灵活多效催化裂化工艺(FDFCC)、两反应区(MIP)工艺、两段提升管工艺(TSRFCC)、多产柴油液化气并降烯烃(MGD)技术等.对各种工艺的特点以及工业应用情况进行了对比.     

Study on Reaction Mechanism for Cracking FCC Gasoline on Acid Catalyst

This article is based on the experimental data on reaction of FCC naphtha in the presence of acid catalysts. The data published in the literature were reprocessed and compared with experimental data and the relationship of hydrogen and methane contained in the dry gas with the conversion rate was identified. The similarity between the route for cracking of olefin enriched FCC gasoline and the route for reaction of individual hydrocarbons was deduced, while the route for formation of ethylene in dry gas was also proposed to identify the relationship between the reaction path for formation of ethylene and the conversion rate.     

FCC轻汽油C_5和C_6烯烃异构化表观反应动力学的研究

采用管式滴流床反应器,在反应压力1.5 MPa、反应温度313～333 K、液态空速15～30 h-1的范围内,对C5和C6烯烃在LNEH-1镍基催化剂上的异构反应进行了研究。实验结果表明,烯烃只发生双键异构和顺反异构,没有发生骨架异构;1-戊烯、3-甲基-1-丁烯、2-甲基-1-丁烯、1-己烯双键异构反应对烯烃浓度的反应级数均为1,异构反应表观活化能分别为27.60,42.24,79.62,27.71 kJ/mol;随烯烃碳数的增加,异构反应阻力增大,同碳数支链烯烃比直链烯烃更难异构化;由实验数据的拟合得到烯烃异构反应动力学方程,1-戊烯转化率的计算值与实验值的相对偏差基本在10%以内,烯烃异构反应动力学方程可用于反应过程模拟和反应器的设计。     

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 the Operating Conditions on Decreasing FCC Gasoline Olefin Content by GOR-Q Catalyst

Abstract

Based on a fixed-fluid-bed reactor and a GOR-Q catalyst, the influence of process parameters on decreasing gasoline olefin content was studied. The results show that the catalyst had an obvious effect on the decreasing gasoline olefins. A higher catalyst-to-oil ratio, lower weighted hourly space velocity, and lower reactor temperature give rise to lower gasoline olefin content. The reduction of fluid catalytic cracking (FCC) gasoline olefin content is achieved by decreasing olefins of low carbon number. Reaction temperature under 520°C and catalyst-to-oil ratio = 7.0 for a GOR-Q catalyst are advantageous for decreasing olefin content of FCC gasoline.     

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.     

调整工艺参数降低催化裂化汽油的烯烃含量

在2 500 kt/a催化裂化装置上,通过提高催化剂活性、降低反应温度、降低原料预热温度、提高烃分压、提高二反区催化剂藏量、注入终止剂、提高剂油比、延长反应时间、提高汽油终馏点等技术措施,能降低催化裂化汽油烯烃含量8.1%,并分析了工艺参数对FCC汽油烯烃含量的影响原因。     

针对原料油性质优化催化裂化操作

针对中国石化某分公司重油催化裂化装置在使用一种降烯烃重油催化裂化催化剂期间由于原料油改变所引起的重油转化能力下降和汽油烯烃含量上升的现象，从催化剂性能、原料油性质和工艺操作参数等方面分析了引起这类现象的原因，给出了优化生产操作的措施和建议。在原料油性质相当的情况下，优化部分操作参数后油浆产率降低1．75个百分点，总轻液收率提高1．34个百分点，汽油烯烃含量降低7．18个百分点，RON提高0．7个单位，MON提高0．9个单位。     

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     

LBO-16降烯烃催化剂在重油催化裂化装置上的工业应用

在锦西石化分公司1.40 Mt/a重油催化裂化装置进行了LBO-16降烯烃催化剂的工业应用试验。标定结果表明,与原使用的LV-33催化剂相比,LBO-16催化剂具有抗重金属污染能力强、轻质油收率高和降低汽油烯烃含量的特点。     

废聚苯乙烯的热裂解与催化裂解

对废聚苯乙烯(WPS)的热裂解与催化裂解进行了研究,考察了反应温度、反应时间及催化剂用量对裂解率、产油率和各产物选择性的影响。实验结果表明,WPS的裂解产物主要是苯乙烯,副产物为苯、甲苯、乙苯和α-甲基苯乙烯。无论是热裂解还是催化裂解,裂解率和苯乙烯选择性均随反应温度的升高而增大;延长反应时间,裂解率增大,但苯乙烯选择性下降。在反应温度380℃、反应时间60min的条件下,催化剂用量(相对于WPS的质量分数)由2.0%增至8.0%时,裂解率由75.0%降至61.2%,产油率在90.0%以上;副产物α-甲基苯乙烯的选择性与催化剂的用量成正比。WPS裂解制取苯乙烯具有工艺简单、成本低等优点,具有较好的经济效益和社会效益。     

Commercial Test of HGY-2000R FCC Catalyst for Maximizing Gasoline Yield

HGY-2000R catalyst developed by Research Institute of Petroleum Processing, SINOPEC was tested in the RFCC unit, Ulsan complex, SK Corporation, Korea from July to August 2002. The primary results of commercial test show that it has good performance of higher activity, good hydrotherrnal stability,higher residue cracking ability, good coke selectivity and good fluidization properties as well as maximizing gasoline yield with a lower olefin content.     

降低催化裂化汽油烯烃含量和硫含量的DSZ工艺

介绍了降低催化裂化汽油硫含量和烯烃含量的DSZ工艺的小试、中试和工业应用结果.以汽油为原料的小型试验结果表明,该工艺对重馏分汽油的脱硫率比全馏分汽油高,较高的反应温度对脱硫有利,但液体收率有所下降,汽油烯烃含量下降,芳烃含量增加.以镇海直馏减压蜡油为原料进行了中型试验,粗汽油回炼采用注入提升管后的流化床反应器的方式,结果表明,汽油烯烃含量和硫含量均有所下降.在荆门分公司DCC工业装置上进行的工业试验结果表明,干气、汽油产率减少,液化气和柴油产率增加,焦炭略有增加,汽油烯烃含量（荧光法）下降7个百分点,汽油硫分布下降16.0%.     

氢转移反应与催化裂化汽油质量

从分析氢转移反应的机理及本质人手，论述了催化剂孔结构、硅铝比、稀土量、晶粒度、沸石与基质相互作用、沸石组成等对催化裂化氢转移反应活性的影响、指出通过改进催化剂制备技术，选择合适的工艺操作条件及氢转移活性适宜的催化剂可以降低催化裂化汽油烯烃含量，不降低其辛烷值，并抑制焦炭的生成。     

降低催化裂化汽油烯烃含量技术措施探索

为满足国Ⅵ(A)标准车用汽油生产,某公司4.8 Mt/a催化裂化装置（MIP工艺）通过优化工艺条件以降低稳定汽油烯烃含量。结果表明：在第一反应区出口温度提高4 ℃时,稳定汽油烯烃体积分数下降2.4百分点;在平衡剂微反活性提高2.8个单位时,稳定汽油烯烃体积分数降低4.6百分点;在粗汽油回炼量为15 t/h时,稳定汽油烯烃体积分数降低1.3百分点;在稳定汽油终馏点提高4 ℃时,稳定汽油烯烃体积分数降低0.3百分点。降低催化裂化汽油烯烃含量技术措施的方向主要是增强氢转移反应和小分子汽油烯烃选择性裂化反应,都属于二次反应,由此会导致焦炭产率增加。大型炼油企业应综合考虑汽油调合池组分,以综合效益为目标选择合适的催化裂化稳定汽油烯烃含量。     

FCC汽油提升管内降烯烃改质工艺条件的研究

利用催化裂化过程本身降低汽油烯烃含量成为近年来新型催化剂和新型工艺技术开发的主要方向，在连续小型提升管装置上，考察FCC汽油降烯烃效果与反应条件的关系。结果表明，采用普通催化裂化催化剂，当汽油烯烃降低15个百分点以上时，轻质油收率超过91％。低温、高剂油比、长反应时间和较低的再生催化剂炭含量有利于汽油烯烃的降低，汽油中C，以上烯烃降烯烃比较容易，C6烯烃有一部分发生反应，而C5烯烃基本不反应。     

流化催化裂化汽油含硫化合物生成规律的考察

在小型固定流化床装置上采用流化催化裂化(FCC)催化剂、以FCC汽油轻馏分和H2S标准气为原料,考察了催化剂类型、原料组成和反应条件(反应温度、催化剂与原料油的质量比(剂油比)和重时空速)对硫化物生成的影响。实验结果表明,FCC汽油中的烯烃与H2S反应主要生成噻吩类硫化物和部分硫醇;在REUSY分子筛催化剂(催化剂A)上的硫化物收率比在ZRP型择形分子筛催化剂(催化剂B)上的高;且硫化物收率随H2S和烯烃含量的增加呈线性增长。受反应温度对烯烃转化程度的影响,较高的反应温度有利于抑制烯烃与H2S反应。因为反应机理及催化剂性质对噻吩类硫化物和硫醇的生成影响不同,两者收率随剂油比和重时空速的变化趋势不同,但变化幅度均不大,因而总硫化物收率随重时空速和剂油比的变化幅度也不大。     

催化裂化汽油脱硫降烯烃技术的选择

介绍了石油化工科学研究院开发的降低催化裂化汽油硫及烯烃含量的技术，并对如何选择这些技术提出了建议。     

降低催化裂化汽油硫和烯烃含量的技术途径

介绍几种降低催化裂化汽油硫及烯烃含量的技术途径,比较这些技术的使用范围及其优缺点。重点介绍国内已工业化的降低催化裂化汽油硫和烯烃含量的技术,包括加氢异构脱硫降烯烃(RIDOS)技术,多产异构烷烃的催化裂化新工艺(MIP)技术等。指出,前加氢法(催化裂化原料加氢预处理)具有诸多优点,但装置投资高,难以满足清洁汽油φ(烯烃)<20％的要求。催化裂化汽油后加氢法中,对于高硫、低烯烃原料,宜采用选择性加氢脱硫技术;对高硫、高烯烃原料,宜采用加氢异构脱硫降烯烃技术。催化裂化降烯烃新工艺、催化剂和助剂具有投资少,见效快等优点,但难以满足汽油φ(烯烃)<20％,ω(硫)<800μg/g的标准。催化裂化降烯烃技术与加氢技术的组合可能是我国生产新标准清洁汽油的适宜途径。