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。     

优化催化裂化操作提高重油转化率降低汽油烯烃含量

通过优化催化裂化装置的操作参数可有效提高重油转化率和降低汽油烯烃含量。在工业催化裂化装置上优化结果表明：当系统催化剂的活性由58提到62，油浆产率降低1．14％，干气产率降低0．18％，汽油烯烃含量降低4．5％；当汽油回炼量由原料量的12％增至20％，干气产率降低0-31％，汽油烯烃含量降低6．5％；当剂油接触时间延长0.2s，汽油烯烃含量降低2％；当反应温度降低5℃、再生温度降低20℃时，汽油烯烃含量降低2．2％，干气产率降低0．28％。     

烯烃催化裂解增产丙烯技术进展

随着石化工业的快速发展,乙烯蒸汽裂解装置和炼油厂催化裂化装置的C4及C4以上烯烃副产物大量增加,采用催化裂解工艺将其转化为丙烯和乙烯,且丙烯乙烯质量比较高,不仅提高了副产物的附加值,而且拓展了低碳烯烃的原料来源。本文综述了烯烃催化裂解技术的特点、研究进展和工业应用情况。     

Highly Selective Conversion of Olefin Components in FCC Gasoline to Propylene in Monolithic Catalytic Reactors

1 Introduction Monolithic reactors have found applications in industrial cata- lytic processes[1]. One of such successful examples is its ap- plication as the mobile exhaust cleaning catalysts installed on thousands of vehicles. The reduction of SOx and NOx from a fixed source is another commercial application. Recently, monolithic catalysts and reactors as an interesting technol- ogy applied in multiphase catalytic processes have been at- tracting more attention[2]. Some chemical and refini…     

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.     

增产丙烯的催化裂化工艺进展

介绍了催化裂化( FCC)工艺增产丙烯的主要思路,围绕这些思路综述了增产丙烯的工艺改造进展.包括深度催化裂化(DCC),催化热裂解技术(CPP),重质油接触裂解(HCC),PetroFCC,选择性组分裂化(SCC),Maxofin,高苛刻度FCC(HS-FCC),Superflex等工艺,并将这些工艺流程特点、使用的催化剂、产品分布和烯烃产品收率与常规FCC工艺相比较,结果表明,丙烯收率均有明显提高.并指出通过FCC工艺技术改造增产丙烯是适合当前我国国情的技术路线.     

降低催化裂化汽油烯烃含量技术进展

介绍了降低催化裂化汽油烯烃含量的途径,包括选择合适的催化裂化工艺、应用降烯烃催化剂和助剂、选择中质中间基FCC原料、对原料进行预处理以及对催化裂化汽油进行后处理等。简述了各种催化裂化工艺和降烯烃催化剂及助剂在部分FCC装置的应用效果。指出要实现油品的清洁化,应开发FCC汽油醚化工艺,建造汽油加氢、重整、异构化和烷基化装置。     

FCC汽油选择性加氢脱硫催化剂的研制

通过对传统加氢脱硫催化剂加以改进,研制出一种FCC汽油深度选择性加氢脱硫催化剂CoMoNi／Al2O3-SiO2。催化剂活性评价结果表明,该催化剂具有较高的脱硫活性和较低的烯烃饱和活性,在压力1．5MPa、反应温度230℃、氢油比300：1、空速2．0h-1的条件下,脱硫率达到93．4％,总硫含量由442．3μg／g降低到29．2μg／g,辛烷值损失仅为0．7个单位。1500h稳定性试验结果表明,催化剂具有良好的活性稳定性。     

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。     

增产丙烯和生产清洁汽油组分技术的工业试验

在中国石油化工股份有限公司镇海炼油化工股份有限公司1.8M t/a的重油催化裂化装置上进行了增产丙烯和生产清洁汽油组分(M IP-CGP)技术的工业试验。工业试验结果表明,采用M IP-CGP技术,丙烯质量收率最高可达8.16%;汽油中的烯烃体积分数最低可降至18%以下。与原来采用的催化裂化工艺相比,汽油与原料油的硫含量(质量分数)之比下降50%~65%,辛烷值提高1.0~1.6个单位;总液体(液化气、汽油、柴油)质量收率约增加1%。该技术具有良好的技术经济效益和社会效益。     

Commercial Test on Technology for High-Temperature Cracking of C5 Fraction to Decrease Olefin Content of Gasoline in DCCU

During June and July 2003,Jingmen Petrochemical Company carried out the commercial test on technology for high-temperature cracking of C5 fraction to decrease olefin content of gasoline in DCCU.The test results showed that the olefin content of DCC gasoline had decreased from 68.32m% to 42.5m%。meanwhile the propylene yield increased by 0.90m%.     

催化裂化多产丙烯工艺

综述了国内外催化裂化多产丙烯工艺的特点、产品分布、催化剂及工业应用情况。详细介绍了中国石油化工股份有限公司石油化工科学研究院开发的多产液化气和柴油的工艺、多产低碳烯烃的重油深度催化裂化工艺、重油直接制取乙烯和丙烯的催化热裂解工艺及西安交通大学、中国石化集团洛阳石油化工工程公司等单位联合开发的灵活多效双提升管催化裂化工艺。     

Energy Optimization Design of ARFCC Process for Reducing Gasoline Olefin

Abstract

In view of the high energy consumption inherent in the auxiliary riser fluid catalytic cracking (ARFCC) process, a new energy optimization design has been suggested in this paper to decrease its auxiliary system energy cost and improve its product quality. The heat distribution of an auxiliary fractional system has been optimized and its surplus heat was used to heat crude gasoline, making low-temperature liquid crude gasoline into gas, which was then fed into the auxiliary reactor. The application in an ARFCC unit with 75 t/h of crude gasoline to be reprocessed showed, after the energy optimization design, that when the crude gasoline feed was heated from 40°C to 219°C, the contact temperature difference between the feed and the regenerated catalyst reduced from 650°C to 322°C, process exergy loss decreased by 77.8%, and less dry gas and coke was formed in the auxiliary reactor. At the same time, the energy-use optimization of the auxiliary fractional system increased its exergy recovery efficiency by 25%, 9.73 GJ/hr more valid heat was recovered, and 23.5 t/h more medium pressure steam was produced by the heat of the regenerated catalyst replaced by gaseous crude gasoline. The total energy consumption of the ARFCC process was reduced by a 6.8 kgEO/t feed.     

The Addition of ZSM-5 to a Fluid Catalytic Cracking Catalyst for Increasing Olefins in Fluid Catalytic Cracking Light Gas

Abstract

The second largest source of propylene supplied for petrochemical application is from fluid catalytic cracking (FCC) units. The primary function of the FCC unit has typically been to produce gasoline. However, refiners have been taking advantage of opportunity to produce and recover more propylene from their FCC unit by increasing reaction severity via riser temperature, adding shape selective catalyst, and installing a propylene recovery unit (PRU). At a conventional FCC process propylene exists in the off gas of FCC and it is about 6 wt% of off gas by changing the FCC process parameter quantity of propylene in off gas can be more than 20 wt% by using ZSM-5 additives and increasing temperature The effects of operating parameters, such as reaction temperature, and ZSM-5 as FCC catalyst additive, on the distribution of the product and the yield of propylene were investigated on a bench-scale fluidized bed reactor. It is the aim of this work to perform an overall analysis of the yields and selectivity of hydrocarbons obtained in the vacuum gas-oil conversion over FCC and ZSM-5 catalysts. The effectiveness of ZSM-5 additive in the FCC process was investigated by doing experimental work in a bench-scale setup. The experiment data of off gas analysis showed that vacuum gas oil cracking at high reaction temperatures of 450–550°C increases the yield of propylene. Similar behavior is observed with the addition of 10–25 wt% ZSM-5 additive. The combination of the two effects (high temperature and ZSM-5 addition) makes the FCC unit an excellent source of light olefins for downstream petrochemical units. Higher FCC reactor temperatures (600–650°C) would not have positive effects for increasing propylene yield.     

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.     

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.     

重油催化裂化装置稳定塔底重沸器内漏原因分析及对策

随着进口原油掺炼比例的增加,0．8Mt／a重油催化裂化装置的原料逐渐劣质化,设备开始出现泄漏,其中以稳定塔底重沸器（E-304／1）的泄漏最为严重。通过分析泄漏原因,确定E-304／1内漏由高温硫腐蚀导致,为此决定更换重沸器。重沸器更换前通过调整控制E304／1管程与壳程的差压维持正常生产,更换过程中采取了凝缩油进1．4Mt／a重油催化裂化装置吸收塔的处理方案,解决了干气、液化气组分放空燃烧污染环境的问题。     

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%.     

Comparison of Downer and Riser Based Fluid Catalytic Cracking Process at High Severity Condition: A Pilot Plant Study

Abstract

Integration of refining and petrochemicals offers economic benefits to both the industries. Converting low value refinery products to high value petrochemicals require novel processes and extra investment. Though FCC is not a new process to the refining industry, it still has a potential for modification to enhance light olefins demanded by reformulated gasoline and the petrochemical industry. In this article a novel, High Severity FCC process based on the downer reactor is presented. Supported by the pilot plant study and comparison with riser, it is shown that the downer FCC reduces backmixing, which is the main cause of gasoline overcracking. Reduction of backmixing reduces coke and dry gas formation, resulting in increased yield of gasoline. Despite the operation at higher temperature, there is reduction in the thermal cracking. Though the light olefins yield is lower in case of downer, the total yield of useful products (gasoline + light olefins) is higher in downer as compared to the same from a riser. The increased yield of gasoline from downer can be converted to light olefins by using ZSM-5 based additives.