FCC再生烟气的脱硫助剂研究进展

大气污染是本世纪全球最重要的环境问题之一,硫氧化物是形成酸雨、酸雾的主要物质,如何有效地控制ＳＯｘ的排放是环保工作的重要课题。本文概括地介绍目前催化法脱硫的基石原理,Ｄｅ－ＳＯｘ助剂的性能基本要求以及目前主要的制备方法,重点对ＦＣＣ系统再生烟气中的ＳＯｘ催化脱除方法研究进展进行了综述。     

Zn／Mg-AI催化裂化汽油脱硫助剂的考察

采用溶胶凝胶法制备了Zn／Mg-Al助剂，在固定流化床装置上考察了该助剂的催化效果。经考察，加入该助剂后，脱硫率可达18．3％，烯烃含量降低4．5％，催化裂化的催化活性提高了0．4％，汽油收率有所提高，焦炭产率有所下降。     

流化催化裂化汽油吸附脱硫金属氧化物吸附剂

制备了不同的金属氧化物吸附剂并采用不同方法进行改性,在常压、温度为360℃、液时空速为1 h-1的条件下,采用固定床吸附法考察了吸附剂改性前后的脱硫性能.结果表明:MoO3和MnO2的脱硫效果较好,对硫含量为511.10 μg/g的流化催化裂化(FCC)汽油脱硫,脱硫率达60%以上;CuO-MoO3,MoO3-MgO和MoO3-Fe2O3复合金属氧化物吸附剂对FCC汽油的脱硫效果可达75%以上,其中脱除乙硫醇效果最好的是CuO-MoO3,脱除噻吩效果最好的是MoO3-MgO,脱除二苯并噻吩效果最好的是MoO3-Fe2O3;采用等体积浸渍法对MoO3和MnO2改性后,对FCC汽油吸附脱硫效果有所增强,其中对MoO3改性效果较好的是NiO,脱硫率可达90.1%,对MnO2改性效果较好的是CoO,脱硫率可达93.2%.     

流化催化裂化汽油脱硫固体吸附剂研究新进展

从固体吸附材料方面综述了流化催化裂化(FCC)汽油脱硫吸附剂.根据吸附剂的种类不同,介绍了分子筛吸附剂﹑金属氧化物吸附剂﹑活性炭吸附剂和粘土吸附剂等的吸附机理﹑改性﹑脱硫效果和再生等方面的研究进展.指出吸附剂吸附选择性和吸附容量的提高和吸附机理的深入研究是脱硫固体吸附剂研究的重要方向.     

Zn/Mg-Al催化裂化汽油脱硫助剂的考察

采用溶胶凝胶法制备了Zn/Mg-Al助剂,在固定流化床装置上考察了该助剂的催化效果。经考察,加入该助剂后,脱硫率可达18.3%,烯烃含量降低4.5%,催化裂化的催化活性提高了0.4%,汽油收率有所提高,焦炭产率有所下降。     

新型流化催化裂化汽油脱硫降烯烃催化剂的研究

以L沸石作为活性组分负载Co-Mo氧化物制备了改性L沸石催化剂,并用X射线衍射、BET测试和红外光谱等方法对催化剂进行表征。以全馏分流化催化裂化(FCC)汽油为原料,临氢条件下,在固定床连续微反应装置上对催化剂脱除硫和烯烃的性能进行了评价,考察了n(Co)∶n(Mo)、金属含量、温度、压力、体积空速和氢油比对催化剂反应性能的影响。结果表明,当催化剂中n(Co)∶n(Mo)=1∶2,w(CoO)=2.5%时,在温度320℃、压力1.5 MPa、体积空速4.0 h-1、V(H2)∶V(FCC汽油)=600∶1的条件下,FCC汽油质量脱硫率达92%左右,烯烃体积饱和率42%左右,汽油抗爆指数损失小于1.0个单位,液体质量收率97%~98%,且催化剂的稳定性好。     

流化催化裂化技术研究进展

流化催化裂化（FCC）技术是我国一项先进的科研成果,广泛应用于各领域,尤其是高温、低压力方面,以及催化剂用于残渣进料与裂解重质油料。本文主要介绍了De—SOX技术的发展,对国内外生产丙烯的技术进行了简要概述,对丙烯技术的研发思路进行了论述,还依据固体吸附材料理论综述了流化催化裂化（FCC）汽油脱硫吸附剂。从加氢脱硫和非加氢脱硫两方面综述如何降低硫含量,得到环保产品。     

催化裂化汽油脱硫助剂的研究

汽油中硫化物的存在加重了汽车尾气中污染物的排放,对环境的影响很大。而且会缩短汽油诱导期,对发动机的影响也很大。因此,降低汽油中的硫含量势在必行。本文旨在开发一种用于流化催化裂化过程的添加剂,以降低催化裂化汽油中的硫含量,为生产清洁汽油做出贡献。     

催化裂化烟气脱硫技术的对比探究

石油能源作为社会发展必不可少的化石能源,为人们提供了巨大的便利,但是由于石油能源中含有较多的硫化物,这些硫化物对环境造成了严重的污染,威胁着人们的生命健康。因此,相关部门必须对相关脱硫技术的研究给予足够的重视,减少能源使用对导致硫化物、氮化物等颗粒物的排放。其中使用催化裂化烟气脱硫技术就能对排放物进行净化,但是在使用催化裂化烟气脱硫技术的过程中依然存在一些问题,研究人员需要对催化裂化烟气脱硫技术进行深入研究。     

催化裂化过程中的热裂化与催化裂化

研究了催化裂化过程中热裂化反应和催化裂化反应的特点和影响因素 .结果表明反应温度、剂油比和反应时间能显著地影响热裂化反应和催化裂化反应 .采用适当的催化剂和短反应时间能抑制催化裂化过程中不利的热裂化反应 ,达到调整产品分布和产品组成的目的 .     

INTEGRATING ALBEMARLE RESOLVE DESULFURIZATION TECHNOLOGY WITH NOVEL PETRO-CANADA PROCESS CONCEPTS IN COMMERCIAL FCCU OPERATIONS

The gasoline and distillate sulfur regulations promulgated throughout the world to reduce tail-pipe emissions are now strongly impacting refinery operations and investments. FCC gasoline is recognized as the principal contributor of sulfur to the gasoline pool and has become the focus for meeting the new specifications. The difficulty in removing sterically hindered sulfur species in the fluid catalytic cracking unit (FCCU) cycle oil drives up the hydrogen and investment costs for treating the distillates. Although installation of pre- and post-treatment facilities is planned by many refiners, other non-capital approaches such as undercutting are being evaluated to meet interim and future sulfur levels. Even when expensive treatment facilities are installed, operating costs can be lowered and the flexibility of the facility increased with improvements in the ability to remove sulfur in the FCCU. In this article, we detail Petro-Canada's experience in integrating Albemarle's RESOLVE sulfur reduction technology with a combination of innovative process ideas. These concepts include heavy naphtha recycle, coprocessing of hydrogen donor feeds, and recycle of light cycle oil (LCO) to a specially designed stripper reactor. Special attention is paid to the interaction of deep FCC feed hydrodesulfurization with the FCC performance. The results demonstrate that very low FCC gasoline sulfur levels can be achieved without significant capital investment through novel approaches to recycle, creative integration of cat feed hydrotreating unit (CFHTU)-FCCU designs and operations, and application of state-of-the-art sulfur reduction additive technology. An added benefit of the RESOLVE 950 sulfur reduction technology is the substantial elimination of sulfur oxides in the FCC flue gas. This has been observed in Petro-Canada operations and numerous other RESOLVE 950 applications around the world.     

INTEGRATING ALBEMARLE RESOLVE DESULFURIZATION TECHNOLOGY WITH NOVEL PETRO-CANADA PROCESS CONCEPTS IN COMMERCIAL FCCU OPERATIONS

The gasoline and distillate sulfur regulations promulgated throughout the world to reduce tail-pipe emissions are now strongly impacting refinery operations and investments. FCC gasoline is recognized as the principal contributor of sulfur to the gasoline pool and has become the focus for meeting the new specifications. The difficulty in removing sterically hindered sulfur species in the fluid catalytic cracking unit (FCCU) cycle oil drives up the hydrogen and investment costs for treating the distillates. Although installation of pre- and post-treatment facilities is planned by many refiners, other non-capital approaches such as undercutting are being evaluated to meet interim and future sulfur levels. Even when expensive treatment facilities are installed, operating costs can be lowered and the flexibility of the facility increased with improvements in the ability to remove sulfur in the FCCU. In this article, we detail Petro-Canada's experience in integrating Albemarle's RESOLVE sulfur reduction technology with a combination of innovative process ideas. These concepts include heavy naphtha recycle, coprocessing of hydrogen donor feeds, and recycle of light cycle oil (LCO) to a specially designed stripper reactor. Special attention is paid to the interaction of deep FCC feed hydrodesulfurization with the FCC performance. The results demonstrate that very low FCC gasoline sulfur levels can be achieved without significant capital investment through novel approaches to recycle, creative integration of cat feed hydrotreating unit (CFHTU)-FCCU designs and operations, and application of state-of-the-art sulfur reduction additive technology. An added benefit of the RESOLVE 950 sulfur reduction technology is the substantial elimination of sulfur oxides in the FCC flue gas. This has been observed in Petro-Canada operations and numerous other RESOLVE 950 applications around the world.     

前置烧焦罐式高效再生器催化裂化装置稳定性分析

对前置烧焦罐式高效再生器催化裂化装置反应-再生系统动态机理模型进行空间离散化,然后做线性化处理,得到了线性化状态空间模型．采用控制理论中的线性系统稳定性判据──特征值分析法分析反应-再生系统的稳定性．在控制二密相床和汽提段藏量的条件下,线性状态空间模型的全部特征值的实部在很宽的操作范围内都为负值,证明所研究的反应再生系统（线性化系统）是稳定的．     

生物质焦油裂解催化剂制备及其催化裂解性能

以萘为生物质焦油模型化合物 ,在以白云石为载体制备的 Ni基催化剂上进行了催化裂解实验研究 ,对催化剂的制备技术、活性、积炭失活性能和再生方式进行了实验分析。结果表明 :在 70 0℃的裂解温度、重量空速 0 .8L· h-1的反应条件下 ,萘的单程转化率可达 95 %,以饱和湿空气为再生气流 ,在程序升温的条件下烧碳 ,催化剂再生时间短 (<0 .5 h) ,与同温度的热裂解相比催化裂解更有利于萘的深度裂解 .     

废塑料催化裂解制油技术的研究

利用自制改性ZSM－5型分子筛催化剂，对废塑料催化裂解制备汽油、柴油的工艺过程和影响因素进行了分析研究。结果表明该催化剂具有活性高、使用寿命长、稳定性好及油品产率高等优点，适合市场推广使用。     

CATALYST FRACTURE DUE TO THERMAL SHOCK IN FLUIDIZED CATALYTIC CRACKER UNITS

The formation of fines in a fluidized catalytic cracker unit (FCCU) due to catalyst attrition and fracture is a major source of catalyst loss. In addition to standard attrition tests described in the literature, the possibility that thermal conditions could lead to catalyst fracture and fines production has been explored. Samples of fresh and used (equilibrium or e-cat) type catalysts were heated up to 600°C and mixed with cold samples to determine the impact of thermal shock on particle stability. It was found that significant fracture occurs under these conditions, leading to loss of larger catalyst particles in the bed and significant gain in the amount of fine particles. Agglomeration of particles was also evident, in some cases leading to an increase in the quantity of larger particles appearing to be present in the catalyst sample.     

催化裂解和蒸汽裂解制烯烃工艺技术经济分析

根据近年来乙烯裂解发展趋势,以炼厂液化气和LNG凝析液等轻烃资源为主要原料,通过实例对比分析催化裂解和蒸汽裂解制烯烃的技术以及经济性,并提出石油石化公司应根据区域丙烯和丁二烯市场需求以及企业自身的发展定位,因地制宜地选取合理的烯烃裂解工艺。     

CATALYTIC CRACKING OF GAS OIL: EFFECT OF THE AMOUNT OF ZEOLITE IN COMPOSITE CATALYSTS

In the present paper the performance of a composite isothermal catalytic pellet in the cracking of Gas-Oil is examined theoretically. The composite pellet contains spherical particles of X-Zeolite uniformly dispersed in a Silica-Alumina matrix. It is assumed that the cracking of gas oil for the production of Gasoline can be described by three-lumped components. The composite pellet deactivates due to coke formation and the deactivation is included in the calculations. The application of the composite pellet model to Thermofor Catalytic Crackers provides a fairly good agreement with available industrial data. The pellet radius and the volume fraction of zeolite play major roles in the behaviour of a composite Catalytic Cracking catalyst.     

EFFECT OF CRACKING REACTIONS KINETICS ON THE MODEL PREDICTIONS OF AN INDUSTRIAL FLUID CATALYTIC CRACKING UNIT

Fluid catalytic cracking (FCC) is one of the most complex processes in the petroleum industry. The large degree of uncertainty in the kinetics of the cracking reactions and catalyst deactivation by coke deposition in the riser reactor are among several factors that contribute to the process complexity. The model developed by the authors (Ali and Rohani, 1995) is used lo investigate the effect of the three-lumped kinetic scheme (Weekman and Nace, 1970) and the four-lumped scheme (Lee ct ah, 1989) on the model predictability and reliability. The effect of changes in the catalyst circulation rate, gas oil feed rate, and oxygen feed concentration on various process variables is compared. It is shown that the three-lumped kinetic scheme, despite its extensive use in the literature (McFarlane et ah, 1993; Elnashaie and Elshishini, 1993; Theologos and Markatos, 1993; Arandes and de Lasa, 1992; Lopez-lsunza and Ruiz-Martinez, 1991), leads to erroneous results and should not be used in the dynamic simulation of the FCC units,