Research on Catalytic Cracking Performance Improvement of Waste FCC Catalyst by Magnesium Modification

In this study,the deactivation mechanism caused by high accessibility of strong acid sites for the waste FCC catalyst was proposed and verified for the first time.Based on the proposed deactivation mechanism,magnesium modification through magnesium chloride impregnation was employed for the regeneration of waste FCC catalyst.The regenerated waste FCC catalyst was characterized,with its heavy oil catalytic cracking performance tested.The characterization results indicated that,in comparison with the unmodified waste FCC catalyst,the acid sites strength of the regenerated waste FCC catalyst was weakened,with no prominent alterations of the total acid sites quantity and textural properties.The heavy oil catalytic cracking results suggested that the catalytic cracking performance of the regenerated waste FCC catalyst was greatly improved due to the suitable surface acidity of the sample.In contrast with the unmodified waste FCC catalyst,the gasoline yield over the regenerated waste FCC catalyst significantly increased by 3.04 percentage points,meanwhile the yield of dry gas,LPG,coke and bottoms obviously decreased by 0.36,0.81,1.28 and 0.87 percentage points,respectively,making the regenerated waste FCC catalyst serve as a partial substitute for the fresh FCC catalyst.Finally,the acid property change mechanism was discussed.

Distribution and State of Ni Contaminants on Resid Fluid Catalytic Cracking Catalysts—Characterization by AEM, EPMA, UV-Vis and TPR

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MAGNETIC SEPARATION OF FLUID CATALYTIC CRACKING EQUILIBRIUM CATALYST

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Catalytic Cracking of Polyolefins in the Molten Phase——Basic Study for the Process Development of Waste Plastics Liquefaction

The cracking of polyolefins, especially polyethylene in the molten state was effectively catalyzed by the powdery spent FCC （Fluid Catalytic Cracking） catalyst which was dispersed in it. The activation energy of the catalytic cracking of polyethylene was about 74 kJ/mol. The cracked product was naphtha and middle distillate as the major product and gaseous hydrocarbon （C1-C4） as the minor product while little heavy oil was produced. The chemical compositions of the product were： aromatic hydrocarbons, isoparaffins and branched olefins, whereas that of the non-catalyzed products were： n-olefins and n-paraffins with minor amount of dienes with increasing the process time. Additionally, the product pattern shifted from naphtha rich product to kerosene and gas-oil rich product. However, any catalytic product showed low fluid point （〈 -10 ℃）, while that of the non-catalyzed product was as high as 40 ℃. Catalyst could process, more than 100 times by weight of polyethylene with fairly small amount （- 30 wt%） of coke deposition. Spent catalyst gave higher hydrocarbons while fresh catalyst gave gaseous product as the major product. Other polyolefins such as polypropylene and polystyrene were tested on same catalyst to show that their reactivity is higher than that of polyethylene and gave the aliphatic products, alkyl benzenes and C6-C9 iso-paraffins as the major product. Product pattern of the cracked product suggested that the reaction proceeded via the primary reactions making paraffins and olefins which were followed by the isomerization, secondary cracking, aromatization and hydrogen transfer which based on the carbenium ion mechanism.

Effects of the properties of FCCS on the removing of catalyst particles from FCCS under a DC electrostatic field

Catalytic cracking is the main method to lighten heavy crude oil,this process can produce high quality oil products such as gasoline and diesel,but also produces a large amount of fluid catalytic cracking slurry(FCCS).The catalyst particles in FCCS seriously restrict the secondary processing of FCCS and need to be removed,and the properties of Fccs is an important factor that affects the removal efficiency of the catalyst particles.Based on the"effective contact point"model proposed by the research group,this study further proposed the"electrostatic separation efficiency calculation"model.In this model,since Fccs has a uniform distribution of catalyst particles,the ratio of the number of catalyst particles can be expressed as the ratio of area to achieve the calculation of separation efficiency.Then the catalyst removal efficiency under different viscosity was analyzed,thus verifying the feasibility of this model.The effects of temperature and mass ratio of four components on the viscosity of FccS were investigated respectively,then the effects of temperature and four components'mass ratio on the electrostatic sep-aration can be directly converted into the effect of viscosity on the electrostatic separation efficiency.All the results show the electrostatic separation efficiency decreases with increasing viscosity,and the best separationtemperatureis120℃.

Effects of Temperature and Catalyst to Oil Weight Ratio on the Catalytic Conversion of Heavy Oil to Propylene Using ZSM-5 and USY Catalysts

It is useful for practical operation to study the rules of production of propylene by the catalytic conversion of heavy oil in FCC （fluid catalytic cracking）. The effects of temperature and C/O ratio （catalyst to oil weight ratio） on the distribution of the product and the yield of propylene were investigated on a micro reactor unit with two model catalysts, namely ZSM-5/Al2O3 and USY/Al2O3, and Fushun vacuum gas oil （VGO） was used as the feedstock. The conversion of heavy oil over ZSM-5 catalyst can be comparable to that of USY catalyst at high temperature and high C/O ratio. The rate of conversion of heavy oil using the ZSM-5 equilibrium catalyst is lower compared with the USY equilibrium catalyst under the general FCC conditions and this can be attributed to the poor steam ability of the ZSM-5 equilibrium catalyst. The difference in pore topologies of USY and ZSM-5 is the reason why the principal products for the above two catalysts is different, namely gasoline and liquid petroleum gas （LPG）, repspectively. So the LPG selectivity, especially the propylene selectivity, may decline if USY is added into the FCC catalyst for maximizing the production of propylene. Increasing the C/O ratio is the most economical method for the increase of LPG yield than the increase of the temperature of the two model catalysts, because the loss of light oil is less in the former case. There is an inverse correlation between HTC （hydrogen transfer coefficient） and the yield of propylene, and restricting the hydrogen transfer reaction is the more important measure in increasing the yield of propylene of the ZSM-5 catalyst. The ethylene yield of ZSM-5/A1203 is higher, but the gaseous side products with low value are not enhanced when ZSM-5 catalyst is used. Moreover, for LPG and the end products, dry gas and coke, their ranges of reaction conditions to which their yields are dependent are different, and that of end products is more severe than that of LPG. So it is clear that maximizing LPG and propylene and restricting dry gas and coke can be both achieved via increasing the severity of reaction conditions among the range of reaction conditions which LPG yield is sensitive to.

Synthesis, Characterization and Evaluation of Sulfur Transfer Catalysts for FCC Flue Gas

In this work, Zr-M(M=Cu, Mn, Ce) type sulfur transfer agent was prepared by impregnation method. Under the condition similar to that in the regenerator of FCC units, the influence of different active metal components and their contents on sulfur transfer agent were investigated. Moreover, the crystalline structure of sulfur transfer agent was characterized by X-ray diffraction(XRD) and Fourier transforms infrared spectroscopy(FT-IR). The result showed that the Zr-Mn sulfur transfer agent could effectively reduce the SO2 content in FCC regenerator flue gas, featuring high SO2 adsorption capacity. The sulfur transfer agent was inactivated in 40—60 min during the test. In the course of reduction reaction, after several reaction cycles, the formation of SO2 ceased and only H2 S was detected as the reduction product.

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%.

Commercial Application of FCC Catalyst RSC-2006

SINOPEC Research Institute of Petroleum Processing has developed a FCC catalyst to crack heavy oil feedstock to improve high-value products yield, and its commercial application has been conducted successfully in RFCCU at SINOPEC Jingmen Branch Company. This catalyst has revealed its excellent bottoms crackability and coke selectivity. Commercial application tests showed that the slurry yield decreased by 2.84%, and the coke make dropped by 0.64%, with the total yield of LPG, gasoline and diesel increased by 3.99%.

FCC废催化剂磁分离技术的工业应用

利用电磁分离设备和永磁分离设备,对4种典型的FCC废催化剂进行分离,考察废催化剂中金属含量对磁分离效果的影响,同时对比分析两种类型磁分离设备的使用效果。结果表明,磁分离对满足特定条件的FCC废催化剂中低金属颗粒的回收有明显效果。在工业应用中,应有选择性地采用磁分离设备对FCC废催化剂进行回收。

CFD SIMULATION OF FLUID CATALYTIC CRACKING IN DOWNER REACTORS

A mathematical model has been developed for the simulation of gas-particle flow and fluid catalytic cracking in downer reactors. The model takes into account both cracking reaction and flow behavior through a four-lump reaction kinetics coupled with two-phase turbulent flow. The prediction results show that the relatively large change of gas velocity affects directly the axial distribution of solids velocity and void fraction, which significantly interact with the chemical reaction. Furthermore, model simulations are carried out to determine the effects of such parameters on product yields, as bed diameter, reaction temperature and the ratio of catalyst to oil, which are helpful for optimizing the yields of desired products. The model equations are coded and solved on CFX4.4.

生产低硫汽油新型FCC催化剂研究进展

介绍了国内外低硫汽油生产技术 ,重点讨论了催化裂化过程硫转化机理及国内外脱硫FCC催化剂的研究开发现状。结果表明 :在B酸或L酸的作用下 ,通过氢转移使FCC汽油中的噻吩硫及其衍生物分解生成H2 S气体 ,以达到降低FCC汽油硫含量的目的 ,这在反应机理上是可行的 ,因此 ,开发新型FCC催化剂 ,对于实现催化裂化过程直接脱硫 ,生产低硫汽油具有实际意义。

贵州高岭土的组成和性质与其FCC催化剂性能的研究

采用化学分析法、XRD、IR、N2静态吸附法、SEM等手段对两种贵州高岭土试样馏分的元素组成、矿物组成、粒度分布、形貌、孔特征等进行了测试和表征，并研究了其所制高岭土型FCC催化剂的性能。结果表明，两种贵州高岭土试样馏分的表观性质相近，1#高岭土的活性硅含量和活性铝含量较2#高岭土多，在原位晶化的碱性体系中，两种高岭土都表现出较快活性硅和适中活性铝的碱溶速率，而且1#高岭土比2#高岭土碱溶速率更快，使得1#高岭土合成的催化复合材料具有更高的硅铝比和结晶度。以1#高岭土合成的催化复合材料经过改性处理后制成的高岭土型FCC催化剂的物化性质和裂化性能与商用土所制催化剂相当，优于以2#高岭土制备的FCC催化剂。

Cu-Ni@S-1催化剂的制备及其脱硝性能

采用溶解-再晶化法将金属Cu和Ni封装到不同粒径的中空Silicalite-1(S-1)分子筛空腔内部,制备了不同金属掺杂量的中空封装型催化剂。采用X射线粉末衍射(XRD)、扫描电子显微镜(SEM)、X射线光电子能谱分析(XPS)等手段对催化剂样品进行了表征,并采用固定床反应器模拟实际工况考察催化剂对催化裂化再生烟气(n(CO)/n(NO)=13/3)中氮氧化物(NO x)的脱除性能。结果表明:在催化剂用量0.15 g、压力0.1 MPa、温度680℃、混合气体积空速60000 mL/(g·h)的条件下,3%Cu@S-1-380的脱硝效率仅为63%,而2%Cu-0.5%Ni@S-1-380的脱硝效率为100%;Ni和Cu之间形成Cu_(x) Ni_(y) O共熔体,促进了Cu^(+)与Cu^(2+)之间快速循环,提高了氧化还原反应速率;催化剂的中空空腔结构有效防止了金属的流失和烧结,极大地提高了反应物的扩散性能和催化剂的催化活性。相同反应条件下,随着分子筛粒径的减小、金属含量的增加,催化剂的脱硝率提高,双金属共同封装对催化活性的提高非常显著。

FRS全馏分FCC汽油加氢脱硫技术开发及工业应用

抚顺石油化工研究院(FRIPP)开发的FRS全馏分FCC汽油加氢脱硫技术具有大幅度降低催化汽油硫含量和烯烃含量而辛烷值损失较低的特点。在中国石油化工股份有限公司九江分公司0.4Mt/a装置上的工业应用结果表明,FRS技术能够为我国炼油厂生产清洁汽油提供灵活、经济的技术解决方案。

催化剂上沉积钒氧化数对降低FCC汽油中硫含量的影响

过滤金属化合物与硫化物相互作用的分子模拟研究结果表明,低氧化数钒的氧化物有利于促进硫化物的转化。然而,工业运转中催化剂在进入反应器前已经历氧化再生,沉积于其上的钒处于高氧化数状态,为此提出了强化降低催化剂上沉积钒氧化数的"择效活化"方法。电子顺磁共振(ESR)结果表明,通过择效活化处理,催化剂上沉积钒的氧化数下降。重油微反评价结果表明,高钒活化剂进一步表现出明显优于高钒再生剂的降硫作用;高钒人工污染再生剂具有强于未污染剂的降硫作用,并且经择效活化后,高钒污染活化剂进一步表现出明显优于高钒污染再生剂的降硫作用,评价实验证实了分子模拟计算的结果。

含碱金属离子的分子筛的添加对FCC催化剂催化性能的影响

通过添加含碱金属离子的分子筛 ,提高了流化床催化裂化 (FCC)催化剂的氢转移反应活性和重油转化能力 ,同时保持了较低的焦炭选择性 .着重考察了碱金属离子和分子筛的类型以及分子筛的硅铝比和晶粒度对催化剂性能的影响规律 .结合分子筛及催化剂的酸碱性质及氢吸附与脱附性能的测试结果 。

酸改性高岭土基质FCC催化剂的反应性能

利用N2吸附法、IR酸性表征、微型和小型反应器等手段研究了改性高岭土基质催化剂的性能特点。结果表明,高岭土经过热和化学改性后形成了一定活性的中孔结构,添加这种新材料制成的FCC催化剂具有较强的抗重金属污染和重质油转化能力。

CGO关键组分结构分析及其对FCC反应性能的影响

以大港焦化蜡油(CGO)400～425℃窄馏分为研究对象,采用盐酸+糠醛分级抽提的方法富集其中的碱性氮化物及稠环芳烃,采用GC-MS对抽出物进行结构分析,并比较了抽提前后油样的FCC反应性能。结果表明,盐酸抽出相中的碱性氮化物主要是氮杂菲系和氮杂芘系,其中以苯并喹啉系及二苯并喹啉系含量最多;这类化合物与催化剂活性中心结合,使催化剂活性下降。糠醛再抽提抽出相中的稠环芳烃包括荧蒽、苯基萘、菲蒽系、芘系及苯并芘系,其中3～4环的稠环芳烃所占比例最大;这类化合物在催化剂表面缩合生焦,降低了CGO的FCC反应性能。盐酸及糠醛抽余油的FCC反应性能均得到了改善,但糠醛抽余油的改善程度不及盐酸抽余油;碱性氮化物对CGO的FCC反应性能的影响比稠环芳烃大。

原位晶化FCC催化剂传质性能的频率响应法辨析

以苯为探针分子,采用频率响应(FR)技术和智能重量分析仪(IGA)研究了原位晶化流化催化裂化(FCC)催化剂上的传质行为。结合N_2吸附和扫描电镜(SEM)剖析所得织构性质数据,并与传统半合成FCC催化剂以及稀土改性Y分子筛传质性能进行对比,结果表明原位晶化FCC催化剂所具有的独特纳米化和高度分散的分子筛组分分布状态,显著改善了基质大孔/介孔结构与分子筛微孔孔道的贯通性,削弱了分子筛孔道与基质界面间的传质阻力,从而优化了成型催化剂颗粒的传质性能。本研究再次证实了频率响应技术可以检测和辨析多孔催化材料体系中发生的复杂吸附-扩散过程,是一种有效的多级孔催化材料传质性能的研究手段。