催化裂化装置防结焦技术研究

结焦是影响催化裂化装置长周期运行的重要原因之一。本文从催化裂化工艺和实际生产出发,根据沉降器的结焦部位、焦块的形态和构成归纳出导致沉降器结焦的三大成因——湿催化剂粘附结焦、重组分油冷凝结焦和缩合反应结焦。文章认为湿催化剂粘附是提升管、旋分器料腿和沉降器内结焦的主要原因;重组分冷凝是旋分器升气管外壁、沉降器内和转油线结焦的主要原因。本文还论述了包括原料性质、原料汽化率、油气停留时间、粗旋与顶旋的连接方式和设备等五大影响沉降器结焦的主要因素,并总结提出避免或减缓沉降器结焦的措施。     

重油催化裂化沉降器结焦的研究进展

分析了重油催化裂化 (RFCC)沉降器结焦的影响因素和机理。反应油气中含有催化剂颗粒以及油气中重组分的冷凝是沉降器结焦的物理因素 ,而重芳烃、胶质、沥青质的高温缩合和油气中烯烃和二烯烃的环化聚合反应则是沉降器结焦的化学因素。通过对液相重组分高温缩合机理、相分离生焦机理和自由基反应机理等沉降器结焦机理的分析 ,认为沉降器中油气的气、液相分别遵循不同的结焦历程 ,抑制沉降器结焦的关键在于抑制反应油气中重组分的冷凝和缩短反应油气的停留时间     

催化裂化沉降器内液滴运动规律的数值模拟研究

催化裂化沉降器结焦将导致非计划停工,严重影响催化裂化装置的长周期运行.首先求取了单位时间沉降器内冷凝的油浆液滴的质量,然后利用颗粒轨道模型对液滴的运动轨迹进行模拟计算,得到液滴的停留时间、运动轨迹和分布区域.模拟计算结果表明,液滴在沉降器内的运动具有很强的随机性,不同大小的油浆液滴的停留时间不同,但大部分的液滴粘附在沉降器内壁和旋风分离器外壁上,进而缩合结焦.加强沉降器的保温可减少油气重组分的冷凝,采用"高温汽提"和"化学汽提"可减少进入沉降器的油气重组分的量,从而减少沉降器结焦.     

ACO装置结焦原因分析及处理措施

针对ACO装置沉降器和油气急冷换热器结焦导致装置运行周期短的问题,对沉降器、油气冷器入口和出口等3处焦块进行了取样分析。根据分析结果对结焦原因进行了分析,得出聚合结焦、缩合结焦及冷凝结焦是最主要的结焦方式,提出沉降器提高汽提蒸汽温度及增加急冷油冷却器的处理措施,实施后,有效地降低了两处结焦对工艺运行的影响,运行周期由不足2个月延长至7个月以上。     

RFCC沉降器内流动及传热过程的数值模拟

针对重油催化裂化(RFCC)沉降器结焦问题,采用计算流体力学方法,建立了一套160万吨/年工业重油催化裂化(RFCC)沉降器油气流动和传热的数学模型。通过模拟研究考察了沉降器内的速度、温度以及油气分压分布,结果表明,油气运动速度低、分压大易导致结焦。通过计算粗旋、顶旋以及汽提段等各部分油气在沉降器内的停留时间分布发现,粗旋料腿处进入沉降器的油气含量高且停留时间很长,对沉降器结焦的影响最大,因此降低粗旋料腿处进入沉降器内的油气量是防结焦的关键。     

沉降器结焦原因及对策

中国石油抚顺石化分公司石油二厂1．5Mt／a重油催化装置自2000年8月开工以来,沉降器内结焦严重,影响了装置的长周期运行。当沉降器内结焦达到一定程度时,如遇切断进料,就会出现焦块脱落,出现催化剂循环不正常或根本不能建立催化剂循环,被迫停工处理。在大量操作数据的基础上,分析结焦部位和结焦结构形态,找出沉降器内结焦的原因,并提出相应的对策。     

催化裂化沉降器的结焦原因和防焦措施

随着炼油厂催化裂化掺渣比的提高，催化裂化沉降器结焦日益严重，并直接影响威胁到催化裂化装置的正常运行。分析了原料性质、催化剂浓度和反应条件等因素对催化裂化沉降器结焦的影响，并通过总结国内外所采取的一些防焦措施，提出了今后的发展趋势和要求。     

FCC沉降器粗旋工作性能的数值模拟

引言 催化裂化工艺(fluidized catalytic cracking, FCC)是目前我国重质油轻质化加工的主要方法之一.重质油裂化反应过程主要在提升管反应器内完成,提升管出口通常设置旋风分离器(简称粗旋)将反应后油气与催化剂快速分离,以避免发生过裂化反应.粗旋工作性能的优劣直接影响装置目的产物的收率、沉降器内部结焦以及油浆固含量.     

催化裂化装置跑剂原因探究及措施

催化装置跑剂是造成装置非计划停工的重要原因之一,某催化装置因沉降器旋风分离器料退断裂而造成大量跑剂而停工,本文从油浆固含、单级旋分线速、再生剂粒径分布、油浆灰分分析等方面分析了沉降器跑剂现象,并深入探讨了催化沉降器旋分跑剂原因、催化沉降器结焦原因。     

CSC快分系统特点与应用及防焦措施探讨

提升管出口CSC(Circulating-Stripping Cyclone)快分系统具有高分离效率、良好的操作弹性及稳定性而在催化裂化装置上得到广泛的应用。其设计的工作原理是在粗旋下部设置一个密相环流式预汽提器,通过改变内外环的汽提蒸汽量来调整内外环的密度差,使催化剂在内外环之间形成密相环流动,以实现降低蒸汽用量、提高汽提效率的目的。工业应用中影响CSC系统性能的因素主要有内外环蒸汽流量、结焦及磨损等。其中,结焦问题是一个大问题,总结认为通过优化原料、选择合适的雾化喷嘴、采用预提升技术、加注反应终止剂、减小汽提蒸汽与油气的温差、停电事故处理时及时将沉降器中的催化剂转出等措施,可以有效防止(或减少)CSC系统结焦问题。     

浅析重油催化裂化装置结焦原因及防止对策

在综合分析了重油催化裂化装置(RFCCU)容易结焦的部位及结焦原因,介绍了防止结焦的技术措施。认为在装置开工前,增强检修清焦质量、延长原料油塔外循环时间;生产中,保持操作平稳、尽量避免切断原料等事件的发生,加强对再生剂温度、预提升段催化剂密度、各喷嘴进料量和雾化蒸汽量、反应温度、沉降器出口温度、分馏塔底温度和塔底液位、油浆循环量、外甩量及油浆中固含量等参数的控制,采用优良的提升管出口技术,添加搅拌油浆等措施都对减少、防止RFCCU结焦有利。     

原料油汽化特性对催化裂化反应结焦过程影响的CFD模拟

为考察原料油汽化特性影响,在一套百万吨级工业FCC提升管中,基于多相欧拉模型耦合EMMS曳力和传质、油滴汽化和十二集总反应动力学模型,采用三维CFD模拟研究气液固三相流动、汽化、反应、结焦的复杂过程,新开发结焦预测模型定量预测结焦状况,对比研究不同原料油雾化液滴粒径和起始汽化温度下各相和反应组分浓度场、温度场分布和结焦程度。结果表明,模拟方法可较准确预测汽化、反应生焦和结焦过程,不同雾化液滴粒径和起始汽化温度通过流场分布和汽化快慢影响液相油滴汽化率和反应转化率;合适液滴粒径(60 μm)和起始汽化温度(654 K)可提升轻油、汽油、液化石油气目标产品收率并改善结焦程度。     

原料油汽化特性对催化裂化反应结焦过程影响的CFD模拟

为考察原料油汽化特性影响,在一套百万吨级工业FCC提升管中,基于多相欧拉模型耦合EMMS曳力和传质、油滴汽化和十二集总反应动力学模型,采用三维CFD模拟研究气液固三相流动、汽化、反应、结焦的复杂过程,新开发结焦预测模型定量预测结焦状况,对比研究不同原料油雾化液滴粒径和起始汽化温度下各相和反应组分浓度场、温度场分布和结焦程度。结果表明,模拟方法可较准确预测汽化、反应生焦和结焦过程,不同雾化液滴粒径和起始汽化温度通过流场分布和汽化快慢影响液相油滴汽化率和反应转化率;合适液滴粒径(60 μm)和起始汽化温度(654 K)可提升轻油、汽油、液化石油气目标产品收率并改善结焦程度。     

Kinetic modeling of FCC process

Catalytic cracking of petroleum fractions a process termed as FCC is usually carried out in a reactor block with somewhat complicated hydrodynamic regime. The reactor block is considered as a combination of two different reactors. The riser is a near ideal plug-flow displacement of the catalyst and reaction mixture, while the main reactor vessel (separator) is considered as an ideal mixing CSTR. Temperature gradient along the plug-flow riser can vary on a linear and non-linear dependence. This is reflected by the thermal effect on the cracking products, along the altitude of the riser. Moreover, it can exert a considerable influence on the selectivity of the process in general, as characterized by the diversity of different hydrocarbon groups both in the gaseous and liquid products. The fluid catalytic cracking (FCC) is a process of conversion of a heavy oil fraction into lighter products in a catalytic fluidized reactor. The chemical composition and the structure of the feed are reflected on the catalyst's selectivity and the amount of coke deposited. It is, therefore, necessary to consider the feed type on modeling the process. Cracking reaction in the model was represented as a five-stage process. Reaction rates for the plug-flow riser and the ideal mixing separator are described mathematically in differential and algebraic forms. The model takes into account, exponential dependence of the specific reaction rate on temperature, as well as reflects the influence of the real and bulk catalyst densities, circulation rate, equilibrium and fresh catalyst's activities, reactor pressure, feed rate and unit construction. The model was developed based on a data taken from an industrial FCC unit, that were used to compute the kinetic constants and other parameters. Concrete computed kinetic parameters were compared with corresponding experimental data for adequacy. FCC process is in constant technological development with modernization of especially the riser reactor. Kinetic modeling of the catalytic FCC reactor will give a further understanding of the process and explain the complicated mechanism involved for an efficient and optimal conversion of the feed stock.     

Processing oil shales with heavy oil recycle

Recycle of heavy oil (>340 °C) to the retort, in order to crack/coke the oil to lighter fractions, was investigated as a means of producing shale oil of more desirable product slates. Conversion of heavy oil to light oil (<340 °C) by thermal cracking and coking in the absence of and during oil shale retorting was studied using the CSIRO BIRCOS retort. As expected, the conversion by thermal cracking increased as temperature increased, with most of the net oil loss in the form of gas. By contrast, the conversion by coking alone decreased as temperature increased, with coke representing all the net oil loss. Thermal cracking was found not to be a first-order reaction, by showing a reduced conversion of heavy oil with reduced concentration of oil vapour. Retorting Stuart oil shale with heavy oil feeding and simultaneous cracking and coking showed a conversion of 19.1 g per 100 g feed heavy oil to 10.9 g light oil, 2.2 g gas and 6.0 g coke, with a net oil loss of 3.8 g per 100 g shale oil produced. These data were used to generate a set of parameters for a mathematical model which simulated a heavy oil recycle loop.     

Demetallization of heavy oil through pyrolysis: A reaction kinetics analysis

By tracking the transfer of vanadium and nickel in pyrolysis products, a seven-lump reaction kinetic model for pyrolysis-based demetallization of heavy oil was established. During pyrolysis, the demetallization of heavy oil is achieved by condensing metal-rich resins and asphaltenes to coke. The condensation of oil components originally contained in heavy oil differs greatly in reaction behavior, having the activation energy between 167 and 361 kJ/mol. As the pyrolysis progresses, the newly formed heavy components show a condensation behavior close to that of the light components. Limited by high activation energy and low initial fraction, the condensation of asphaltenes to coke and the resulting removal of metals contained in asphaltenes are hindered. Meanwhile, the condensation of light components has a major contribution to coke formation. An increase in reaction temperature accelerates the demetallization, but hardly changes the yield and component distribution of liquid products at the same metal removal rate.     

分子筛催化剂积炭失活行为探讨

反应过程中生成的重质副产物积炭堵塞孔道是造成酸性分子筛催化剂失活的主要因素.影响积炭的因素有催化剂的孔道结构、酸性以及操作条件.对分子筛催化剂积炭失活机理、积炭表征技术、影响因素和抑制措施进行了综述,并介绍了一种积炭分离方法,对分子筛催化剂积炭研究的发展趋势进行了分析.     

竞争吸附对催化裂化反应过程的影响

以大港焦化蜡油为原料,利用催化裂化工业平衡剂LBO-16在小型固定流化床实验装置上研究了竞争吸附效应对催化裂化反应的影响,并对特征组分竞争吸附行为进行分析。结果表明,竞争吸附效应对催化裂化转化率影响很大,通过提高剂油比可以基本消除竞争吸附对反应过程的影响。原料中含氮化合物及稠环烃类化合物竞争吸附效应很强,阻滞烃类裂化反应的正常进行,是催化裂化过程快速生焦的重要原因。随着竞争吸附效应的减弱,脱氢缩合反应比例下降,氢转移反应显著加强。     

Coking behavior and catalyst deactivation for catalytic pyrolysis of heavy oil

For the catalytic pyrolysis of heavy oil on catalyst CEP-1, coking behavior was investigated in a confined fluidized bed reactor. Coke content on the spent catalyst decreases with the increase of H/C mol ratio of feeds and catalyst-to-oil weight ratio, while it increases with the enhancement of reaction temperature. An empirical model is proposed to predict the coke content based on feed properties and operating conditions. The predicted coke content is close to the experimental data. The relationship between micro-activity index of catalysts and coke content is studied. A coking deactivation model for pyrolyzing catalysts is established, and then model parameters are determined by the least square regression analysis. According to the deactivation model, the variations of relative activity of catalysts with both residence time of catalysts and catalyst-to-oil weight ratio are predicted.