前置烧焦式催化裂化装置的过程建模、模拟及工艺优化
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摘要
针对前置烧焦式催化裂化装置对原料适应性强、焦炭在没有或少量CO助燃剂作用下完全燃烧和再生剂含碳量低的特点，考虑到提升管、沉降器、一段烧焦罐和二段密相床再生器互相耦连以及一段烧焦罐气固流动复杂性，本文建立其严格稳态机理模型，并开发相应过程模拟程序。
提升管模型的建立基于Gupta等的一维稳态模型，采用实组分与虚拟组分反应动力学，并与物料衡算方程、能量衡算方程与流化状态计算模型相耦合；流化状态计算基于固体颗粒团聚模型；鉴于反应网络中存在大量反应，模型方程建立采用体积单元法。沉降器模型包括自由域模型和汽提段模型；自由域中不存在化学反应，仅考虑出口旋风分离器压降效应；可汽提焦炭量的计算基于多级汽提模型，并与物料衡算方程和能量衡算方程耦合，构成汽提段模型。前置烧焦罐的流化状态计算基于固体颗粒团聚模型，耦合焦炭燃烧动力学模型、物料衡算方程和能量衡算方程，考虑出口快速分离装置压降效应。二段密相床再生器模型包括密相区模型和稀相区模型；密相区流化状态计算采用气固全混流模型，床层空隙率采用经验关联式计算，耦合焦炭燃烧动力学模型、物料衡算方程和能量衡算方程；稀相区采用纯气相平推流反应器模型，并考虑了轴向气相静压损失、气相与器壁摩擦压力损失和出口旋风分离器压降损失。
基于Aspen Custom ModelerTM软件平台，开发了前置烧焦式催化裂化装置的过程模拟程序。为突破该软件难于求解拥有庞大变量总数及复杂常微分方程组数学模型的限制，对提升管模型、烧焦罐模型和二段密相床再生器稀相区模型的求解采用软件平台基础上Fortran语言补充编程的方法。
本文考察了原料油流率和原料油温度等七个关键工艺参数对全装置稳态运行影响，以期为装置现场操作、工程设计及工艺优化提供有益借鉴。本文对提升管注入终止剂技术、再生器催化剂取热器技术和富氧再生技术在装置上应用进行模拟分析。提升管注入终止剂可控制高温条件油气与催化剂接触时间，装置产品分布能够得到调节。再生器增设取热器，调节取热器负荷，可控制提升管原料油进口处气固平衡温度和装置剂油比。富氧再生技术应用强化了再生器烧焦能力，改善了装置平衡剂活性及选择性。三种技术优劣互补、互相配合所形成的新型组合工艺，提高了装置操作灵活性，可达到装置剂油比可控、油气裂化反应温度可控、高温条件油气与催化剂接触时间可控及强化再生器再生效果的目的。
The fluidized catalytic cracking unit (FCCU) with high efficiency combustor wasdeveloped to process various types of feedstocks. Coke on spent catalyst could betotally converted to CO2with few or no CO promoter in regenerator, while the cokecontent of regenerated catalyst was still kept to be a very low level. Considering thecoupling effects of riser reactor, disengagement vessel,1ststage high efficiencycombustor, and2ndstage dense bed regenerator and the complexity of flow pattern in1ststage combustor, this work developed the rigorous fundamental steady state modeland the corresponding process simulation platform for this type of FCCU.
The riser model was based on the one dimensional steady state model proposedby Gupta et al, applying the oil cracking kinetice method of true and pseudocomponents, which was coupled with mass balance equations, energy balanceequations, and gas/solid flow pattern description model. The solid cluster model wasbased on to develop the gas/solid flow pattern model. Considering the huge number ofcracking reactions existing within the oil cracking reaction network, the volumeelement method was used to develop the key model equations. The disengagementvessel model included the free board model and the stripper model. The free boardmodel assumed no chemical reactions occurred there, which could account for thepressure drop effects of multistage cyclones within the equipment. The stripping cokeon spent catalyst was featured by the published multistage stripping model, which wasthen coupled with the mass balance equations and the energy balance equations. Thegas/solid flow pattern within the combustor was calculated via the solid cluster model,which was then coupled with coke combustion kinetics model, mass balanceequations, and energy balance equations, forming the steady state model for thecombustor. And the model could account for the effects of pressure drop of thecyclones located at the outlet of combustor. The2ndstage dense bed regeneratormodel included the dense region model and the free board model. The gas/solidcontinuous stirred tank model was based on to feagure the flow pattern within thedense bed region. The bed voidage was calculated via the published industrialcorrelations. These was then followed by coupling with the coke combustion kineticsmodel, mass balance equations, and energy balance equations. The free board modelassumed no solid particle existing within the reactor, so PFR based reactor model wasused to simulate the free board region. The developed model could account for the different pressure loss including the static pressure lose, pressure loss due to frictionbetween gas phase and wall, and pressure loss within the outlet multistage cyclones.
The process simulation platform for the combustor-style FCCU was developedusing the Aspen Custom ModelerTMsoftware. In order to overcome the shortcomingsof this software which could not handle models with huge number of variables or withcomplex ODEs, this work applied the method of Fortran programming based on thesoftware platform to solve the models of riser reactor, combustor, and the free boardregion of2ndstage dense bed regenerator.
This work observed the effects of seven key process operating variables such asfeed flow rate and feed temperature on the run state of the whole FCCU, hoping togive instructive guidelines for the field operation, engineering design, and processoptimization of this type of FCCU. The technologies of quench injection in riserreactor, catalyst heat remover, and combustion air oxygen enrichment were analysedfor their application potential on the FCCU. Applicatioin of quench injection on theriser could control the residence time of hot oil gas and catalyst within the reactor, sothe products distribution could be tuned up. The addition of catalyst heat removerimproved the operator’s ability to adjust the unit heat balance, so that the gas/solidtemperature at the feed inlet of riser reactor and the ratio of regenerated catalyst flowrate to mixed feed flow rate could be controlled. The technology of oxygenenrichment in combustion air intensified the ability of catalyst regeneration ofcombustor-style regenerator, improved the initial activity and selectivity of unitbalance catalyst. The three technologies could complement with each other, formingthe combined process intensification technology. The simulation results showed thatthe application of this technology elevated the field operation level, considering itsablity to comtrol the ratio of regenerated catalyst flow rate to feed flow rate, theenvironmental temperature of oil cracking reactions, the residence time of hot oil gasand catalyst in riser reactor, and the coke content of regenerated catalyst.
提升管模型的建立基于Gupta等的一维稳态模型，采用实组分与虚拟组分反应动力学，并与物料衡算方程、能量衡算方程与流化状态计算模型相耦合；流化状态计算基于固体颗粒团聚模型；鉴于反应网络中存在大量反应，模型方程建立采用体积单元法。沉降器模型包括自由域模型和汽提段模型；自由域中不存在化学反应，仅考虑出口旋风分离器压降效应；可汽提焦炭量的计算基于多级汽提模型，并与物料衡算方程和能量衡算方程耦合，构成汽提段模型。前置烧焦罐的流化状态计算基于固体颗粒团聚模型，耦合焦炭燃烧动力学模型、物料衡算方程和能量衡算方程，考虑出口快速分离装置压降效应。二段密相床再生器模型包括密相区模型和稀相区模型；密相区流化状态计算采用气固全混流模型，床层空隙率采用经验关联式计算，耦合焦炭燃烧动力学模型、物料衡算方程和能量衡算方程；稀相区采用纯气相平推流反应器模型，并考虑了轴向气相静压损失、气相与器壁摩擦压力损失和出口旋风分离器压降损失。
基于Aspen Custom ModelerTM软件平台，开发了前置烧焦式催化裂化装置的过程模拟程序。为突破该软件难于求解拥有庞大变量总数及复杂常微分方程组数学模型的限制，对提升管模型、烧焦罐模型和二段密相床再生器稀相区模型的求解采用软件平台基础上Fortran语言补充编程的方法。
本文考察了原料油流率和原料油温度等七个关键工艺参数对全装置稳态运行影响，以期为装置现场操作、工程设计及工艺优化提供有益借鉴。本文对提升管注入终止剂技术、再生器催化剂取热器技术和富氧再生技术在装置上应用进行模拟分析。提升管注入终止剂可控制高温条件油气与催化剂接触时间，装置产品分布能够得到调节。再生器增设取热器，调节取热器负荷，可控制提升管原料油进口处气固平衡温度和装置剂油比。富氧再生技术应用强化了再生器烧焦能力，改善了装置平衡剂活性及选择性。三种技术优劣互补、互相配合所形成的新型组合工艺，提高了装置操作灵活性，可达到装置剂油比可控、油气裂化反应温度可控、高温条件油气与催化剂接触时间可控及强化再生器再生效果的目的。
The fluidized catalytic cracking unit (FCCU) with high efficiency combustor wasdeveloped to process various types of feedstocks. Coke on spent catalyst could betotally converted to CO2with few or no CO promoter in regenerator, while the cokecontent of regenerated catalyst was still kept to be a very low level. Considering thecoupling effects of riser reactor, disengagement vessel,1ststage high efficiencycombustor, and2ndstage dense bed regenerator and the complexity of flow pattern in1ststage combustor, this work developed the rigorous fundamental steady state modeland the corresponding process simulation platform for this type of FCCU.
The riser model was based on the one dimensional steady state model proposedby Gupta et al, applying the oil cracking kinetice method of true and pseudocomponents, which was coupled with mass balance equations, energy balanceequations, and gas/solid flow pattern description model. The solid cluster model wasbased on to develop the gas/solid flow pattern model. Considering the huge number ofcracking reactions existing within the oil cracking reaction network, the volumeelement method was used to develop the key model equations. The disengagementvessel model included the free board model and the stripper model. The free boardmodel assumed no chemical reactions occurred there, which could account for thepressure drop effects of multistage cyclones within the equipment. The stripping cokeon spent catalyst was featured by the published multistage stripping model, which wasthen coupled with the mass balance equations and the energy balance equations. Thegas/solid flow pattern within the combustor was calculated via the solid cluster model,which was then coupled with coke combustion kinetics model, mass balanceequations, and energy balance equations, forming the steady state model for thecombustor. And the model could account for the effects of pressure drop of thecyclones located at the outlet of combustor. The2ndstage dense bed regeneratormodel included the dense region model and the free board model. The gas/solidcontinuous stirred tank model was based on to feagure the flow pattern within thedense bed region. The bed voidage was calculated via the published industrialcorrelations. These was then followed by coupling with the coke combustion kineticsmodel, mass balance equations, and energy balance equations. The free board modelassumed no solid particle existing within the reactor, so PFR based reactor model wasused to simulate the free board region. The developed model could account for the different pressure loss including the static pressure lose, pressure loss due to frictionbetween gas phase and wall, and pressure loss within the outlet multistage cyclones.
The process simulation platform for the combustor-style FCCU was developedusing the Aspen Custom ModelerTMsoftware. In order to overcome the shortcomingsof this software which could not handle models with huge number of variables or withcomplex ODEs, this work applied the method of Fortran programming based on thesoftware platform to solve the models of riser reactor, combustor, and the free boardregion of2ndstage dense bed regenerator.
This work observed the effects of seven key process operating variables such asfeed flow rate and feed temperature on the run state of the whole FCCU, hoping togive instructive guidelines for the field operation, engineering design, and processoptimization of this type of FCCU. The technologies of quench injection in riserreactor, catalyst heat remover, and combustion air oxygen enrichment were analysedfor their application potential on the FCCU. Applicatioin of quench injection on theriser could control the residence time of hot oil gas and catalyst within the reactor, sothe products distribution could be tuned up. The addition of catalyst heat removerimproved the operator’s ability to adjust the unit heat balance, so that the gas/solidtemperature at the feed inlet of riser reactor and the ratio of regenerated catalyst flowrate to mixed feed flow rate could be controlled. The technology of oxygenenrichment in combustion air intensified the ability of catalyst regeneration ofcombustor-style regenerator, improved the initial activity and selectivity of unitbalance catalyst. The three technologies could complement with each other, formingthe combined process intensification technology. The simulation results showed thatthe application of this technology elevated the field operation level, considering itsablity to comtrol the ratio of regenerated catalyst flow rate to feed flow rate, theenvironmental temperature of oil cracking reactions, the residence time of hot oil gasand catalyst in riser reactor, and the coke content of regenerated catalyst.
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