渣油加氢反应动力学及组合工艺研究
摘要
随着燃油标准的日趋严格,以及重质燃料油需求量的逐渐下降,经济环保的渣油加氢处理技术已成为当今世界各国在石油化工领域争相开发的热点之一
为了优化渣油加氢反应过程,降低催化剂使用成本,利于装置长周期稳定运行和现场操作,本文采用FZC系列渣油加氢催化剂,从渣油加氢反应过程的催化剂失活、渣油加氢主要影响因素、催化剂组合装填比例等方面建立了渣油加氢反应动力学模型,同时开发了SFI渣油加氢与催化裂化深度组合系列技术,可以大幅度提高炼化企业总体经济收益。
渣油加氢处理技术开发的关键之一是催化剂的研制和各类催化剂的组合。本文首先根据渣油加氢反应和催化剂的特点,研究了FZC系列各类催化剂的物化性质和活性、稳定性评价结果,为FZC系列催化剂组合研究提供技术依据。研究结果表明,FZC系列催化剂的主要物化性质和反应活性均达到了国外同类催化剂的水平,而且具有良好的稳定性。
其次,依据采用FZC系列催化剂的渣油加氢工业装置实测数据,应用经验动力学模型和催化剂时变失活模型分别对茂名、齐鲁、海南三套装置的实测操作数据进行模拟和分析,建立了渣油加氢失活动力学模型,求取了各装置的反应动力学参数和失活动力学模型表达式。结果表明,该建模方法是切实可行的。运用渣油加氢失活动力学模型可以预测产品杂质含量和催化剂使用寿命。
在此基础上进一步对FZC系列催化剂的性能进行中试试验,分别研究了原料油性质和操作条件对渣油加氢处理过程的影响,建立了包括原料油影响因子校正和操作条件影响因子校正的渣油加氢反应动力学模型。同时,针对工业装置各种催化剂没有达到同步失活的现状,提出了催化剂组合装填比例优化的动力学研究方法。
最后,针对现有组合工艺的不足开发了SFI渣油加氢与催化裂化深度组合技术,其主要特征是渣油加氢装置不设产品分馏系统和催化裂化重柴油、回炼油及油浆外循环到渣油加氢装置。该组合技术实现了重油深度转化最大量生产高价值汽油产品的预期目标,显著地提高了原油资源利用率；而且该组合技术工艺流程简单,装置建设投资和操作费用低,从而大幅度地提高了炼化企业总体经济收益。
With more and more stringent standards of fuel oils and less and less demand on heavy fuel oil in recent years, the R & D on economic profitable and environmental friendly residue hydrotreating process has become increasing attention to petroleum industry worldwide.
In order to optimize the residue hydrotreating process, lower the cost of catalyst, longer stable running and easier operate, the FZC series catalysts are been selected to study. By the study of FZC catalyst, the deactivation of catalysts, key influent factors and grading loading during the residue hydrotreating process, the residue hydrotreating model has been built up. At the same time, a series of SFI combination technologies of residue hydrotreating and RFCC are developed, which can greatly increase the benefit of refineries in whole.
One of the key factors in residue fixed bed hydrotreating is the catalyst development and catalyst combination technology.
Firstly, on the base of the characteristics of residue hydrotreating reaction and catalyst, various types of FZC catalyst are introduced and evaluation results of activity and stability are outlined, which provides the basic information for FZC series catalyst combination.
The performance test results showed that, the catalyst of FZC series can be the same technical tier as the reference catalyst both in physic-chemical specification and reactive activity and has well long-term stability.
Secondly, based on simulation and analysis of the operation data with FZC series catalysts in three commercial units of Maoming, Qilu and Hainan, residue hydrotreating deactivation kinetics models have been established. And reaction kinetics model parameters and deactivation kinetics model formula have been set up, which is used in predicting the impurities in products and catalyst cycle length and the calculation results well match with those of commercial running.
On the basis of reaction kinetics model parameters and deactivation kinetics model formula, pilot plant test had been conducted to show the effects of the properties of feedstock and operating conditions on residue hydrotreating process, and correction factors impacting on feedstock and operating conditions have thus been established. Meanwhile, a kinetics research method of optimization of various types of catalyst combination loading ratio has been proposed due to catalyst un-synchronous deactivation in commercial applications.
Finally, to overcome the shortage of existing combination process, a series of SFI combination technologies of residue hydrotreating and RFCC are developed, whose main feature is that there is no fractionation system in residue hydrotreating unit, and FCC diesel, recycle oil and/or FCC slurry oil recycle back to the residue hydrotreating unit. SFI combination technologies can achieve maximum production of high value gasoline by residue deep conversion and therefore increase the utilization of crude resources. SFI combination technologies are also characterized by simpler process flow, lower capital and operation cost, which can greatly improve the overall economic benefits for refineries.
为了优化渣油加氢反应过程,降低催化剂使用成本,利于装置长周期稳定运行和现场操作,本文采用FZC系列渣油加氢催化剂,从渣油加氢反应过程的催化剂失活、渣油加氢主要影响因素、催化剂组合装填比例等方面建立了渣油加氢反应动力学模型,同时开发了SFI渣油加氢与催化裂化深度组合系列技术,可以大幅度提高炼化企业总体经济收益。
渣油加氢处理技术开发的关键之一是催化剂的研制和各类催化剂的组合。本文首先根据渣油加氢反应和催化剂的特点,研究了FZC系列各类催化剂的物化性质和活性、稳定性评价结果,为FZC系列催化剂组合研究提供技术依据。研究结果表明,FZC系列催化剂的主要物化性质和反应活性均达到了国外同类催化剂的水平,而且具有良好的稳定性。
其次,依据采用FZC系列催化剂的渣油加氢工业装置实测数据,应用经验动力学模型和催化剂时变失活模型分别对茂名、齐鲁、海南三套装置的实测操作数据进行模拟和分析,建立了渣油加氢失活动力学模型,求取了各装置的反应动力学参数和失活动力学模型表达式。结果表明,该建模方法是切实可行的。运用渣油加氢失活动力学模型可以预测产品杂质含量和催化剂使用寿命。
在此基础上进一步对FZC系列催化剂的性能进行中试试验,分别研究了原料油性质和操作条件对渣油加氢处理过程的影响,建立了包括原料油影响因子校正和操作条件影响因子校正的渣油加氢反应动力学模型。同时,针对工业装置各种催化剂没有达到同步失活的现状,提出了催化剂组合装填比例优化的动力学研究方法。
最后,针对现有组合工艺的不足开发了SFI渣油加氢与催化裂化深度组合技术,其主要特征是渣油加氢装置不设产品分馏系统和催化裂化重柴油、回炼油及油浆外循环到渣油加氢装置。该组合技术实现了重油深度转化最大量生产高价值汽油产品的预期目标,显著地提高了原油资源利用率；而且该组合技术工艺流程简单,装置建设投资和操作费用低,从而大幅度地提高了炼化企业总体经济收益。
With more and more stringent standards of fuel oils and less and less demand on heavy fuel oil in recent years, the R & D on economic profitable and environmental friendly residue hydrotreating process has become increasing attention to petroleum industry worldwide.
In order to optimize the residue hydrotreating process, lower the cost of catalyst, longer stable running and easier operate, the FZC series catalysts are been selected to study. By the study of FZC catalyst, the deactivation of catalysts, key influent factors and grading loading during the residue hydrotreating process, the residue hydrotreating model has been built up. At the same time, a series of SFI combination technologies of residue hydrotreating and RFCC are developed, which can greatly increase the benefit of refineries in whole.
One of the key factors in residue fixed bed hydrotreating is the catalyst development and catalyst combination technology.
Firstly, on the base of the characteristics of residue hydrotreating reaction and catalyst, various types of FZC catalyst are introduced and evaluation results of activity and stability are outlined, which provides the basic information for FZC series catalyst combination.
The performance test results showed that, the catalyst of FZC series can be the same technical tier as the reference catalyst both in physic-chemical specification and reactive activity and has well long-term stability.
Secondly, based on simulation and analysis of the operation data with FZC series catalysts in three commercial units of Maoming, Qilu and Hainan, residue hydrotreating deactivation kinetics models have been established. And reaction kinetics model parameters and deactivation kinetics model formula have been set up, which is used in predicting the impurities in products and catalyst cycle length and the calculation results well match with those of commercial running.
On the basis of reaction kinetics model parameters and deactivation kinetics model formula, pilot plant test had been conducted to show the effects of the properties of feedstock and operating conditions on residue hydrotreating process, and correction factors impacting on feedstock and operating conditions have thus been established. Meanwhile, a kinetics research method of optimization of various types of catalyst combination loading ratio has been proposed due to catalyst un-synchronous deactivation in commercial applications.
Finally, to overcome the shortage of existing combination process, a series of SFI combination technologies of residue hydrotreating and RFCC are developed, whose main feature is that there is no fractionation system in residue hydrotreating unit, and FCC diesel, recycle oil and/or FCC slurry oil recycle back to the residue hydrotreating unit. SFI combination technologies can achieve maximum production of high value gasoline by residue deep conversion and therefore increase the utilization of crude resources. SFI combination technologies are also characterized by simpler process flow, lower capital and operation cost, which can greatly improve the overall economic benefits for refineries.
引文
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