Scale-up and thermal stability analysis of fluidized bed reactors for ethylene polymerization

A set of hydrodynamic similarity laws is applied to the scale-up of ethylene polymerization fluidized bed reactors(FBRs)under the condensed mode operation.The thermal stability of open-loop controlled FBRs is investigated by the homotopy continuation method.And the Hopf bifurcation point is selected as an index of the thermal stability similarity.The simulation results show the similarity in state variables,operation parameters,the space-time yield(STY),and the thermal stability of FBRs with different scales.Furthermore,the thermal stability behaviors and similarity of the closed-loop controlled FBRs with different scales are analyzed.The observed similar trend of Hopf bifurcation curves reveals the similarity in the thermal stability of closed-loop controlled FBRs with different scaling ratios.In general,the results of the thermal stability similarity confirm that the hydrodynamics scaling laws proposed in the work are applicable to the scale-up of FBRs under the condensed mode operation.

Modelling and simulation of two-bed PSA process for separating H2 from methane steam reforming

Methane steam reforming is the main hydrogen production method in the industry. The product of methane steam reforming contains H2, CH4, CO and CO2 and is then purified by pressure swing adsorption(PSA) technology. In this study, a layered two-bed PSA process was designed theoretically to purify H2 from methane steam reforming off gas. The effects of adsorption pressure, adsorption time and purgeto-feed ratio(P/F ratio) on process performance were investigated to design a PSA process with more than99.95% purity and 80% recovery. Since the feed composition of the PSA process changes with the upstream process, the effect of the feed composition on the process performance was discussed as well.The result showed that the increase of CH4 concentration, which was the weakest adsorbate, would have a negative impact on product purity.

Assessment of the TFM in predicting the onset of turbulent fluidization

Accurate prediction of the onset of turbulent fluidization still remains elusive owing to the dependence of the transition velocity on several factors including measurement methods and interpretation of results. In this work, numerical simulations using the two fluid model (TFM) are performed in an attempt to predict the regime change reported by Gopalan etal.(2016) in a small scale pseudo-2D gas-solid fluidized bed containing Geldart D particles. Various time and frequency domain analyses were applied on predicted absolute and differential pressure time series data to reveal the bed dynamics. Numerical predictions of the transition velocity, Uc are in reasonably good agreement with experimental results from the small scale challenge problem. The literature correlations completely fail to predict the transition velocity for the system considered in this work. This work thus provides a different approach for validating the CFD model against experimental measurements.

Numerical simulations and comparative analysis of two- and three-dimensional circulating fluidized bed reactors for CO2 capture

Carbon dioxide(CO2),the main gas emitted from fossil burning,is the primary contributor to global warming.Circulating fluidized bed reactor(CFBR)is proved as an energy-efficient method for post-combustion CO2 capture.The numerical simulation by computational fluid dynamics(CFD)is believed as a promising tool to study CO2 adsorption process in CFBR.Although three-dimensional(3D)simulations were proved to have better predicting performance with the experimental results,two-dimensional(2D)simulations have been widely reported for qualitative and quantitative studies on gas-solid behavior in CFBR for its higher computational efficiency recently.However,the discrepancies between 2D and 3D simulations have rarely been evaluated by detailed study.Considering that the differences between the 2D and 3D simulations will vary substantially with the changes of independent operating conditions,it is beneficial to lower computational costs to clarify the effects of dimensionality on the numerical CO2 adsorption runs under various operating conditions.In this work,the comparative analysis for CO2 adsorption in 2D and 3D simulations was conducted to enlighten the effects of dimensionality on the hydrodynamics and reaction behaviors,in which the separation rate,species distribution and hydrodynamic characteristics were comparatively studied for both model frames.With both accuracy and computational costs considered,the viable suggestions were provided in selecting appropriate model frame for the studies on optimization of operating conditions,which directly affect the capture and energy efficiencies of cyclic CO2 capture process in CFBR.

Pore plugging effects on the performance of ZSM-5 catalyst in MTP reaction using a discrete model

Coke is an important medium for connecting reaction and regeneration of the methanol to propylene process on the ZSM5 catalyst.Coke grows in the meso and macro pores,it gradually worsens the diffusion inside the catalyst particle.Furthermore,pore plugging is inevitable which causes the deactivation of ZSM5 catalyst.However,current continuum model cannot reflect the changes in pore structure with clear physical concepts.A discrete model that is verified by the carbon deposition experiments is introduced to indicate the behavior of pore plugging effects.Results show that the pore plugging has a significant effect on the performance of the catalyst.The time varying profile of effectiveness factor is obtained,indicating a regular reduction with the increase of the pore plugging effect.Spatial distributions of pore size that would significantly enhance the plugging effect are also identified.

Polyhedral Feasible Set Computation of MPC-Based Optimal Control Problems

Feasible sets play an important role in model predictive control(MPC) optimal control problems(OCPs). This paper proposes a multi-parametric programming-based algorithm to compute the feasible set for OCP derived from MPC-based algorithms involving both spectrahedron(represented by linear matrix inequalities) and polyhedral(represented by a set of inequalities) constraints. According to the geometrical meaning of the inner product of vectors, the maximum length of the projection vector from the feasible set to a unit spherical coordinates vector is computed and the optimal solution has been proved to be one of the vertices of the feasible set. After computing the vertices,the convex hull of these vertices is determined which equals the feasible set. The simulation results show that the proposed method is especially efficient for low dimensional feasible set computation and avoids the non-unicity problem of optimizers as well as the memory consumption problem that encountered by projection algorithms.

Alternating Copolymerization of Epoxides and Isothiocyanates to Diverse Functional Polythioimidocarbonates and Related Block Polymers

Synthesis of diverse polythioimidocarbonates via ring-opening copolymerization of epoxides and isothiocyanates catalyzed by organoboron catalyst was reported herein.Both aromatic and aliphatic isothiocyanates underwent successful copolymerization with terminal and internal epoxides,allowing for the precise tuning of the performance of the resultant copolymers over a broad range.The wide scope of available isothiocyanates and epoxides enables the direct construction of sulfur-containing functional polymers featuring both high glass transition temperature and refractive index.Additionally,it was observed that aromatic isothiocyanates polymerize much faster than aliphatic ones,and the reactivity difference facilitated the one-step synthesis of block polymers from mixed aromatic isothiocyanates,aliphatic isothiocyanates and epoxides due to the preferential incorporation of aromatic isothiocyanates over the aliphatic analogues during their alternating copolymerization with epoxides.The produced polythioimidocarbonates can be used as positive resists for electron beam lithography(sensitivity of 130μC/cm^(2) and contrast of 1.53 for poly(CHO-alt-EITC)).Coupling with their high refractive index(1.58—1.68),polythioimidocarbonates might find functional applications in optics.These results render ring-opening copolymerization of epoxides and isothiocyanates a facile route to enrich functional polymer library.

高性能聚乙烯产品设计

聚烯烃是国民经济建设和日常生活必不可少的重要基础材料和战略物资.目前,我国聚烯烃行业严重依赖进口,高端聚烯烃产品占进口量的一半以上,行业发展严重受制于人.金属有机催化理论的迅猛发展极大地增强了对聚合物分子结构的调控能力,使人们有可能设计出更多性能优异的聚烯烃新产品.但是,如何实现聚烯烃新产品的工业生产,并使之转化成为商品,是制约聚烯烃产品高性能化的瓶颈,涉及化学工程和高分子科学的深度交叉.本文分别从催化剂结构设计、非均相催化剂结构解析、聚合反应工艺以及产品加工工艺的层面介绍了当前聚乙烯高性能化的重要进展;重点介绍了从活性中心聚合微环境设计出发,通过与催化剂聚合行为的匹配,开发的高性能聚乙烯产品制备新工艺.利用烃类冷凝液的喷射蒸发,在单一流化床反应器中构建温度、浓度差异化的持液颗粒聚合和气相聚合共存的复合流型,打破流化床固有的温度浓度均一性特点,相继开发了超低/极低密度聚乙烯高端产品数万吨,率先生产热收缩膜、拉伸套管膜、双向拉伸聚乙烯膜等高端产品;利用催化剂在惰性组分纳微气泡富集区域的穿梭和碰撞,在生长的聚乙烯颗粒周围营造反应组分的传质开关,使分子链生长和结晶有节奏地交替进行,降低了初生态聚乙烯的链缠结程度,开发了易加工的超高分子量聚乙烯产品.

Important mesoscale phenomena in gas phase fluidized bed ethylene polymerization

Gas phase fluidized bed processes have been widely applied to polyethylene production.In these processes,the flow,mass transfer,and reaction rate on the microscale and macroscale are strongly coupled because of the multiphase and multiscale nature of the fluidization system.Understanding mesoscale phenomena is therefore essential to the quantitative translation of the knowledge obtained from the microscale to the macroscale.This paper reviews the development of ethylene polymerization gas phase processes while focussing on studies regarding mesoscale phenomena.These include experimental characterizations,mathematical modelling and control strategies.Trends and future developments in this field are also discussed.