Liquid-phase polymerization of propylene with a highly active Ziegler-Natta catalyst. Influence of hydrogen, cocatalyst, and electron donor on the reaction kinetics

Samson, Job Jan C.; Bosman, Peter J.; Weickert, G.; Westerterp, K.R.

doi:10.1002/(sici)1099-0518(19990115)37:2<219::aid-pola12>3.0.co;2-3

Cited by 43 publications

(10 citation statements)

References 7 publications

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“…The effect of hydrogen on the rate of polymerization has been extensively studied in the literature. Samson et al [41] and Alshaiban and Soares [42] found that hydrogen can enhance the catalyst activity considerably, an effect that is attributed to the activation of dormant sites. Additionally, Samson et al [41] showed that the reduction of the cocatalyst/donor ratio can diminish the polymerization rates in the analyzed experimental conditions.…”

Section: Kinetic Modelmentioning

confidence: 99%

“…Samson et al [41] and Alshaiban and Soares [42] found that hydrogen can enhance the catalyst activity considerably, an effect that is attributed to the activation of dormant sites. Additionally, Samson et al [41] showed that the reduction of the cocatalyst/donor ratio can diminish the polymerization rates in the analyzed experimental conditions. On the other hand, Garoff et al [53] observed that the increase of the cocatalyst/donor ratio can enhance the productivity, although a point of maximum productivity can be attained, beyond which the productivity diminishes.…”

Section: Kinetic Modelmentioning

confidence: 99%

“…Samson et al. [ 41 ] and Alshaiban and Soares [ 42 ] found that hydrogen can enhance the catalyst activity considerably, an effect that is attributed to the activation of dormant sites. Additionally, Samson et al.…”

Section: Model Developmentmentioning

confidence: 99%

“…Additionally, Samson et al. [ 41 ] showed that the reduction of the cocatalyst/donor ratio can diminish the polymerization rates in the analyzed experimental conditions. On the other hand, Garoff et al.…”

Section: Model Developmentmentioning

confidence: 99%

“…The interesting point is that TEAL, PEEB, and hydrogen can also affect the catalyst activity, coupling the productivity of the polymer resin and the variables that describe the end‐use properties of the product. [ 41–43 ]…”

Section: Introductionmentioning

confidence: 99%

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Optimization of Grade Transitions in Bulk Poly(propylene) Polymerizations

Silva

Melo

Pinto

2023

Macro Reaction Engineering

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In the present paper, a dynamic optimization problem regarding grade transitions in bulk poly(propylene) polymerization processes is formulated and solved for the first time. Initially, a detailed dynamic process model is presented and implemented, comprising mass and energy balances, some of the polymer properties (such as the melting flow index and the xylene solubles) and regulatory control loops. Additionally, the effects of cocatalyst and electron donor on the propagation rate constant are taken into account. Then, the dynamic optimization problem is formulated and an evolutionary algorithm is used to solve the resulting nonlinear programming problem. It is shown that there is significant coupling among the manipulated variables and the controlled performance and polymer property variables, which adds complexity to the grade transition problem and demands the simultaneous manipulation of multiple variables during transitions. Despite the inherent open‐loop unstable nature of the analyzed process, it is shown that smooth grade transition trajectories can be accomplished through proper adjustment of the objective function weights. Finally, it is shown that the obtained optimum trajectories can significantly diminish the transition time, which can be of paramount importance for the plant economics.

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Section: Kinetic Modelmentioning

confidence: 99%

Section: Kinetic Modelmentioning

confidence: 99%

Section: Model Developmentmentioning

confidence: 99%

Section: Model Developmentmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Optimization of Grade Transitions in Bulk Poly(propylene) Polymerizations

Silva

Melo

Pinto

2023

Macro Reaction Engineering

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Effects of low hydrogen partial pressures on propylene polymerization by Cp*TiMe2(?-Me)B(C6F5)3

Ewart

Parent

Baird

1999

J. Polym. Sci. A Polym. Chem.

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Method for quantitative evaluation of kinetic constants in olefin polymerizations. I. Kinetic study of a conventional Ziegler–Natta catalyst used for propylene polymerizations

Matos¹,

Neto²,

Pinto

2001

J. Appl. Polym. Sci.

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A method for quantitative evaluation of kinetic constants in Ziegler–Natta and metallocene olefin polymerizations is presented. The method comprises some fundamental steps, which include the initial design of a statistical experimental plan, the execution of the designed experiments, the development of simple mathematical models to describe the polymerization, and the estimation of kinetic parameters from available rate, gel permeation chromatography, and NMR data. The method is applied to the slurry propylene polymerization, using a conventional first generation Ziegler–Natta catalyst, in a lab‐scale polymerization reactor. It is shown that the proposed method allows the successful interpretation of experimental olefin polymerization data and the quantitative evaluation of kinetic constants, which can be inserted into a process simulator to provide an accurate picture of actual industrial plant behavior. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2076–2108, 2001

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Liquid-phase polymerization of propylene with a highly active Ziegler-Natta catalyst. Influence of hydrogen, cocatalyst, and electron donor on the reaction kinetics

Cited by 43 publications

References 7 publications

Optimization of Grade Transitions in Bulk Poly(propylene) Polymerizations

Optimization of Grade Transitions in Bulk Poly(propylene) Polymerizations

Effects of low hydrogen partial pressures on propylene polymerization by Cp*TiMe2(?-Me)B(C6F5)3

Method for quantitative evaluation of kinetic constants in olefin polymerizations. I. Kinetic study of a conventional Ziegler–Natta catalyst used for propylene polymerizations

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