Theses and Dissertations

Issuing Body

Mississippi State University

Advisor

Hill, Priscilla J.

Committee Member

Toghiani, Rebecca K.

Committee Member

Walters, Keisha B.

Committee Member

Schneider, Judy

Date of Degree

8-6-2011

Document Type

Dissertation - Open Access

Major

Chemical Engineering

Degree Name

Doctor of Philosophy

College

James Worth Bagley College of Engineering

Department

Dave C. Swalm School of Chemical Engineering

Abstract

Crystallization is a key unit operation in the fine chemical and pharmaceutical industries, many of which employ batch stirred vessels for crystallization. Although using stirred vessels for crystallization has advantages such as better mixing and faster cooling, one of the disadvantages is that due to the presence of mechanical parts in the vessel such as baffles, impeller etc., crystals break up while stirring and generate unwanted secondary nucleation. This process contributes to a wide crystal size distribution with a smaller than desired mean crystal size. For studying crystal breakage phenomenon, experimentalists choose to use nonsolvents for crystal breakage experiments to isolate breakage from simultaneously occurring phenomena such as Ostwald-ripening, aging and agglomeration. Although performing experiments in non-solvents eliminates other phenomena and helps isolate breakage, the results can not always be correlated to saturated solutions due to density and viscosity differences between the two conditions. In this research, the effects of Ostwald ripening, aging and agglomeration on the crystal size and shape distributions are quantitatively measured. Micro and macro scale experiments were performed in both non-solvents and saturated solutions and the results were compared to determine the effects. Both in situ focused beam reflectance method (FBRM) and off-line analyses were performed to characterize the crystal size distributions. Results from experiments show that there is significant difference between the breakage behavior of crystals in non-solvents and in saturated solutions, mplying significant impacts of Ostwald ripening, aging, agglomeration and dissolution in saturated solutions. Calculations using Zwietering correlation also show that the difference between the viscosities and densities in the two systems may also be a contributing factor to the difference in the breakage profiles. It was also found that growth rates of crystals can differ when they are subjected to stress and strain. In macroscale experiments, dissolution was found to have a significant impact on the crystal size distribution. Abrasion was found to be the dominating fracture mechanism for most systems. Extent of breakage and morphological changes were found to be dependent on stirring rates, suspension density, shape and hardness of crystals and the type of system.

URI

https://hdl.handle.net/11668/19411

Comments

batch crystallization||stirred vessels||crystals||crystallization||particle||Breakage

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