Adsorption Isotherm Parameter Estimation in Nonlinear Liquid Chromatography

• This thesis concerns the development and validation of methods for the industrially important area of adsorption isotherm parameter estimation in preparative, nonlinear high performance liquid chromatography (HPLC). Preparative chromatography is a powerful separation method to get pure compounds from more or less complex liquid mixtures, e.g., mixtures of mirror-image molecules. Computer simulations can be used to optimize preparative chromatography, but then competitive adsorption isotherm parameters are usually required. Here two methods to estimate adsorption isotherm parameters are treated: (i) the perturbation peak (PP) method and (ii) the inverse method (IM).A new theory for the PP method was derived and led to a new injection technique which was validated experimentally. This injection technique solved the severe problem with vanishing peaks and enabled us to use the PP method to estimate binary competitive adsorption isotherms valid over a broad concentration range. Also, the injection technique made it possible to estimate competitive adsorption isotherms for a quaternary mixture for the first time. Finally, an interesting perturbation peak phenomenon, known as the “Helfferich Paradox”, was experimentally verified for the first time.The IM is a relatively new method to determine adsorption isotherm parameters. It has the advantage of requiring very small samples, but also requires an advanced computer algorithm. An improved implementation of this computer algorithm was developed and tested experimentally. Also, a variant of the IM called “the inverse method on plateaus” was tested experimentally and the estimated adsorption isotherm parameters were shown to be valid over a broader concentration range than those estimated with the standard IM.

Ämnesord

NATURVETENSKAP  -- Matematik -- Beräkningsmatematik (hsv//swe)

NATURAL SCIENCES  -- Mathematics -- Computational Mathematics (hsv//eng)

NATURVETENSKAP  -- Kemi -- Analytisk kemi (hsv//swe)

NATURAL SCIENCES  -- Chemical Sciences -- Analytical Chemistry (hsv//eng)

Nyckelord

High performance liquid chromatography (HPLC)

Preparative chromatography

Competitive adsorption isotherm parameters

Perturbation peak (PP) method

Inverse method (IM)

Computer simulation

Parameter estimation

Numerical method

Scientific Computing

Beräkningsvetenskap

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