Date of Award

8-2016

Level of Access Assigned by Author

Open-Access Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Chemical Engineering

Advisor

Joseph M. Genco

Second Committee Member

Hemant P. Pendse

Third Committee Member

Adriaan R.P. van Heiningen

Additional Committee Members

Raymond C. Fort, Jr.

Barbara J. W. Cole

David J. Neivandt

Abstract

The objective of this dissertation was to develop a process for the production of acetic acid in kraft mills. Acetyl groups in hardwood can be hydrolyzed using alkali at 50 °C. The product from this process contains about 15 g/L of sodium acetate and was determined to be suitable for the production of acetic acid.

Experiments performed using aqueous sodium acetate to evaluate the ability of electrodialysis (ED) to separate and concentrate sodium acetate showed that sodium acetate can be concentrated up to 275 g/L starting with an initial concentration of 17 g/L. The transport of water with sodium and acetate ions through ED membranes limited the maximum obtainable concentration.

To avoid the deleterious effects of white liquor on ED, selectivity experiments were performed using synthetic oxidized white liquor extract. These experiments showed a decrease in the efficiency of ED process due to the presence of sodium carbonate and sodium sulphate in the extract. Hence, it was concluded that caustic should be used as the extraction solvent.

Bi-polar electrodialysis (BPMED) experiments performed using sodium acetate showed that up to 200-280 g/L of acetic acid can be produced using BPMED. Although higher concentrations of sodium hydroxide can also be produced using BPMED, 30 g/L concentration was considered to be sufficient for recycle to the extraction process.

Feed and bleed mode BPMED experiments were performed to determine the current efficiencies and the suitable inlet concentration of sodium acetate for the production of up to 200 g/L of acetic acid. Both feed and bleed mode and batch experiments showed that the current density was the major driving force for BPMED.

Two types of concentrated wood extracts; namely (1) clarified and (2) unclarified were prepared with and without the lignin removal pre-treatment, respectively. The results of the ED and BPMED experiments performed using these extracts were similar to those of the synthetic sodium acetate. A major difference involved an increase of about 15% in electric energy consumption arising from the transport of formate, lactate and glycolate salts. The color of the anionic membranes slightly changed after processing unclarified extract through ED and BPMED.

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