Combustion properties of kraft black liquor solids were studied using a laminar entrained flow reactor. The tendency of black liquors to release fume (compounds containing Na⁺, K⁺, Cl⁻, SO₄²⁻, SO₃²⁻, S₂0₃²⁻ and C0₃²⁻) during combustion were observed at 1000°C. Black liquor solids with a size fraction of 63 to 100 μm were burned in a mixture of 4% 0₂ and 96% N₂ at a residence time of 0.67 seconds. Combustion properties of one black liquor (liquor #3) were studied by varying the solids feed rate from 0.47 to 1.08 g/min (liquor feed rate study). Combustion properties of five North American and Finnish black liquors were studied at a target solids feed rate of 0.73 g/min (liquor to liquor study). Black liquor fuming was observed to be a decreasing function of solids feed rate and an increasing function of excess oxygen. The appearance of char residues varied from black and porous at high solids feed rates to white and dense at low solids feed rates. Combustion may have been enhanced at low solids feed rates by liquor swelling due to a combination of heat and mass transfer effects and limited at high solids feed rates by inter-particle and bulk gas mass transfer limitations. For the liquor to liquor study, black liquors were observed to release fume differently. Chars produced during this study varied in appearance, indicating that the black liquors had unique combustion properties. Variations in temperature and mass transfer effects resulting from liquor swelling properties were likely responsible for the variability in liquor fuming behavior. The liquors that contained the most NaCl and had the highest anionic equivalents as C0₃²⁻ (or other chemical species) produced the most fume. Sodium vaporization varied from 25.2% to 33.7%: Liquors #2 and #5 vaporized the most sodium and also had the lowest concentrations of measured anions in their char residues. Potassium and chloride enrichment factors for the five liquors were slightly lower than those of common industrial boilers. Liquor #3 had a concentration of Cl⁻ that was (roughly) an order of magnitude higher than the other liquors studied; however, it also had the lowest chloride enrichment factor. / Graduation date: 2002

Jeffery S. Hsieh

As part of CSIR Biosciences’ interest in aroma chemicals, the processing of crude sulphated turpentine (CST) into high value aroma products was investigated. The primary target product, linalool, was obtained from a mixture of α- and β-pinene in four steps. It can be transformed into a wide range of high value added aroma chemicals. Isomerisation of linalool in the presence of a transition metal catalyst furnishes geraniol and nerol. The scientific work described in this report was part of a bigger project aimed at developing innovative processes to manufacture aroma, flavour & fragrance chemicals through beneficiation of industrial waste streams and other raw materials, available locally from the Forestry, Paper & Pulp industries. The evaluation of a process for the preparation of precursor aroma, flavour & fragrance compounds, in particular geraniol and nerol, from locally available raw materials and industrial waste streams, was investigated. Preparation of geraniol and nerol from linalool (ex α-pinene stream) was investigated using acids or organometallic complexes as catalysts for the corresponding isomerisation reaction. The investigation was conducted in an effort to find a less costly process utilising milder conditions than via the conventional cleavage of β-pinene to myrcene under extreme pyrolysis conditions (>650°C). The transformation of linalool to geraniol/nerol using mineral acids was found to be dominated by secondary reactions such as dehydration and cyclisation, resulting in poor product selectivities and yields. On the other hand, organometallic complexes, in particular vanadium-based complexes (e.g. (OV(OBu)3) produced satisfactory results in the preliminary assessment (conversion of 79.8 percent and selectivity of 98.3 percent). A set of statistically designed experiments was carried out on the (VO(BuO)3 + [(Bu)4N+]OH¯) catalyst system where three variables were tested, i.e. substrate concentration, temperature, and catalyst loading. The selected model for conversion was significant with the “Probability > F” being < 0.0001. The most important contributing variable to the model for conversion was temperature i.e. 83.9 percent. Temperature was still the most important variable for the selectivity response at 65.0 percent contribution level. The response surface generated for the selectivity response was flat indicating a robust method within the parameter range selected.

Submitted in the fulfillment of the requirements for the degree of Master of Technology, Durban University of Technology, Durban, South Africa, 2011. / The main objective of this study was to evaluate the feasibility of conversion of crude tall oil and tall oil fatty acids into biodiesel. During the Kraft pulping process, Crude Tall Oil originates as tall oil soap, which is separated from recovered black liquor. The soap is then converted to Crude Tall Oil by acidulation with sulphuric acid. The Crude Tall Oil is then fractionated by distillation to produce tall oil fatty acids (TOFA), rosin and pitch. There were a number of conversional methods that were considered but proved to be inappropriate. A base-catalyzed method was inappropriate with due to the high free fatty acid content on the feedstock, and the acid-base catalyzed method was inappropriate due to the long reaction times and large excess of methanol required. An enzyme based conversion method was also found to be inappropriate because of the high price attached to the purchasing of the enzymes and the stability of the enzyme. A procedure of choice was the supercritical methanol treatment, due to the fact that it requires no separate catalyst. A procedure was developed for both the feedstocks (i.e. crude tall oil and tall oil fatty acids) using the supercritical methanol treatment. In supercritical methanol treatment, feedstock and methanol were charged to a reactor and were subjected to temperatures and pressures beyond the critical point of methanol (Tc = 240 °C, Pc = 35 bar). The maximum biodiesel yield obtained from Crude tall oil was 66% and was 81% for the tall oil fatty acids that was produced in a single stage process. The temperature and methanol to feedstock ratio effects was also found to yield a maximum biodiesel yield at 325°C and 40:1 respectively. A 20 minutes reaction time was found to be appropriate for the maximum yield of biodiesel. The final biodiesel produced was also evaluated against a commercial biodiesel product and its parameters measured. The biodiesel resulting from the tall oil fatty acid yielded parameters that were acceptable according to ASTM D6751 specifications for biodiesel. The biodiesel produced from the crude tall oil did not meet the ASTM D6751 specification, and this was mostly attributed to the presence of unsaponifiables which hindered the conversion of oil into biodiesel. / M

Graduation date: 1995

Graduation date: 1994