Silicon-containing species in used lube oil re-refining

Nowadays, the re-refining of the used lube oils has gained worldwide a lot of attention due to the necessity for added environmental protection and increasingly stringent environmental legislation. One of the parameters determining the quality of the produced base oils is the composition of feedstock. Estimation of the chemical composition of the used oil collected from several European locations showed that the hydrocarbon structure of the motor oil is changed insignificantly during its operation and the major part of the changes is accounted for with depleted oil additives. In the lube oil re-refining industry silicon, coming mainly from antifoaming agents, is recognized to be a contaminant generating undesired solid deposits in various locations in the re-refining units. In this thesis, a particular attention was paid to the mechanism of solid product formation during the alkali treatment process of silicon-containing used lube oils. The transformations of a model siloxane, tetramethyldisiloxane (TMDS), were studied in a batch reactor at industrially relevant alkali treatment conditions (low temperature, short reaction time) using different alkali agents. The reaction mechanism involving solid alkali metal silanolates was proposed. The experimental data obtained demonstrated that the solids were dominant products at low temperature and short reaction time. The liquid products in the low temperature reactions were represented mainly by linear siloxanes. The prolongation of reaction time resulted in reduction of solids, whereas both temperature and time increase led to dominance of cyclic products in the reaction mixture. Experiments with the varied reaction time demonstrated that the concentration of cyclic trimer being the dominant in the beginning of the reaction diminished with time, whereas the cyclic tetramer tended to increase. Experiments with lower sodium hydroxide concentration showed the same effect. In addition, a decrease of alkali agent concentration in the initial reaction mixture accelerated TMDS transformation reactions resulting in solely liquid cyclic siloxanes yields. Comparison of sodium and potassium hydroxides applied as an alkali agent demonstrated that potassium hydroxide was more efficient, since the activation energy in KOH presence was almost 2-fold lower than that for sodium hydroxide containing reaction mixture. Application of potassium hydroxide for TMDS transformation at 100° C with 3 hours reaction time resulted in 20 % decrease of solid yields compared to NaOH-containing mixture. Moreover, TMDS transformations in the presence of sodium silanolate applied as an alkali agent led to formation of only liquid products without formation of the undesired solids. On the basis of experimental data and the proposed reaction mechanism, a kinetic model was developed, which provided a satisfactory description of the experimental results. Suitability of the selected siloxane as a relevant model of industrial silicon-containing compounds was verified by investigation of the commercially available antifoam agent in base-catalyzed conditions.

Wooden packaging waste reuse and refining

The aim of the thesis was both to study wooden packaging waste reuse and refining generated in the forestry machine factory environment, and to find alternative wooden packaging waste utilization options in order to create a new operating model which would decrease the overall amount of waste produced. As environmental and waste legislation has become more rigid and companies' own environmental management systems’ requirements and control have increased, companies have had to consider their environmental aspects more carefully. Companies have to take into account alternative ways of reducing waste through an increase in reuse and recycling. A part of this waste is from different forms of packaging. In the metal industry the most heavily used packaging material is wooden packaging, as such material is heavy and the packaging has to be able to bear heavy stress. In the theoretical part of the thesis, the requirements of packaging and packaging waste legislation, as well as environmental management systems governing companies’ processing of their packaging waste, are studied. The theoretical part includes a process study of systems, which direct packaging waste and wooden packaging waste refining. In addition, methods related to the continuous improvement of these processes are introduced. This thesis concentrates on designing and creating a new operating model in relation to wooden packaging waste processing. The main target was to find an efficient model in order to decrease the total amount of wooden packaging waste and to increase refining. The empirical part introduces methods for approaches to wooden packaging waste re-utilization, as well as a description of a new operating model and its impact.