Oxidation and Ignition Behaviour of Saturated Hydrocarbon Samples With Crude Oils Using TG/DTG and DTA Thermal Analysis Techniques
Authors: Li J. , Mehta S.A. , Moore R.G. , Ursenbach M.G. , Zalewski E. , Ferguson H. , Okazawa N.E. 
Published: March 2010

Abstract
This research is aimed at providing a better understanding of the oxidation behaviour of fractions of crude oil, and to then develop an approach to improve ignition for air injection processes.
In this research, Thermogravimetric and Differential Thermal Analysis (TG/DTA) techniques were used to investigate oxidation behaviour using thermal fingerprinting effects on pure paraffin samples and mixtures of pure components with crude oil. The results demonstrated that each paraffin sample shows different oxidation behaviours at low temperatures and high temperatures. The fractions lighter than C16 distill before they reach a temperature where oxidation reactions are significant. Only low temperature exothermic activities are apparent for the fractions between C16 and C26. The heavier fractions show both low and high temperature exothermic activities. The lower molecular weight samples show lower onset temperatures for oxidation reactions. With increasing molecular weight, the exothermic peak temperatures both in the low and high temperature regions shift to higher temperatures and increased energy release.
When low activity Oil B and the more reactive Oil C were mixed with a small amount of paraffin sample heavier than C26, both crude oils showed intensified low temperature oxidation behaviour, with a greater magnitude of heat evolution. The addition of heavier paraffins offers the potential to accelerate reactions and improve ignition.

Introduction
High Pressure Air Injection (HPAI) has been proven as a potential and viable process for improving oil recovery from several light oil reservoirs. When air is injected into an oil reservoir, the oxygen contained in the air can potentially react with the oil in place by various oxidation reaction schemes. Success of such a process depends mainly on the crude oil properties and rock properties, as well as operating conditions. The oxidation behaviour and the conditions typically favouring auto-ignition of crude oils are of the utmost importance for light oil air injection. However, because of the low initial temperature of many of the formations, and the poor reactivity of some crude oils, the magnitude of timedelay is often so great that spontaneous ignition is not economically attractive. Chemical ignition is one of the options to improve ignition(1, 2). Unfortunately, little research has been documented.
The potential for using thermal analysis techniques to investigate oxidation behaviour of crude oils during combustion has been realized. Thermal analysis techniques include Thermogravimetric (TG) and Differential Thermal Analysis techniques (DTA) or Differential Scanning Calorimetry (DSC). In TG, a small amount of a sample of crude oil, with or without sand, is heated in the presence of flowing air and the change in weight of the sample is recorded as a function of temperature. In DTA or DSC, the difference in temperature or energy input/output during hemical or physical transitions based on the differences between the sample and a reference material is recorded as a function oftemperature or time.