The catalytic esterification reaction was used to decrease total acid number(TAN) of crude oil by converting naphthenic acids to naphthenic acid esters in the presence of Zn-Al hydrotalcite used as the catalyst and glycol used as the reactant. The crude oil and its corresponding esterified oil were characterized by the negative-ion electrospray ionization(ESI) Fourier transform ion cyclotron resonance mass spectrometry(FT-ICR MS). Six acidic class species, O_2, O_1, N_1, N_2, N_1O_1 and N_1O_2 were assigned in the negative-ion spectrum both in the crude oil and its esterified oil. Among the identified acidic compounds, the O2 class was dominant. The relative abundance of O_2 class species was much higher than other acidic class species in crude oil, while it was significantly decreased after esterification. The most abundant O_2 class species had a carbon number of 30-34 and a double-bond equivalence(DBE) value of 5 before and after esterification. It could be concluded that the naphthenic acids in crude oil can be esterified to lower its TAN value, and each of them seems to exhibit identical esterification efficiency approximately due to the similar DBE versus the-carbon number distribution before and after esterification.
Liaohe super-heavy crude oil was separated into its components, namely saturates, aromatics, resins, and asphaltenes(SARA), by the group separation method. Several solvents were used to extract different forms of metallic elements from crude oil. The metallic elements, such as calcium, nickel, iron and manganese, in crude oil, SARA and extract samples were analyzed by inductively coupled plasma atomic emission spectroscopy(ICP-AES). The results demonstrate that the contents of calcium, nickel, iron, and manganese gradually increase in saturates, aromatics, resins, and asphaltenes, suggesting that the abundance of the four metallic elements in asphaltenes is much higher than that in the other groups. For example, the content of calcium in asphaltenes reaches a maximum of 7,920 μg/g. Among the SARA components of Liaohe super-heavy crude oil, resins account for more than 50 wt%, suggesting that the total amount of the four metallic elements are higher in the resin component than in other components. The four metallic elements mainly exist in the form of organic metallic compounds in crude oil. Further analysis shows that calcium and manganese elements exist mainly as metal salts of petroleum acids, and the majority of the iron and all the nickel exist mainly as metalloporphyrin and non-metalloporphyrin compounds.
