Transformation of dissolved organic matter during advanced coal liquefaction wastewater treatment and analysis of its molecular characteristics

Abstract

Coal liquefaction wastewater (CLW) contains numerous toxic and biorefractory organics. A series of advanced treatment processes were designed to remove the dissolved organic matter (DOM) from CLW. Here, the reactivity and state of the DOM in the treatment train were studied in relation to its chemical composition by a Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) analysis. Within an isobaric group, the raw CLW possessed a high average double-bond equivalent (DBEwa) and low H/Cwa values with the N- and S-containing compounds accounting for approximately 77% of the raw CLW, which represented lignin (73.6%) and condensed aromatic structures (19.8%). In addition, the flotation process removed some hydrophobic DOM compounds with highly unsaturated states, which were biorefractory compounds. Ozonation and catalytic oxidation processes preferentially removed the highly unsaturated compounds and produced more oxidized molecules. The biofiltration process impacted the organics composition by consuming oxygen-rich substances, whereas the anoxic/oxic (A/O) process converted the reactive compounds into newly formed compounds through the loss of hydrogen (unsaturation) from the original compounds. The membrane bioreactor (MBR) process was more efficient in removing the N-containing compounds with higher unsaturated states. The compounds resistant to the applied CLW treatment processes were characterized by lower molecular weights (approximately 250–350 Da), higher oxidation states (O/S > 6), numerous carboxylic groups, and non-biodegradable features.