Lab-simulated downhole leaching of formaldehyde from proppants by high performance liquid chromatography (HPLC), headspace gas chromatography-vacuum ultraviolet (HS-GC-VUV) spectroscopy, and headspace gas chromatography-mass spectrometry (HS-GC-MS).
The ability of different methods to analyze formaldehyde and other leachates from proppants was investigated under lab-simulated downhole conditions. These methods include high performance liquid chromatography (HPLC), headspace gas chromatography-vacuum ultraviolet spectroscopy (HS-GC-VUV), and headspace gas chromatography-mass spectrometry (HS-GC-MS). Two different types of resin-coated proppants, phenol-formaldehyde- and polyurethane-based, were examined. Each proppant was tested at different time intervals (1, 4, 15, 20, or 25 hours) to determine the timeframe for chemical dissolution. Analyses were performed at room temperature and heated (93 °C) to examine how temperature affected the concentration of leachates. Multiple matrices were examined to mimic conditions in subsurface environment including deionized water, a solution surrogate to mimic the ionic concentration of produced water, and recovered produced water. The complexity of these samples was further enhanced to simulate downhole conditions by the addition of shale core. The influence of matrix components on the analysis of formaldehyde was greatly correlated to the quantity of formaldehyde measured. Of the three techniques surveyed, HS-GC-MS was found to be better suited for the analysis of formaldehyde leachates in complex samples. It was found that phenol-formaldehyde resin coated proppants leached higher concentrations of formaldehyde than the polyurethane resin coated proppants.