Method for Isolation and Detection of Ketones Formed from High-Temperature Naphthenic Acid Corrosion

Abstract

Corrosion control at refineries remains a challenge because the mechanism of naphthenic acid (NAP) corrosion is still not fully understood. The rate of NAP corrosion does not correlate with acidity (as measured by total acid number); therefore, it has been suggested that a subset of NAP in petroleum fractions may be more corrosive than others. Because the primary corrosion product (iron naphthenates) may thermally decompose to ketones at corrosion temperatures (250–400 °C), ketones in corrosion fluids could potentially be used to implicate specific problematic acids in corrosion tests. To that end, we have developed a method for isolating and characterizing ketones in corrosion test solutions. Ketones from tests on palmitic and 4-cyclohexyl pentanoic acids (C16H32O2 and C11H20O2) have been successfully isolated with a strong anion exchange solid-phase separation. Gas chromatography/mass spectrometry identifies ketones formed as a result of model acid corrosion. Fourier transform ion cyclotron resonance mass spectrometry further confirms the detection of these ketones and structurally confirms ketones by use of a commercially available reagent that targets ketones and aldehydes. Additional oxygen species generated in the corrosion test likely result from reactions between dissolved atmospheric oxygen and the mineral oil matrix. With this method now validated, it can be applied in future studies of more complex acid mixtures to determine any structural specificity in naphthenic acid corrosion.

High-Temperature Corrosion by Carboxylic Acids and Sulfidation under Refinery Conditions—Mechanism, Model, and Simulation

“…First, kinetic constants of the dissolution rate of iron sulfide by NAP (reaction ) have only been estimated indirectly as discussed above; exact values of activation energy and pre-exponential factor should be determined directly. The formation of magnetite by thermal decomposition of iron carboxylates (reactions and ) has been confirmed by the detection of ketones in post-test corrosion oils . The reaction has been studied extensively in the preparation of nanoparticulate magnetite and the synthesis of ketones in concentrated solutions of model acids in relatively inert solvents.…”

High Resolution Mass Spectrometry Advances in Oil Spill Analysis

“…Although the photo-microcosm results confirm the in situ generation of surfactants and reveal the oxygen dependence of chemical behavior, they do little to reveal what weathering process (bio-or photo-) is responsible for oxidized transformation products observed in field samples. To address this goal, a chemical functionality dependent method was employed to target ketone/aldehyde transformation products, as both biodegradation and photo-oxidation have been shown to produce them (Krajewski et al, 2017;Lao et al, 1979;Overton et al, 1980;Ruddy et al, 2014). Oil from a bio-only and photo-only microcosm as well as multiple field samples collected after the Deepwater Horizon oil spill, were fractionated by strong cation exchange chromatography to isolate potential ketones/aldehydes (Krajewski et al, 2017).…”

“…To address this goal, a chemical functionality dependent method was employed to target ketone/aldehyde transformation products, as both biodegradation and photo-oxidation have been shown to produce them (Krajewski et al, 2017;Lao et al, 1979;Overton et al, 1980;Ruddy et al, 2014). Oil from a bio-only and photo-only microcosm as well as multiple field samples collected after the Deepwater Horizon oil spill, were fractionated by strong cation exchange chromatography to isolate potential ketones/aldehydes (Krajewski et al, 2017). They were subsequently subjected to a ketone/aldehyde specific chemical derivatization and analyzed by FT-ICR mass spectrometry (Alhassan & Andersson, 2013).…”

“…Ketones were isolated and derivatized from field and microcosm samples by a strong cation exchange method previously reported (Krajewski et al, 2017;Krajewski et al, 2019).…”

Dynamics of Reactive Carbonyl Species in Pea Root Nodules in Response to Polyethylene Glycol (PEG)-Induced Osmotic Stress

“…In the most reliable way, the RCC-metabolome can be addressed by carbonyl-specific derivatization agents, like o -phenylenediamine, O -alkyl hydroxylamines, hydrazines, cysteine amines, and aminoguanidine or similar carbonyl-trapping compounds [ 28 , 29 ]. However, application of each derivatization agent is typically limited to some specific classes of carbonyl-containing molecules—either α-dicarbonyls, like glyoxal, methylglyoxal and 3-deoxyglucasone, or hydroxyaldehydes and ketones, which can be, in turn, either short or long chained [ 28 , 30 ]. In this context, application of such a derivatization reagent as 7-(diethylamino)coumarin-3-carbohydrazide (CHH) might be advantageous [ 15 ].…”