Quantification of Amines in Refinery Process Water via Surface-Enhanced Raman Spectroscopy

Abstract

Amines are used in crude oil production, natural gas recovery, and hydrocarbon refining as hydrogen sulfide scavengers, corrosion inhibitors, and pH control neutralizers. Residual amines can be detrimental to the refining process, such as forming heat-stable salts that lead to corrosion-inducing deposits or causing nitrification of wastewater streams. Traditional methods for amine analysis such as ion chromatography are complex, time-consuming, and not adapted to field deployment. We present a new method using surface-enhanced Raman spectroscopy for amine quantification with a focus on two problem-causing tramp amines: monoethanolamine and methylamine. This method is calibration-free, accurate across spectrometers, stable over years in laboratory-standard solutions and in real-world process samples, and can be performed by minimally trained operators within less than 5 min.

Advances in Surface-Enhanced Raman Scattering Sensors of Pollutants in Water Treatment

“…Herein, the detection of pharmaceuticals, personal care products (PCP), and heavy ions in water treatment is introduced (see Table 2). We begin with the detection of pharmaceuticals and PCP [69][70][71][72][73][74][75][76][77][78][79], and we end with those of heavy ions [80][81][82][83][84].…”

“…This was assessed at 10 mg/L for CMIT molecules in lake water [72]. By another strategy, Benhabib et al showed the SERS detection of the monoethanolamine (MEA) in the water of the refinery process [73]. In this study, the authors employed gold nanoparticles for enhancing the SERS signal, but also an internal standard, which is an isotopologue of MEA, which is structurally identical, but can be distinguished in a spectroscopic manner (see Figure 5a).…”

“…This method does not require calibration and is stable for several years (see Figure 5b). With this method, the authors reached a LOD of 1.8 mg/L for MEA in the water of the refinery process [73]. Burtsev et al showed an SERS detection of ibuprofen in water by using gold multibranched nanoparticles (AuMNPs) coupled to an extraction process, both in a microfluidic chip [74].…”

Development of a Raman-Based Test for Rapid Thiol Scavenger Detection in Oil and Gas Applications

“…20 The method proved to be very useful for the quality control of triazinebased commercial H 2 S scavengers and the quantification of residual reactants during the scavenging process. On the other hand, a recent study showed the possibility of detecting ppm levels of amines in refinery wastewaters using the ultrasensitive surface-enhanced Raman spectroscopy (SERS) technique, 21 laying the groundwork for the detection of ultralow levels of substituted 1,3,5-triazines or other known nitrogen-containing H 2 S scavengers in downstream processes. Despite the increased use of Raman spectroscopy in H 2 S removal processes, its application in the field of thiol scavengers has been very limited.…”