Synthesis and Characterization of Functionalized Poly(glycidyl methacrylate)-Based Particles for the Selective Removal of Nitrogen Compounds from Light Gas Oil: Effect of Linker Length

Abstract

In this work, four poly­(glycidyl methacrylate-co-ethylene glycol methacrylate) [PGMA-co-EDGMA] functionalized particles were synthesized and characterized, and tested in gas oil adsorption. Particles consisted of identical polymer support (PGMA-co-EDGMA, henceforth referred to as PGMA) and π-acceptor moiety (2,4,5,7-tetranitroflorenone, TENF), while the linkers (linear diamines) were varied from a two- (diaminoethane, DAE (2)), a three- (diaminopropane, DAP­(3)) to a four-carbon (diaminobutane, DAB­(4)) containing compounds. The particles notation takes the form: PGMA-DAE­(2)-TENF, PGMA-DAP­(3)-TENF, PGMA-DAB­(4)-TENF and PGMA-DAB­(4)­5-TENF, where 5 denotes the synthesis in 5% (vol./vol.) linker and 95% (vol./vol.) toluene solution, while for other three, 100% (vol./vol.) linker was used. Particles were characterized by, among others, Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), elemental carbon, hydrogen, nitrogen and sulfur analysis (CHNS) and scanning electron microscopy (SEM). The change in linker length did not result in a significant effect on loading as similar amounts of TENF were immobilized on the polymeric particles regardless of the linker length. From the adsorption studies of light gas oil (LGO), results showed that diaminopropane (PGMA-DAP­(3)-TENF) substituted particles gave the highest % adsorption of nitrogen compounds, followed by the diaminobutane (PGMA-DAB­(4)-TENF)-based particles, while no significant differences between the particles with diaminoethane (PGMA-DAE­(2)-TENF) and PGMA-DAB­(4)­5-TENF were observed. The results further showed that all the four types of particles selectively adsorbed nitrogen compounds, while the sulfur concentration in LGO remained unchanged under the following adsorption process conditions: ambient temperature (24 °C), time (24 h), particles to oil loading ratio (1:4 wt./wt.) and stirring speed (400 rpm). Generally, steric hindrance around the TENF molecules, on the surface of the particles, had a major role to play in the adsorption process than the length of the linker.

Insights into the integrated effects of polymeric pretreatment and catalytic hydrotreatment of light gas oil

“…To ensure that the removal of nitrogen compounds was solely due to the polymer alone, blank tests were performed. Although nitrogen adsorption was higher in the batch scale, Chitanda et al also experienced a 6% (from 19% to 13%) decrease in total nitrogen adsorption after just one regeneration of the polymer. Similarly, in this study, there was a 4% (from 10.5% to 6.5%) decrease in nitrogen adsorption after the first regeneration.…”

“…Based on the following results, it can be concluded that bulk polymer mass had an effect on polymer activity with regard to nitrogen adsorption. Higher nitrogen adsorption was experienced on the batch scale as compared with the pilot scale. However, for sulfur adsorptions, there was no difference between the batch and pilot scale because both had no change in sulfur removal, indicating that bulk polymer mass had no effect on sulfur removal.…”

“…Synthesis and characterization of PGMA‐DAP(3)‐TENF have been previously studied by Chitanda et al The light gas oil used in this study was provided by Syncrude Canada Ltd. and contains 30,500 ppm of sulfur and 1,700 ppm of nitrogen. The adsorption study was carried out at a temperature of 23°C where the PGMA‐DAP(3)‐TENF polymer was added to the light gas oil in a 1:4 (wt/wt) ratio.…”

“…Hence, in the course of this study, a synthesized polymer particle consisting of a polymer support, copolymer of glycidyl methacrylate and ethylene glycol dimethacrylate (PGMA‐co‐EDGMA), a π‐acceptor moiety (2,4,5,7‐tetranitrofluorenone, TENF), and a three‐carbon linker (diaminopropane, DAP (3)) hereafter referred to as PGMA‐DAP(3)‐TENF was used. Prior research by Chitanda et al has been conducted to synthesize and characterize different functionalized polymers with varying physical and chemical characteristics. Among these functionalized polymers, PGMA‐DAP(3)‐TENF had the highest nitrogen removal efficiency, hence the polymer choice for this research.…”

One simple and stable coating of mixed‐charge copolymers on poly(vinyl chloride) films to improve antifouling efficiency

“…In this study, we aimed to develop a simple and effective strategy for PVC‐based medical films to enhance their antifouling properties and long‐term stability. It is well known that glycidyl methacrylate (GMA) with epoxy pendants is able to react with functional groups, such as amino, hydroxyl, or carboxyl groups, on the surface of a substrate . Therefore, poly(3‐sulfopropyl methacrylate–methacrylatoethyl trimethyl ammonium chloride–glycidyl methacrylate) (PSTG) copolymers were synthesized by free‐radical polymerization.…”