320q Divinylbenzenes and Methacrylates Copolymeric Adsorbents for the Denitrogenation of Straight Run Gas Oils

Beatriz Castro, Claudia Perez-Miranda, and Florentino Murrieta-Guevara. Research Program on Reactors and Processes, Mexican Institute of Petroleum, Eje Central Lazaro Cardenas 152 Col San Bartolo Atepehuacan, Mexico DF, 07730, Mexico

There are several applications among the oil industry where the application of denitrogenation processes is feasible. The first is the denitrogenation of gas oils as a hydrodesulfurization pretreatment which is aimed to avoid catalyst inhibition achieving the ultra deep desulfurization of diesel. Secondly, the denitrogenation of naphthas is worthwhile as a process for pretreating this fraction as it goes into the reforming unit. This paper deals with the preparation of polymeric adsorbents for the removal of non-basic and basic nitrogen compounds present in straight-run gas oil (SRGO). Copolymeric materials were synthesized by free-radical bulk polymerization for the adsorption of nitrogen compounds either basic or neutral, such as quinoline or carbazole respectively. Two adsorbents are ethyleneglycoldimethacrylate (EGDMA)-co-methacrylic acid (MAA) which were obtained using either chloroform (P1) or a mixture of acetonitrile and toluene (P2) as porogens. A second set corresponds to EGDMA-co-methyl methacrylate with chloroform (P3) and ACN-Toluene (P4). Divinylbenzenes (DVB) were copolymerized with methacrylic acid to give copolymers P5 (Chloroform) and P6 (ACN-Toluene), and finally two DVB-co-methyl methacrylate copolymers were obtained employing chloroform (P7) and ACN-toluene (P8). Nitrogen uptake assays from straight run gas oil were performed in a batch stirred tank microreactor, at a fixed temperature of 30 oC. The gas oil concentration of total nitrogen was 543 ppmw and sulfur concentration was 14,860 ppmw. Basic nitrogen as well as neutral nitrogen species were quantified. Textural characteristics of the copolymers were assessed including surface area, porosity, average pore size, pore size distribution by nitrogen adsorption isotherms. Chemical analysis for carbon, nitrogen and oxygen was performed as well. These results were correlated to FT-IR spectra of the materials to quantify the carboxylic and carbonyl groups that are interacting with the adsorbates. The contribution of interactions through pi-complexation in the case of DVB materials is relevant, whereas the interactions through carboxylic or carbonyl functional groups are more important for the EGDMA copolymers. Thermal analysis of the materials revealed that they can be used up to temperatures of 200 oC without a significant transformation of the polymeric network and mass loss. An in situ FT-IR experiment was performed to assess the modification of the network while the temperature is increasing. The adsorbents are able to remove either basic or neutral nitrogen compounds, preferable the latter. They removed organosulfur compounds to a lesser extent from the gas oils tested (2% of the initial concentration). A discussion on the selectivity of the materials towards nitrogen compounds is presented taking into account the chemical interactions established between adsorbent and adsorbate as well as the textural properties of the polymeric material.