Predicting the concentration of hazardous phenolic compounds in refinery wastewater-a multivariate data analysis approach.

The present study focused on the methodology for identification of the wastewater stream that presents the highest phenolic impact at a large oil refinery. As a case-study, the oil refinery, Petrogal S.A., in Sines, Portugal, was selected. Firstly, stripped sour water from the cracking complex was identified as the most relevant wastewater stream concerning phenolic emission. Secondly, multivariate data analysis was used, through projection to latent structures (PLS) regression, to find existing correlations between process parameters and phenols content in stripped sour water. The models developed allowed the prediction of phenols concentration with predictive errors down to 20.16 mg/L (corresponding to 8.2% average error), depending on the complexity of the correlation used, and R2 values as high as 0.85. Models were based in input parameters related to fluid catalytic crackers (FCC) feedstock quality, crudemix and steam injected in the catalyst stripper. The studied data analysis approach showed to be useful as a tool to predict the phenolic content in stripped sour water. Such prediction would help improve the wastewater management system, especially the units responsible for phenol degradation. The methodology shown in this work can be used in other refineries containing catalytic cracking complexes, providing a tool which allows the online prediction of phenols in stripped sour water and the identification of the most relevant process parameters. An optimised system at any refinery leads to an improvement in the wastewater quality and costs associated with pollutant discharge; thus, the development of monitoring online tools, as proposed in this work, is essential.

A corrosion evaluation of mild carbon steel in reclaimed refinery stripped sour water.

Reclaiming water for cooling systems in oil refineries has been strongly encouraged over the past years for decreasing the large consumption of fresh water, thus contributing to the efficient use of this valuable resource. In a recent study [Journal of Environmental Management 261 (2020) 110229], some of the authors studied the retention of phenols in refinery wastewater through reverse osmosis (RO) and found rejections of up to 98% of phenols and 99% of both chemical oxygen demand (COD) and total organic carbon (TOC). The permeates complied with the quality standards for make-up water in cooling processes. A missing aspect, important for the water to be used in the oil and gas industry, was the level of corrosivity of the new permeates. In this work the corrosion of mild carbon steel in the permeates and in the original cooling tower make-up water was studied by electrochemical techniques. The corrosion rate of steel in the permeates in aerated conditions was lower (between 0.053 ± 0.006 and 0.123 ± 0.011 mm year-1) than in the make-up water (0.167 ± 0.030 mm year-1), confirming their suitability for replacing make-up water in the cooling towers. The low corrosion of carbon steel was attributed to the low conductivity and absence of oxidizing species in the fluids, compared to fresh water.

Reverse osmosis performance on stripped phenolic sour water treatment - A study on the effect of oil and grease and osmotic pressure.

Technologies for water recycling within oil refineries have been gaining interest at an extensive rate due to the large volume of wastewater generated, high dependency of water and the progressive scarcity of this valuable resource. Phenols are part of a specific class of organic pollutants that have been contributing to a low-quality effluent in oil refineries due to their hazardous nature and strict environmental legislation associated. The reuse of stripped sour water within refineries is often blocked due to its rich phenolic content. This study evaluates the retention of phenols in refinery wastewater through reverse osmosis (RO) at its major source of emission, for water reclamation. The RO membrane selected exhibited rejections of up to 98% of phenols and 99% of both chemical oxygen demand (COD) and total organic carbon (TOC). Permeate quality remained intact despite flux decline caused by phenolic and hydrocarbon adsorption when the oil content, in the feed, reached 771 ppm. The effluent's low conductivity due to lack of salts led to minor osmotic pressure differences (less than 2.5 bar at a volume concentration factor of 3), therefore, showing appealing performances of reverse osmosis filtration. Characterization of all permeates obtained from cross-flow filtration experiments showed COD levels in line with water reuse quality standards for make-up water in cooling processes.

Oil refinery hazardous effluents minimization by membrane filtration: An on-site pilot plant study.

Experiments for treating two different types of hazardous oil refinery effluents were performed in order to avoid/minimize their adverse impacts on the environment. First, refinery wastewater was subjected to ultrafiltration using a ceramic membrane, treatment, which did not provide an adequate reduction of the polar oil and grease content below the maximal contaminant level allowed. Therefore the option of reducing the polar oil and grease contamination at its main emission source point in the refinery - the spent caustic originating from the refinery kerosene caustic washing unit - using an alkaline-resistant nanofiltration polymeric membrane treatment was tested. It was found that at a constant operating pressure and temperature, 99.9% of the oil and grease and 97.7% of the COD content were rejected at this emission point. Moreover, no noticeable membrane fouling or permeate flux decrease were registered until a spent caustic volume concentration factor of 3. These results allow for a reuse of the purified permeate in the refinery operations, instead of a fresh caustic solution, which besides the improved safety and environmentally related benefits, can result in significant savings of 1.5 M€ per year at the current prices for the biggest Portuguese oil refinery. The capital investment needed for nanofiltration treatment of the spent caustic is estimated to be less than 10% of that associated with the conventional wet air oxidation treatment of the spent caustic that is greater than 9 M€. The payback period was estimated to be 1.1 years. The operating costs for the two treatment options are similar, but the reuse of the nanofiltration spent caustic concentrate for refinery pH control applications can further reduce the operating expenditures. Overall, the pilot plant results obtained and the process economics evaluation data indicate a safer, environmentally friendly and highly competitive solution offered by the proposed nanofiltration treatment, thus representing a promising alternative to the use of conventional spent caustic treatment units.