Efficient Removal of Sulfides from Oil Industry Effluents using Advanced Processes

Chemical Chemical Engineering Engineering 2016 2016 REMOVAL REMOVAL OF EFFLUENTS OF THE OIL INDUSTRY EFFLUENTS OF THE OIL INDUSTRY OF SULFIDES SULFIDES FROM AQUEOUS FROM AQUEOUS Dr. Ana Karla Costa de Oliveira Dr. Ana Karla Costa de Oliveira Instituto Federal do RN Instituto Federal do RN - - BRASIL BRASIL

PRODUCED PRODUCED WATERS WATERS Produced waters are complex mixtures which contain a large number of contaminants including finely dispersed oil, metals, and gases such as H2S and CO2, that are originated from oil and natural gas.

WATER SAMPLE CONAMA RESOLUTION 357/2005---to reuse water, with respect to class 3, the values allowed for H2S and oil content are 0.3ppm and 20 ppm, respectively.

OTHER PROCESSES PROCESS PROCESS DESCRIPTION DESCRIPTION OXIDATION WITH HYDROGEN PEROXIDE The hydrogen sulfide removal process, in the form of sulfur or sulfuric acid via anodic oxidation of sulfuric acid. CAUSTIC EXTRACTION Thet are able to extract sulfur compounds in the form of mercaptans.

PROCESS DESCRIPTION The process consists of putting the hydrocarbon solution into contact with the contaminant, and the adsorbent impregnated with metals that show affinity with sulfides. ADSORPTION PHYSICOCHEMICAL SOLVENTS Processes with physicochemical solvents use a mixture of physical and chemical solvent. The physical solvent is responsible for removing the largest amount of acid gases, while the chemical solvent puts on the finishing touches.

AMINES Amines with carbon chains longer than 6 are practically insoluble in water by hydrophobicity. The basic nature of amines increases their reaction power with sulfuric acid.

AMINES AMINES TESTED AMINES TESTED MOLECULAR FORMULA MOLECULAR FORMULA DUOMEEN DUOMEEN O O OLEYL-RNHCH2CH2CH2NH2 ARCUAD ARCUAD 2 2C C- -75 75 R2N+((CH2)2Cl) DUOMEEN DUOMEEN T T TALLOW-RNHCH2CH2CH2NH2

CONDITIONS Amines DUOMEEN O ARCUARD 2C-75 DUOMEEN T Amount of amine/ % Jet Fuel (v:v) 0.01; 0.05; 0.10; 0.25;0.50 O/A Ratio (Organic/Aqueous) (v:v) 1/3

SAMPLE WITH LARGE AMOUNT OF SULFIDE (BLUE COLOR)

PROCESS PROCESS The batch system is shown in Figure 1. It consists of a magnetic shaker (Tecnal-Brazil) (1) used to homogenize the extractant with the solvent (jet fuel), which was kept in a beaker (2). The organic material is sent through a micropump (Cole-Parmer, Brazil) (3) to a separation funnel (4), where the organic and aqueous phases, contaminated with sulfides and fine oil, are mixed. At the base of the separation funnel, the treated water was analyzed in a DR 2000

RESULTS AMINES REMOVAL OF SULFIDES(%) 76% 59% 42% DUOMEEN O ARQUAD 2C-75 DUOMEEN T

RESULTS The figure The figure below O O produced produced the below presents presents the the best best result. the results results of of sulfide result. sulfide removal removal with with the the use use of of three three amines amines, , showing showing that that DUOMEEN DUOMEEN

RESULTS

RESULTS RESULTS

CONCLUSION It was concluded that the Duomeen O amine, solubilized in jet fuel caused a higher percentage of H2S removal (76%) and resulted in a low TOG value of 5mg/L in the treated water, at a fraction of 0.25% amine/jet fuel. Despite the similarity between the amines Duomeen o and Duomeent, the latter did not obtain satisfactory results, due to the large unsaturation in the structural composition of Duomeen T, making it more soluble in water, which was not the aim of this study, and resulting in low sulfide and oil removal efficiency. The turbidity results confirm good oil removal with Duomeen O.

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