Experimental Study of a Pilot Plant Deasphalting Process in Supercritical Conditions

Crdenas V. O. C., Lodi L., Souza. R. A., Wolf Maciel M. R., Maciel F. R., Medina L. C.
1

Laboratory of Separation Processes Development, University of CampinasUNICAMP; zip code: 13083852, CampinasSP, Brazil 2 Laboratory of Optimization, Project and Advanced Control, University of CampinasUNICAMP, zip code: 13083852, CampinasSP, Brazil 3 Petrobras SA, CENPES/PDEDS, Center of Research and Development, zip code: 21941915, Rio de JaneiroRJ, Brazil Corresponding author: viktor.cardenas@yahoo.com.br, phone: +55 19 35213971, fax.: +55 19 35213965.

ABSTRACT
In view of the great economic development of emerging nations such as Brazil, projections indicate that asphalt production in the country may double in the next five years due to the large consumption of this product in both internal and external markets. This paper aims to study the deasphalting process on laboratory scale through the design and development of a supercritical extraction experimental unit. In this unit, extractions in different conditions are being carried out, in order to evaluate the properties of the obtained products and their future applications in the production of both type I lubricants and better quality asphaltenes. The experimental unit was developed in the Laboratory of Separation Processes Development (LSPD - UNICAMP) in partnership with PETROBRAS. Extractions in both subcritical and supercritical conditions were carried out using petroleum residue as the main feedstock and propane as the solvent. During the experiments, temperature and pressure were manipulated in order to maintain the solvent in the required conditions, thus facilitating the extraction process and avoiding sharp changes in the system. In this paper, the physical structure of the extraction unit and data obtained during the extractions are presented. The results show that, in supercritical conditions of extraction, the products in the deasphalted oil (DAO) streams present adequate characteristics for the production of lubricant oils and those in the asphalt residue (AR) stream present an elevated concentration of asphalt molecules.

INTRODUCTION
Nowadays, the asphalt demand in Brazil has increased due to the construction and reconstruction of roads. This makes the investment in technology essential to guarantee the supply of this material, not only in a quantitative aspect but also to improve the asphalt quality. At the same time, the demand for lighter oil is forcing the oil industry to research and develop new refining processes, which must be employable to both crude oils and increasingly heavy residues. This aims to obtain final products of refining process with better quality and according to government specifications. Currently, refineries face the challenge to process heavy oils which higher levels of nitrogen compounds and naphthenic acidity. Therefore, the deasphalting process of heavy petroleum

and petroleum residues, in supercritical conditions, is a promising and efficient alternative to the separation of asphalt from oil, which is used in lubricants production [1,2]. In 1936, Wilson et al.[3] developed a separation process based on phase equilibrium, which became the basis for the propane deasphalting process that is still in use in lubricant oil refining. Although this process isnt a supercritical extraction conceptually, it uses the changes in solvency power of a liquid around its critical point. Its known that propane characteristics as a solvent can be easily changed in the pressure-temperature space. With the increase of these properties, propane turns into a very selective solvent, which facilitates the separation of the desired products (paraffinic oils and asphaltenes). The aim of this paper is to design and develop a deasphalting experimental unit on lab scale, which can process petroleum with low API degree, such as atmospheric and vacuum residues. The extractions were carried out according to the parameters used in the deasphalting process in supercritical and subcritical conditions, always considering the equipment limits. In addition to the equipment installation and the experiment, analytical techniques were used to characterize the properties of the obtained products.

MATERIALS AND METHODS

The extraction unit was designed and constructed by the LSPD team, at the School of Chemical Engineering (UNICAMP), with the company PETROBRAS as a partner. Basically this experimental unit consists of an extractor vessel and a separator vessel, besides accessories such as pumps, valves and control systems (pressure and temperature). It is interesting to emphasize that this equipment is peculiar due to its dimensions (the extractors internal volume is of 3L), allowing it to process high volumes of samples. The sample used in the deasphalting process was a residue from an imported petroleum, called SACI. One solvents were used: propane, the best indicated solvent for this kind of extraction due to its selectivity. The extractions were performed considering previous studies by the laboratory team [4]. The parameters used in this study (Table 1) were chosen aiming both quality and yield of the final products. Table 1. Temperature and pressure conditions used in the extractions Condition 1 Subcritical Temperature C Pressure (bar) 75 36 Condition 2 critical 95 55 Condition 3 supercritical 100 70

The extraction process consists firstly in the unit preparation, in which leaks and pressure and temperature controls were checked. Approximately 1L of the raw material, previously characterized, was heated to reduce its viscosity and poured into the extractor. After

closing the extractor, the solvent started to be slowly pumped until the desired working pressure, while the system was heated until the desired set point. Upon reaching the operating conditions, the extraction occurs for approximately 60 minutes. After this, the system was depressurized, forcing the overhead stream (a mixture of solvent and DAO) out to the separator vessel, where DAO condensation and solvent evaporation take place. In the separator vessel, the overhead final product was collected (Figure 1) and stored for analysis. The bottom stream from the extractor vessel, called asphalt residue (AR), was also collected for analysis.

Figure 1. Simplified flowchart of the process and samples. Different properties of the fractions were analyzed: molar weight and asphaltenes content (high performance size exclusion chromatography), turbiscan and minerals, according to the obtained volume of each sample. With this characterization, it was possible to check the potential of the products to lubricants and asphalt production.

RESULTS AND DISCUSSION

Table 2 shows the results of the analyses for both molar weight and asphaltenes content in the extractors feed and in each stream obtained under different process conditions. Table 2 Sample molar weight and asphaltenes content in the studied conditions Feed Molar weight (g/gmol) Asphaltenes content (%) 1471 3,66 Condition 1 DAO 734 0,1 RASF 1607 4,87 Condition 2 DAO 658 0,04 RASF 1539 4,27 Condition 3 DAO 795 1,16 RASF 1575 4,71

DAO deasphalted oil; AR asphaltic residue Through the analysis of Table 2, it is verified that the results obtained with condition 2 presented the most interesting values for lubricant production due to the low molar weight of the the DAO stream. The low asphaltenes content in the DAO stream contributes to lower its molar weight. It is important to notice that condition 2 is the one closest to propanes critical point, in which the solvent, as it is known, presents a greater selectivity. In condition 3 (supercritical), despite the molar weight of the DAO stream not being as low as in condition 2, a high concentration of asphaltenes is still observed. This shows that the process is able to concentrate the asphaltenes in the AR stream. Turbiscan analysis is an optical scanning technique which shows the dispersion of asphaltenes in the samples. The asphaltenes presence in the analyzed samples is verified through the separability number (SN). Through Figures 1 A, B and C, it is verified that both the feed and the RASF presented greater values in comparison with the DAO, respectively SN = 6,52; 5,87; 0,31. This value indicates that, in the DAO sample, the asphaltenes content is low or nearly null, which is very important since it shows that the extraction was free from contaminants (such as metals and sulfur) and selective, precipitating the higher weight molecules (asphaltenes and maltenes) in the extractor and extracting low molar weight hydrocarbons.

C Figure 1. Optical scanning analysis: A) feed; B) DAO; C) AR, obtained through supercritical deasphaltation Another form of observing the asphaltenes presence in Figure 1 is through the analysis of the flocculation area for each sample. In Figures 1A and 1C (respectively feed and AR), the flocculation area is greater, which shows the asphaltenes dispersion in the sample; in Figure 1B (DAO), practically no area above the reference line is observed, indicating minimum or nearly null presence of dispersed asphaltenes in the sample. Table 3 presents the results for metal presence analyses in each process stream, as well as sulfur content and Conradson carbon residue. These results are compared to the feed stream (petroleum residue, API degree = 10) analyses, which demonstrate the changes that the deasphalting process in supercritical conditions induces in the feed stream. Table 3 Characterization of the feed stream and the resulting streams of a supercritical deasphalting process of SACI petroleum Assay Density (20C) Total sulfur (% massa) Micro Conradson Carbon Residue (% mass) Iron (mg/Kg) Nickel (mg/Kg) Vanadium (mg/Kg) Separability number (SN) 6,52 0,32 5,87 11,8 41,5 29,13 <1 <1 3,6 4,2 11,6 42,1 19,62 1,45 23,26 Feed 594,03 3,3018 DAO 0,9814 2,8481 AR 702,79 3,0911

It is observed that the obtained results for this residue, in the specified conditions, were satisfactory and coherent. Through the metal analyses results, it is verified that its presence in DAO is minimal in relation to the feed and AR streams. This demonstrates that the used extraction conditions present a low selectivity towards metals, since their majority remains concentrated in the AR stream. The described phenomenon can also be observed in the total sulfur analysis, since the DAO stream presents a low sulfur level. This result is of great interest, since there is a rising concern of refineries in producing sulfur-free products, due to its high contamination potential. In relation to Conradson carbon residue analysis, a signification diminution is observed in the DAO stream, which is beneficial to lubricant production.

CONCLUSIONS In observance of the obtained results, it is possible to conclude that the deasphaltation process with propane is an efficient process for light oil extraction from heavy petroleum residues. The critical and supercritical conditions present the best results in view of the products properties, which are directed to the production of asphalt and lubricants. It is important to emphasize that the supercritical condition generates products with superior quality and greater yield of the final products, as verified during the extractions. This paper, however, was aimed at the products quality study, not its yield.

ACKNOWLEDGMENTS
The authors acknowledge the financial support from FAPESP (processes 2010/12955-7 and 2011/00875-1), to REPLAN for analytical support and CENPES/PETROBRAS for the partnership and supply of raw material.

REFERENCES
[1] Rodrigues, J.C. (2006). Internal Report. LDPS, Campinas Brazil. [2] Mendes, M.F., Ferreira, C.Z. and Pessoa, F.L.P., 2005, Deasphaltation of Petroleum Using nd nd Supercritical Propane. 2 Mercosur Congress on Chemical Engineering, 4 Mercosur Congress on Process Systems Engineering, Enpromer, Costa Verde Brazil. [3] WILSON, R. E.; KEITH, P. C.; HAYLETT, R. E. Liquid-propane Use in Dewaxing, Deasphalting, and refining heavy oils. Industrial & Engineering Chemistry Research, Washington, v.28, n.9, p.1065-1078, 1936. [4] CARDENAS, C. V. O. ; PhD Thesis, LOPCA/LDPS, UNICAMP, 2010