J. Chem. Chem. Eng. 9 (2015) 51-55 doi: 10.17265/1934-7375/2015.01.007 D DAVID PUBLISHING Influence of Pressure to the Hydrocracking Process of Goudron in the Presence of a Modificated Suspended Halloysite Gulbeniz Mukhtarova National Academy of Sciences of Azerbaijan, the Y. H. Mamedaliyev Institute of Petrochemical Processes, Baku 1025, Azerbaijan Abstract: The main results of hydrocracking of goudron under reduced pressure in the presence of a suspended catalyst have been analyzed. It was investigated the influence of pressure to hydrocracking process of goudron. It was determined that with increasing from 0.5 to 4.0 MPa, the yield of light oil products increased from 47% to 58% mass. Key words: Hydrocracking, goudron, suspended catalyst, modificated catalyst, gasoline, diesel fraction. 1. Introduction Development of the existing refinery technologies and creating of new technological processes allowing to increase the depth of oil refining and to improve the quality of oil products the urgent economical and technical problems of oil-refining industry, the solution of which is associated with the involvement in the processing of residual oil feedstock types. New technologies of oil refining in OR should become energy- and resource-saving of non-waste or low-waste, non-polluting, economically feasible. The range and quality of products and materials, produced by oil refineries also should meet the current requirements. Thermal and thermal-oxidative processes of oil residua refining are characterized by low quality of the obtained products and limited possibilities to enhance the depth of oil refining and production of valuable motor fuels and feedstock for petrochemistry. Hydrocracking process is one of the most efficient processes for obtaining high-quality motor fuels from heavy oil residues (fuel oil, goudron) [1-9]. * Corresponding author: Gulbeniz Mukhtarova, Docent/Ph.D., research fields: hydrocracking of heavy petroleum residues, increase of oil refining and refining and technology of oil. E-mail: gulermuxtarova@yahoo.com. 2. Experiments The purpose of the work is to investigation the obtaining process of fuel components from low-pressure hydrocracking of the goudron obtained from Baku oils in the presence of modificated,suspended halloysite with transition metals (Ni, Co) for obtaining additional (extra) light oil products in order to deepen the oil refining. The influence of the pressure in the range of 1.0-4.0 MPa at 450 о C to the processing of the goudron hydrocrackingin, the presence of the modificatedsuspended high-dispersed halloysite with transition metals has been investigated. 3. Results and Discussion As the experiment results showed, the depth of goudron hydrocracking with the catalytic additive dispersed in the feed essentially depend on the process temperature and pressure. The yield of light oil products increased from 27% to 52% mass with rise of temperature from 400 to 450 C (1.0 MPa pressure). With increasing of pressure from 1.0 to 4.0 MPa (temperature: 450 C) the yield of light oil products increased from 52% to 57% mass, the yield of gas decreases from 12% to 10%, amount of cock is
52 Influence of Pressure to the Hydrocracking Process of Goudron in the Presence decrease from 7% to 4% (Table 1). In the Table 2, it is shown that the quality characteristics of gasoline and diesel fractions obtained by the hydrocracking of goudron in the presence of the modificated suspended high-dispersed halloysite with transition metals. As seen from the Table 2 with increasing of pressure from 1.0 to 4.0 MPa (temperature: 450 C) amount of aromatic hydrocarbons containing in the gasoline decrease from 7.21% to 5.0%, amount of unsaturateds from 3.52% to 0.458%, amount of sulfur from 633 ppm to 548 ppm, iodine number from 8 to 4 g J 2 /100 g. Amount of iso-paraffins increased from 38.79% to 45%, octane number makes 74 points according to the research method. The change of pressure also influence to the quality characteristics of obtained diesel fractions. So that, with increasing of pressure from 1.0 to 4.0 MPa (temperature: 450 C) amount of sulfur decrease from 0.17% to 0.10%, iodine number from 17 to 15 g J 2 /100 g, amount of aromatic and unsaturated hydrocarbons decrease and Table 1 Influence of pressure to the hydrocracking process of goudron in the presence of a modificated suspended halloysite. Yield of products (% mass) P H = 1.0 МPа; 2 P H = 2.0 МPа; 2 Gas C 1 -C 4 12 11 10 Gasoline i.b.p.-200 C 26 26.5 28.0 Fraction 200-360 C 26 27.5 29.0 Σ fraction < 360 C: 52 54 57 Residue > 360 C 29.0 29.6 29 Coke 7 5.4 4 = 4.0 МPа; Table 2 Influence of pressure to the qualitative characteristics of products of hydrocracking process of goudron. Indices = 1.0 МPа; = 2.0 МPа; Gasoline fraction Density at 20 C (kg/m 3 ) 0.702 0.673 0.665 Paraffins 37.08 38.7 37.932 Iso-paraffins 38.79 45.46 44.94 Unsaturateds 3.52 2.026 0.658 Naphthenes 13.4 8.694 11.56 Aromatics 7.21 5.12 5.0 Octane number 71.65 74.06 74.98 Content of sulphur (% mass) 0.0633 0.0564 0.0548 Iodine number (g J 2 /100 g) 8 7 4 Diesel fraction Density at 20 C (kg/m 3 ) 0.840 0.8393 0.8346 Content of sulphur (% mass) 0.17 0.16 0.10 Iodine number (g J 2 /100 g) 17 16 15 Freezing temperature ( С) -30-28 -32 Flash point +46 +48 +50 Hydrocarbon content (% mass): by method NMR (nukleer magnet resonance) Aromatics 22.0 23.0 20.0 Unsaturateds 1.0 0.5 izi Naphthenes-paraffins 78.0 76.0 79.5 Cetane number 49.4 50.0 51.0 =4.0 МPа;
Influence of Pressure to the Hydrocracking Process of Goudron in the Presence 53 cetane number makes 50-51p. In the Figs. 1 and 2, they have been described NMR spectrum of the diesel fraction obtained from the hydrocracking of goudron at pressure of 2.0 and 4.0 MPa (temperature: 450 о C). Table 3 shows the quality data of bottom fractions obtained by the hydrocracking of goudron in the presence of the modificated suspended high-dispersed halloysite with transition metals. Fig. 3 has been described by NMR spectrum. Fig. 1 NMR spectrum of the diesel fraction obtained from the hydrocracking of goudron at pressure of 2.0 MPa and 450 о C. Fig. 2 NMR spectrum of the diesel fraction obtained from the hydrocracking of goudron at pressure of 4.0 MPa and 450 о C.
54 Influence of Pressure to the Hydrocracking Process of Goudron in the Presence Table 3 Qualitative characteristics of the residual fraction (fr > 360) obtained from the hydrocracking of goudron. Indices Density at 20 C (kg/m 3 ) 0.9125 Content of sulphur (% mass) 0.47-0.55 Freezing temperature ( С) +19 Flash point +184-(+190) Viscosity (mm 2 /s 20 o C) 62.50-64.60 Ash content (%) 0.1 Hydrocarbon content (% mass): (by method NMR) Aromatics 26.0 Unsaturateds 0.7 Naphthenes-paraffins 73.3 Fig. 3 NMR spectrum of the residual fraction obtained from the hydrocracking of goudron. 4. Conclusions Thus, the gasoline and diesel fractions obtained from the hydrocracking of goudron in the presence of the modificated halloysite with the suspended transition metals can be used as a component for motor fuels after hydrocleaning. The obtained gasoline fraction can be used as a feedstock in the pyrolysis process, but the compositon of the obtained gas allows to use it as fuel in oil refineries. References [1] Yu, P. S. 2006. Refining of Heavy Petroleum Residues Using Various Aromatic Additives. Chemistry of Solid Fuel 6: 57-62. [2] Khadzhiyev, S. N., and Kadiyev, K. M. 2009. The Future of Petroleum Deep Refining. The Chemical Journal 9:34-37. [3] Suvorov, Y. P. 2007. Hydrogenation of Petroleum Residues Using Co-Mo and Mo-Mn Catalysts. Chemistry of Solid Fuel 6: 26-30. [4] Ryabov, V. A. 2009. Problems of Development of
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