17th WORLD PETROLEUM CONGRESS BLOCK 2: FORUM 3: Excelling in Refining and Delivering Quality Petrochemicals From High-Sulphur Crudes

to Ultra Low Sulphur Fuels

TITLE: HYDROCRACKING A WAY TO PRODUCE HIGH QUALITY LOW SULPHUR MIDDLE DISTILLATES Authors: Donizeti Aurlio Silva Belato, Jorge Roberto Duncan Lima, Maria Regina Rezende Oddone (Petrobras/Brazil) INTRODUCTION During the last 20 years, Petrobras has been making a strong effort to be self-sufficient in petroleum production. More than 20 billion US$ were invested in crude oil exploration and production. Most of Brazils oil production is Offshore, mainly in deep water. The deeper we explore, the heavier the crude becomes. Nowadays, Brazils crude production is around 1,5 million bbl/d. 80 % of which comes from Campos Offshore Basin, located in Rio de Janeiro. These oils have peculiar characteristics like low paraffin, low sulphur and high nitrogen content. Many efforts have been made in downstream area in order to optimize their refining. Process schemes are being evaluated and some new units are being built. Aiming at fitting the higher market share of Brazilian heavy crude, the heavy fuel oil displacement by Natural Gas and higher middle distillate demand many conversion units have been requested to match fuel production and demand, such as: Catalytic Cracking (FCC), Residue Catalytic Cracking (RFCC), Delayed Coking. Hydrotreating units have been also built to process unstable streams from these conversion units. Due to a more severe environmental regulation and new requirements for engines Hydrocracking process seems to be a good alternative to fit supply and demand, producing high yields of high quality middle distillates. CRUDE PROPERTIES Here, the typical Brazilian Crude and Light Arabian Crude properties are presented. Despite having high sulphur content, Light Arabian crude is more paraffinic, lighter and has lower nitrogen content than the Brazilian one. Properties API Characterization Factor Sulphur Content (weight %) Total Nitrogen Content (weight %) Basic Nitrogen Content (weight %) CRUDE DISTILLATION YIELDS The average product profiles obtained in a crude distillation unit processing Brazilian and Light Arabian crude are presented bellow. Comparing the yields obtained from both crude oils it is clear that the Brazilian one requires higher conversion capacity than the Light Arabian. In order to get lighter products FCC, RFCC, Delayed Coking and Hydrocracking units could be used to convert Vacuum Gasoil and Vacuum Residue. In addition some hydrotreating units would also be required to reduce sulphur and nitrogen to the specification levels of transportation fuels. Cuts Naphtha (IBP 180C) Kerosene (180 250C) Full Range Diesel (180 380C) Vacuum Gasoil (380 560C) Vacuum Residue (560C+) Light Arabian(2) Yields (volume %) 24 14 36 24 16 Brazilian Campos Basin (1) Yields API Sulphur (volume %) (wtppm) 9 55 270 8 38 1900 33 29 5100 29 17 7900 29 6 9600 Nitrogen (wtppm) < 10 600 3800 8900 Brazilian Campos Basin (1) 20 11.6 0.7 0.5 0.16 Light Arabian 33 11.9 2.0 0.1 0.03
(2)

HYDROCRACKING Hydrocracking is a very flexible process to convert heavy fractions into middle distillates. Since 1987, Petrobras has been deeply studying this process in order to include it in its refining complex. More than 100 pilot plant tests have been performed at Petrobras Research Center using as feedstock: Vacuum Gasoil, Deasphalted Oil, Heavy Coker Gasoil, Light Cycle Oil and blends. These feeds, when obtained from Brazilian crude, have low paraffin and high nitrogen content exhibiting particularly low reactivity. Tests have been performed in two steps. In the first one, feedstock is pretreated in order to reduce nitrogen content to a desired level. In the second one, final hydrotreating and hydrocracking reactions take place. Three pilot plants (1, 3 and 7 liters catalyst capacity) have been used. Both partial and total conversion modes, with zeolite and amorphous catalyst types have been tested according to product targets (maximum middle distillates or Group II lube stock). A wide range of operational conditions has been explored and both mild and severe hydrocracking have been covered as follows: Pressure: Temperature: Total Space Velocity (LHSV): Hydrogen/Feed Ratio: Hydrogen Consumption: 90 180 bar 320 410C 0.25 1.0 h-1 3 3 600 1600 Nm /m 1.5 3.5 wt %

All products have been characterized in detail and the results have been compared with current and future Brazilian specifications. Middle distillates obtained at high severity mode surpass future specifications. Kinetic models were developed and two basic engineering projects were made. The first one was designed to work at total conversion in order to maximize fuels (mainly high quality middle distillates). The second one was designed for partial conversion in order to maximize lube oil base stocks. As the feeds have low reactivity and high quality products were required, both units were designed to work at high severity mode. A two step zeolite scheme was chosen in both designs. Concerning the hydrocracking product quality and yields some data are shown bellow. Even at low severity operation all products have low sulphur content (< 50 wtppm) and reach the ultra low sulphur levels (< 10 wtppm) at high severity conditions. Middle distillates have excellent ignition properties being appropriate for new engines. The unconverted fraction (Residue) obtained at high severity can be used to produce high VI lube oil base stocks classified as Group II. Residues produced at low or medium severity are excellent feedstock to FCC since they are highly hydrogenated and have low contaminant contents (sulphur, nitrogen, basic nitrogen, metals, polyaromatics and carbon residue). HCC PRODUCTS: YIELDS AND PROPERTIES RANGES (3,4) Product Yields (volume %) 6 - 25 8 - 40 25 - 40 33 75 4 - 60 API Sulphur(a) Nitrogen(a) Special Properties(a) (wtppm) (wtppm) < 10 <1 RON = 60 - 70 < 10 <1 Smoke Point = 23 28 mm < 10 <2 Cetane Number = 46 - 58 < 10 <2 Cetane Number = 43 - 53 < 10 <5 Viscosity Index = 92 110(b)

Naphtha (15-150C) 55 - 62 Kerosene (150-240C) 40 - 44 Heavy Diesel (240-380C) 30 - 40 Full Range Diesel (150-380C) 33 - 41 Residue (380C+) 25 - 35 (a) At high severity operation. (b) Viscosity Index after solvent dewaxing and with Pour Point = -12C. CONCLUSION

Hydrocracking Process is a good and flexible way to convert heavy cuts from Brazilian crude into high yields of high quality middle distillates easily achieving the future environmental requirements. When operating in partial conversion mode under high severity conditions the unconverted feed can be used to produce Group II lube oil base stocks.

REFERENCES 1- Zilio E.L., Guimares R.C.L. Avaliao Padro de Combustveis do Petrleo Marlim P-32 (19,6API) Petrobras Research Center Internal Report: CT-TAP n 054/01 CENPES/PDEAB/TAP 2- Irio S.M.B.M. Avaliao Padro de Lubrificantes de Petrleo rabe Leve (32,6API) Petrobras Research Center Internal Report: CT n 094/96 CENPES/DIQUIN/SETAV 3- Belato D.A.S., Oddone M.R.R., Silva R.M.C.F.da The Use of hydrocracking Process to Produce High Quality Diesel Oil from Brazils High Nitrogen Feedstocks Chapter 5 in Chemistry of Diesel Fuels, New York: Taylor & Francis. 4- Belato D.A.S., Chaves C. Confirmao das Condies de Projeto do HCC REDUC 2 Estgio Etapa de HCC HC-5 Petrobras Research Center Internal Report: CT-THPE n 055/01 CENPES / PDEAB /THPE