PETROBRAS, Marlim Crude and Delayed Coking Units (DCU): A Perfect Trio

Weimar Lzaro, PETROBRAS / DOWNSTREAM - REFINING, Brazil, Francisco Carlos da Costa Barros, PETROBRAS / R & D , Brazil, Cludio Neves Borges, PETROBRAS / Cubato Refinery, Brazil. Abstract
There is a direct correlation among Marlim crude, the Delayed Coking Unit and PETROBRAS, owner of huge crude oil reserves in deep water reservoirs, from which the giant Marlim field stands out. Processing growing volumes of crudes with such deep-water characteristics has set challenges that the Company dealt with by fitting its refining plant facilities. These crudes generate large volumes of residues, which call for the construction of conversion units. In this specific case, the choice for the delayed coking process has a fundamental explanation: the process is profitable and adjustable to the fuel demands, parallel to the production of a petroleum green coke that fits anode grade specifications. Internationally recognized coke quality is also an indication of good operation. To complete the correlation, PETROBRAS has developed its own delayed coking technology. A combination of basic engineering, pilot plant research and industrial tests are the key for the present technological stage, keeping pace with the latest industrial developments. Today, PETROBRAS operates four Delayed Coking Units - DCU, three of which designed internally. Three new other units have already concluded their basic design and are in EPC phase.

Introduction
Campos basin reservoirs, which comprise a considerable portion of Brazilian reserves being Marlim the biggest field are known to produce deep water, heavy, naphthenic crudes. The research, exploration and production of this kind of deep water crude have ushered the Company to the world leadership in this area. PETROBRAS has been adapting its refining scheme to best exploit this crudes characteristic. Some papers and magazines have been published by PETROBRAS, focusing either on the geological or exploration aspects of Campos basin development. Other papers1 are focused on the impact of processing Marlim crude in its units and how the Company has dealt with that challenge. The growth of heavy crude production, the environmental restrictions on the burning of fuel oils and the increasing natural gas production, led to development and building of conversion and hydrotreatment (naphtha and diesel) units. Delayed Coking Technology (DCT) is an important route to increase liquid yields from these heavy crudes. The development of PETROBRAS technology both in Delayed Coking and Residue Fluid Catalytic Cracking units began during the 1980s, when Brazil had many constraints to import, forcing it to manage its own technological developments. Nowadays, the scenario has changed and the Company is a strong player in the petroleum product open market.

Development of Campos Basin and Marlim Crude

In 1974, the Campos basin, located offshore of Rio de Janeiro State, was discovered. Campos basin is presently responsible for almost 80% of the Brazilian domestic crude production. From the first oil discovery to 1985, when the giant fields of Albacora and Marlim were discovered, Brazilian oil reservoirs were found at increasing water depths. Marlim field stands in water depths varying from 400 to 1050 m. Today, the Company is facing the challenge of exploiting at 3,000-m water depths. Table 1 shows the typical quality analysis of these crudes.

Gravity, API Sulfur, wt.% Characterization Factor Total Nitrogen, wt.%

19.6 0.7 11.6 0.4

Table 1: Typical quality of Marlim Crude 2. The investments, efforts and contributions to the development in deep-water exploration and production have been recognized by being twice awarded with the OTC Distinguished Achievement Award. Today, PETROBRAS processes, in its refineries, a blend consisting of 80% of domestic crudes complemented with imported lighter ones. In 1997, the participation of Marlim field was responsible for 11% of the total refineries crude feed; in 1998, it increased up to 15%; in 1999, it rose to 23% and nowadays it exceeds 40%. During the period of 1990 to 1999, the largest individual component was 24,7 oAPI Cabinas crude. Since 2000, Marlim crude has taken the first place and is now responsible for 43% of Brazilian crude and 58% of Campos basin production. Though the peak in Marlim crude production is expected for the year 2002, other deep water heavy crude fields already discovered are expected to start and increase their production, meaning that the medium domestic oAPI gravity and heavy crude production will practically remain at current levels. Table 2 shows comparative typical yields for Marlim crude and Brendt, emphasizing residue yield, and Figure 1 shows the proportion of domestic crude processed in the refineries.

Yield ( vol %) LPG Naphtha Diesel (400C- ) Vacuum gas oil (FCC feed) Vacuum Residue (570 C+)

Marlim Crude Source: CENPES data bank 1 9 31 30 29

Brent Crude Source: BP data bank 1 37 38 14 10

Table 2: Typical yields for Marlim crude and Brent crude.

Figure 1: Brazilian crude processing at PETROBRAS refinery complex (tbpd x year)3.

PETROBRAS Refining Scheme

In some of the eleven refineries in Brazil, Marlim crude adds up to 80% of the Atmospheric Distillation Unit feedstock. To process this kind of crude it was necessary to adapt and to improve the refineries hardware. To reach its strategic goals, the Company is massively investing on fuel quality and to remain competitive and profitable in the deregulated market, there is no other alternative but to invest on bottom-of-the-barrel units. The Delayed Coking Process has proved to be the most attractive approach to decrease fuel oil production. The ability to process naphthenic crudes is a strategic objective. Considering the world growth reserves of such type of crudes (North Sea, West Africa, South America) and their price discount in relation to Brent, refiners that have already adapted their hardware to mitigate naphthenic corrosion problems, secure economic advantages in their processing4. In parallel, several factors are determining the changes in the refining schemes, among which we highlight: environmental restrictions, resulting in the production of cleaner fuels, thus decreasing refining margins, growing reserves of heavier and higher sulfur crude whereas the demand for highsulfur fuel oil is being reduced. Therefore, refiners are making their choice and examining technologies for the reduction of residual fractions and for the increase in low-sulfur distillates production. Today, the choice rests on a scheme combining conversion and hydrotreatment units. The chosen solutions for the Brazilian refining complex include Residue Catalytic Cracking and Delayed Coking Units in addition to Naphtha and Diesel Hydrotreatment Units (DHTU). There has been a continuous adjustment of the refineries to match the domestic market trend as shown in Figure 2.
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Figure 2: Domestic market trend for petroleum products . The involvement of imported crudes will prevail, despite Brazils reaching a domestic crude production similar to the internal market for petroleum products. The reason is that many products can not reach the market specifications if only Marlim crude is used. In December 2001, PETROBRAS reached 50 million barrels of Marlim crude exported to several countries worldwide.

PETROBRAS Delayed Coking Technology (DCT) Development

The Delayed Coking Unit converts heavy residual fractions vacuum residue, asphaltic residue or decanted oil into desirable liquid products, gases and coke. Nowadays, these units are essential to increase the tightened refining margins and to destroy the fuel oil surplus, especially when the crude generates a lot of residues. The yields for a DCU can be varied to meet the refiners objectives through the selection of operational parameters. DCU`s can be characterized by feedstock quality, operation conditions, equipment configuration and coke type, both anode and fuel grades, which are produced in accordance to those specific markets.

PETROBRAS experts published several papers5,6,7 showing the feasibility of optimizing the process with some simple modifications coming from research and development and basic design improvements. Over the years, the Company has been modifying its units to improve the reliability, profitability, flexibility and DCU operation, aiming at better operation performance for the Brazilian feedstock quality. A high production of residual oils and environmental restriction on the burning of heavy fuel oils are making the DCU process attractive to maximize the liquid yields. PETROBRAS also takes part in an international multiclient project (the consortium managed by University of Tulsa). Its main objective is to better understand the coking process, focused on kinetic experiments, by changing the process variables that affect the coke yield, residue cracking into higher quality products and reducing coke formation. Typical vacuum residue properties are shown in Table 3. On the other hand, Table 4 shows the comparison between a typical delayed coking pilot plant for Marlim vacuum residue and the refinery yields for the same feedstock. Properties o API Conradson Carbon Residue, wt% Sulfur, wt% Basic Nitrogen, ppmw Total Nitrogen, ppmw Vanadium, ppmw Nickel, ppmw Asphaltenes, wt% 100% Marlim 6.9 17.7 0.96 1.03 76 62 10.0 Refinery with 70% Marlim 7.5 19.6 1.01 0.32 1.0 55 45 8.3

Table 3: Properties comparison for Marlim vacuum residue and Feedstock with 70% Marlim in crude. Pilot Plant 7 100 % Marlim VR High pressure 11.6 3.5 15.1 41.7 10.1 27.6 Refinery I3 100 % Marlim VR Low pressure Fuel 5.4 3.2 14.4 46.4 16.6 25.1 Refinery II 3 70 % Marlim VR High pressure anode 4.6 4.5 22.2 27.9 22.9 27.7

Feedstock Coke drum operating Coke type Y Gas (C2 -), wt% I LPG (C3 C4), wt% E Naphtha, vol% L Light Gas Oil, vol% D Heavy Gas Oil, vol% S Green Coke, wt%

Table 4: Typical yields of DCU for Marlim vacuum residue operation.

PETROBRAS Coking Units

Presently, there are four DCU in operation: two units at RPBC Cubato Refinery, one unit at REPLAN Paulnea Refinery and one unit at REGAP Betim Refinery. Three other units have already completed the basic design phase and are planned to start up in the next few years. The first unit will be built at REPLAN. This second unit at that refinery is similar to the existing one except for some improvements. The second unit will be built at REFAP Canoas Refinery, and the third one will be erected at REDUC Duque de Caxias Refinery. Table 5 shows the summarized information on Delayed Coking Units. A new DCU basic design has just started for REVAP - Vale do Paraba Refinery, which will have a peculiar project base of processing 55% of asphaltic residue in its feedstock. There is also a plan for a new coking unit (linear program solution indication) for RLAM (Mataripe Refinery) for the year 2009. Its implementation is still pending on a strategic decision.

Design Start up Capacity m3 / d UCP- I / RPBC LUMMUS/ 1972 1,850 1974 UCP- II / RPBC PETROBRAS / 1982 2,318 1986 UCR / REGAP PETROBRAS / 1987 3,300 1994 UCR / REPLAN PETROBRAS / 1994 5,000 1999 UCR / REFAP PETROBRAS / 1997 2,000 2004 (**) UCR II / REPLAN (*) 5,000 2004 (**) UCR / REDUC PETROBRAS / 2001 5,000 2005 (**) (*) This unit is similar to UCR-I/REPLAN with improvements. (**) It is planned to start up this year. 3 Table 5: Summary PETROBRAS DCU . Unit Design/Year Some highlights of PETROBRAS DCU technology are:

Actual Capacity m3 / d 2,600 2,700 3,850 5,600 -

Average Coke Production t/d 740 750 1,050 1,400 -

Double fired heaters. Company started using the double-fired heaters design in DCU since the UCR/REFAP design, in 1998. These heaters have individual pass controls and are widely considered the most desirable ones for achieving long and profitable run length. A special support in the radiant coil section was developed, patent application number BR9707097A, in order to make horizontal arrangement of the tubes viable. Because of environmental restrictions on the burning of fuels, the Company has recommended the use of low NOx burners in the design as well as in all units in operation. Coke drums. In these drums, hot hydrocarbons from heaters are converted into vapors of lower molecular weight and petroleum coke. It is the most critical equipment due to the severity of the process conditions. From the accumulation of historical data, with coke drums inspection and identification of possible causes that contribute to failures, there are opportunities to improve design. A series of studies have been carried out to enable the evaluation of the coke drum skirt/shell geometry. During the decoking operation, when the bottom and top flanges are removed, there is risk of steam, hot water and coke fallout from the drum. To avoid this situation, newer designs provide a remote system for coke drum bottom and top head removal, patented number US005800680A, Sept. 1, 1998. Fractionation optimization. In order to maximize liquid yields and, especially, to produce coker diesel with properties acceptable to DHTU, the fractionator design has three gas oil cuts: light gas oil, medium gas oil and heavy gas oil. The light gas oil and medium gas oil streams are sent to DHTU. To minimize the pressure drop, the fractionators are designed with packed internals, vapor distribution and liquid collectors to maximize the valuable streams. Closed blowdown system. This system is designed to operate integrated with a sour water treatment unit, complying with the environmental requirements. The oil is recovered and sent to the feed drum or fractionator and the gases are routed to the fractionator overhead drum. The condenser, an air cooler on the top of blowdown drum, has a monitoring system that reduces the energy consumption. Coke fines settling system. The coke is discharged directly from the drums into the pit area via a
chute under the drum bottom head. In this pit area, the coke is dewatered prior to further downstream handling. The water is sent to a settling area where the coke fines are separated from the water, which is pumped back to a storage tank. PETROBRAS designing philosophy is low cost, and effective for operation and maintenance. The coke fines settling area is a series of flow settling chambers, followed by baffles with a sump for pumping out the clarified water. The bridge crane periodically removes the coke fines. In all of our designs, we have a good performance of this system.

Operating conditions. Today, PETROBRAS has designed cokers operating at low pressure on the coke drum and with low recycles.
PETROBRAS DCU operates with recycle lower than 10%, minimizing the coke and increasing liquid yields. Its coker design has a maximum 10% volume recycle ratio to provide flexibility as it has shown

to be needed in normal operations. In this design, pilot plant tests6 indicated which was the best recycle ratio that maximizes the light and the medium gas oil yields. The design feedstock for UCR/REDUC has 40% of asphaltic residue. This design has options to change some of operating conditions, as recycle ratio, or modifying the feedstock properties to adjust the coke quality (fuel or shot). There is no rule to decide which is the best type of operation to adopt because the market is changing. PETROBRAS design has enough flexibility to meet the requirements of modern refinery operations.

Instrumentation, interlocks and safety. DCU have been provided with instrumentation and
interlocks to increase operability and safety. In recent designs, for instance, permissive interlock of switch valves, inlet coke drum valve, vapor and water coke drum (utility) header valves, for coke drum quenching, have been added to further automate active action and increase safety. multivariable controller algorithms based on dynamic matrix control8. The development and implementation of this control in DCU are integrated with control software designed by PETROBRAS. This platform is also implemented in other processes (Distillation, FCCU, Alkylation, etc.) and other of the Companys Refineries. In order to predict product yields, it was developed the DCU simulator SIMCOQUE, whose input data include feedstock property variables, some operational conditions and also uses the simulator PETROX so as to calculate the mass and energy balance. The DCU design and operating conditions are important to maximize the use of heavy feedstock, as Marlim vacuum residue.

Advanced control. Both DCUs of Cubato Refinery have been running since 1998 with

Coke Quality Issues

To produce anode grade green coke, it is necessary to have optimum operational conditions, such as pressure, temperature, cycle time, recycle ratio and quality of appropriate feed. The conditions of the DCU at Cubato Refinery are adjusted to produce this type of coke from Marlim crude. Anode grade coke is used for producing carbon anodes that are consumed in the manufacturing of aluminum. Anode grade coke has a distinctive sponge appearance; however, this appearance by itself can be misleading since a fuel grade coke may also be sponge coke. What differentiate good anode cokes is not only the crude quality and contaminants, but also the particular operational concerns taken during its production. The destination of Cubato Refinery anode coke is to supply PETROCOQUE calcining Company or to export to United States and Canada. The fuel coke, which is produced by REPLAN and REGAP Refineries, is sold to the domestic market. Table 6 shows the typical characteristics of the green and calcined anode coke and fuel coke. The quality of the green coke from Cubato has good acceptance in the international market, especially because of its consistency during the calcination process and its low sulfur. Stream VCM, wt% dry basis HGI Ash, wt% Sulfur, wt% Vanadium, ppmw Nickel, ppmw Fixed Carbon, wt% Green Anode Coke 9.7 70 0.12 0.80 200 190 90 Calcined Anode Coke 0.1 31 0.11 0.73 230 210 Green Fuel Coke 10.8 80 0.20 0,80 205 150 88

Table 6: Typical characteristics of the green fuel coke.

Conclusions
PETROBRAS margins are directly related to its domestic crude production, mainly from Campos basin, being expected that it will steadily increase in the next decade. The medium API gravity of total domestic production is expected to remain fairly constant, considering the fields programmed to begin their productive phases, even taking into account some new heavier crudes that have been discovered. The Company has extensively invested on fuel quality, optimizing the liquid yields, the ability to process Marlim crude and the bottom-of-the-barrel technology as strategic objectives. And the Delayed Coking Process has proved to be the most attractive way to decrease fuel oil production and maximize liquid yields. The strategy of developing the processing of heavy crudes includes operating plant, pilot plant studies, engineering, technology and participation in international partnership research groups, such as the one with Tulsa University. It is important to include on the economic benefit of heavy crudes processing the re-optimization cost of the existing refinery configurations, prices of available crudes, capital costs of new units plus the cost of continuing to meet environmental limits. PETROBRAS Delayed Coking Technology is composed of research and development, operating and troubleshooting experience.

References:
1. Marsiglia, M.E.P.L., Absoro de Petrleo Marlim pela PETROBRAS. Paper presented at the Rio Oil and Gas Expo and Conference 2000, Rio de Janeiro, Brazil, Oct. 2000. 2. Zlio, E.L. and Guimares, R.C.L., Avaliao Padro de Combustveis do Petrleo Marlim P-32 (19.6 API). PETROBRAS Research and Development Center Internal Report: CT-054/01. CENPES/PDEAB/TAP, Rio de Janeiro, Brazil, 2001. 3. PETROBRAS Confidential Report. 4. Skippins, J., Johnson, D. And Davies, R., Corrosion-Mitigation Program, Oil & Gas, Sept. 2000. 5. Lzaro W., Santos C.A.R., Barros F.C.C., Molleri O.G.L., Lucredi H.A., PETROBRAS Runs Delayed Coking Heater Discontinuously. Paper presented at the AIChE 2001 Spring Meeting, Houston, USA. 6. Barros F.C.C., Bernardo F.C. A., Chan A., Bria M., Maximum Distillate Yields in a Delayed Coking Unit. Paper presented at the AIChE 1998 Spring Meeting, New Orleans, USA. 7. Filgueiras, R.O.C., ... , Coqueamento Retardado de RV Marlim. PETROBRAS Research and Development Center Internal Report: CT-04/92. CENPES, Rio de Janeiro, Brazil, 1992. 8. Oliveira, L. L. and Carrapio, O. L., Multivariable Control Increases Coke Unit, Refinery Throughput, Hydrocarbon Processing, July, 1998, pp. 77-83.