IBP1330_12 THE COKE DRUM THERMAL KINETIC EFFECTS Maria M.

Aldescu1, Sim Romero2, Mel Larson3

Copyright 2012, Brazilian Petroleum, Gas and Biofuels Institute - IBP

This Technical Paper was prepared for presentation at the Rio Oil & Gas Expo and Conference 2012, held between September, 1720, 2012, in Rio de Janeiro. This Technical Paper was selected for presentation by the Technical Committee of the event according to the information contained in the final paper submitted by the author(s). The organizers are not supposed to translate or correct the submitted papers. The material as it is presented, does not necessarily represent Brazilian Petroleum, Gas and Biofuels Institute opinion, or that of its Members or Representatives. Authors consent to the publication of this Technical Paper in the Rio Oil & Gas Expo and Conference 2012 Proceedings.

Abstract
The coke drum thermal kinetic dynamics fundamentally affect the coker unit yields as well as the coke product properties and unit reliability. In the drum the thermal cracking and polymerization or condensation reactions take place in a semi-batch environment. Understanding the fundamentals of the foaming kinetics that occur in the coke drums is key to avoiding a foam-over that could result in a unit shutdown for several months. Although the most dynamic changes with time occur during drum filling, other dynamics of the coker process will be discussed as well. KBC has contributed towards uncovering and modelling the complexities of heavy oil thermal dynamics.

1. Introduction
The delayed coker process is one of the refinerys most complex processes due to the batch processing in the coke drums being coupled with the more or less continuous operation of the product fractionation section of the unit. The heart of the process is the exposure of the heaviest crude fraction (usually vacuum resid) to thermal cracking temperatures in a fired heater at short residence time, followed by a longer soaking time in coke drums where the coke is formed and hydrocarbon vapors are disengaged. The delayed coker process is a multi-variable constrained process, with non-linear relationships between its variables. The process incorporates very dynamic changes with time.

2. Brief History of the Delayed Coking Process

The thermal kinetic process was invented by Vadimir Shukhov, a Russian engineer, and it was patented in 1891. Later on the Shukhov process was modified by William Burton and Robert Humphrey to enhance gasoline yield. In 1929 the first delayed Coker Unit, based on the Burton process, was built by the Standard Oil of Indiana at Whiting. Arguably the process of thermal cracking has not significantly changed since its development almost 100 years ago. However, significant improvements have been made in the equipment design and metallurgy. Due to an increased emphasis on safety, refineries have focused on several aspects that minimize personell exposure around the delayed coker unit such as: automatic heading and unheading devices, remote coke cutting tools, etc. As a result, the delayed coker has become one of the refinerys most safe, reliable and profitable processes.

3. Thermal Reaction Types

Generally, when one discusses the delayed coking mechanisms which occur in the coke drums, the over-all descriptive phrase black art is invoked. This is largely due to the fact that the coking mechanisms cannot be altered as

______________________________ 1 Consultant - KBC ADVANCED TECHNOLOGIES 2 Principal Consultant KBC ADVANCED TECHNOLOGIES 3 Principal Consultant KBC ADVANCED TECHNOLOGIES

Rio Oil & Gas Expo and Conference 2012 much by changing operating variables as compared with other heavy upgrading processes such as catalytic cracking. The delayed coking process can be divided into two sections: 1. the heater and transfer line acting as a plug flow reactor 2. the coke drums acting as a batch reactor There are two types of semi-batch reactions that occur in the coke drum: polymerization/condensation and thermal cracking. The polymerization reactions are preferentially favored by the presence of the larger and heavier molecules. These reactions directly impact the delayed coker unit yields, the coke product properties and the unit reliability. They also require that various adjustments be made in the unit to ensure that the heat and material balances changes do not upset the delayed coker process as well as the associated downstream unit operation. Commercial cokers produce coke that is a combination of both of these reaction mechanisms. The reactions that occur in the fired heater tubes (where most of the unit feed passes through before entering the coke drums) are usually steady state thermal kinetic reactions. There are some exceptions, such as during the drum switches, when the reactions in the heater may become more dynamic. This occurs when refineries use the heater ramping philosophy in the last hours of the drum filling, whereby the heater outlet temperature is ramped up as the drum is filled. The reason for this strategy is to ensure a somewhat homogeneuos coke quality and to maximize the production of liquid yields. In a coke drum the coke product that forms in the top of the drum has higher volatile material content (VCM) than the coke formed in the middle of the drum due to the lower residence time of the coke near the top of the drum.

4. Coke Drum Thermal Dynamics

At the beginning of a drum filling, the drums are relatively cold and act as a heat sink until the drums come up to normal operating temperatures. The cold drum metal wall causes some of the vapors generated in the heater and transfer line to condense and cool the material collecting in the drum. Initially the amount of product leaving the drums is significantly lower than later in the drum filling cycle. The drum pressure and the unit combined feed ratio influences the coke produced; higher drum pressure or higher recycle ratio will increase the coke yield and quality, reduces the ash content and increases the crystalline coke structure. Drum stripping and cooling after the drum has been filled also affects the overall unit thermal kinetics. The temperature rate of change on the coke drum walls is translated into stress on the drum. The drum stripping and blowdown operations also influence the final steps into the drum kinetics. Full coke drums are stripped with steam and water (or, in some cases, with water only). During the latter part of this drum stripping process the exit vapors (a combination of steam and hydrocarbons) are routed not to the main fractionator but to a blowdown system which separates the water and the oil. Coke drums must be stripped and cooled down before the coke can be drilled out via drills and super high pressure water. The drum insulation is critical in ensuring that the reactions happen at the needed temperature for cracking and polymerization. The penalty for having poor insulation around the drums is temperature drop and reduced liquid yields. The vapors leaving the coke drums are at bubble point conditions. Most cokers are injecting a quench medium in the overhead vapor line to ensure that no dry points are present, thus arresting any potential propagation of cracking reactions which could plug the overhead line with coke. The quench medium is usually a coker gasoil or a slop oil from the coker unit drum quench system. The unit yields and coke product qualities such as hardgrove index, volatile carbon material, and coke density are strongly affected by the proper balance between time and temperature. Petroleum coke is generated through two types of mechanisms: precipitated asphaltenes and polymerization of large molecular weight components.

5. Coke Drum Reaction Path

The coke drum reaction path can be defined as thermal cracking and polymerization reactions. These are two parallel reactions, as shown in figure 1. The light part of the oil will crack to lighter components, while much of the heavy part of the oil will polymerize to semi-coke or pitch. The smaller aliphatic side chains attached to the semi-coke will crack off as lighter gas products.

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Figure 1: Coke Drum Kinetic Reaction Path

6. Reaction Products

Figure 2: Statistical Distribution of Reaction Products Figure 2 shows a snap shot of an oil feed molecule that is in the coke drum at a given time. The lighter part of it will crack to lower boiling range material, while the heavier part of the oil feed will polymerize to higher boiling range material. Coker yields depend on the type of crude mix which the refinery processes as well as key operating parameters in the coker unit itself, especially coking temperature, pressure, and the recycle ratio. Typically the temperature can only be adjusted within a narrow range in order to control volatiles in the petroleum coke by-product; if the volatility is too low, it will take longer to drill and cut the coke out of the drum when it is full. Most refiners with delayed cokers generally try to run them at a pressure and recycle ratio that is as low as practical without sacrificing unit throughput or allowing the coke quality to deteriorate too much. In addition to crude assay qualities and coker operting conditions, another key factor which affects the coker yields is steam stripping in the upstream vacuum tower. Steam stripping is affected by the amount of steam used and the number and condition of the stripping steam trays. Yields at the coker is also affected by the flash zone temperature in the vacuum tower. Higher flash zone temperatures are indicative of deeper cut points, which in turn generate a heavier coker feed. A deeper cut feed has a significant impact on the heat balance in the coker, which ultimately affects the overall thermal cracking in the delayed coker.

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Figure 3: Theoretical Batch Kinetic Model Figure 3 represents a snap shot of a oil feed molecule at a given time in the coke drum. The heavy oil feed molecule will react generating light gas, liquids and pitch or intermediate coke. As time progresses, the pitch or intermediate coke will react to finished coke and additional vapor.

7. Foaming Kinetics
Maintaining the appropriate operating temperature mitigates foamover effects during drum filling and during the initial steam stripping. Once the foam front is generated it is hard to supress it, unless antifoam material is injected. The challenge that the antifoam offers to the refiner is that it is a silica based product; silica is a noted catalyst poison for the downstream units, including naphtha hydrotreaters. Most delayed coker unit operators are trying to minimize the antifoam consumption to mitigate the negative impact to the hydrotreating units where coker products must be treated. Fortunately, advances have been made in applied gamma-ray technology which makes it easier to monitor the foam level in a coke drum as it is filling. Figure 4 shows a snap shot of the resid/ pitch entering the coke drum. In the very first hour the pitch/ foam front will be at the peak of its formation. As time progresses, the resid-pitch and the pitch-foam will react to pitchsolid coke.

Figure 4: Foaming Kinetics If the drum switch is performed too fast, the foaming can recur. During the initial drum switch there may appear a foam front again, also known as post-switch foaming, as the drum vapors are lined up to the main coker fractionator. 4

Rio Oil & Gas Expo and Conference 2012 Foaming tendancy can depend on the type of crude mix being processed. Refiners find different crude mixtures to have varying potential to cause foam in the coke drum. KBC evaluated the potential to foam of a mixture of Maya crude which is high asphalenic and M-100 Ural crude which is paraffinc.

Figure 5: Foaming Potential for Maya/ M-100 Crude Mixture Figure 5 shows that regardless of the crude slate, if the temperature in the drum is low, the potential to foam is very high. In a situation when the temperature in the drum is extremly low (below 815 oF), then there can be a 100% probability of foaming. If, on the other hand, the temperature in the drum in extremly high the potential to foam, regardless of the crude mixture, will approach 0% probability. The challenge in achieving such high temperatures in the drums comes from the risk of coking in the heater tubes when running at a very high coil outlet temperature (COT). While crude M-100 could allow for higher COTs of up to 935 oF, the Maya crude will only allow COTs of up to 925 o F. When processing this mixture of Maya/ M-100 crude slate there is a challenge in finding the optimum temperature that doesnt prematuarely coke the heater but at the same time mitigates the foam potential in the coke drums.

8. Drum Cooling Dynamics

KBC studied the dynamics that occur during the drum cooling, also known as the drum quenching step. Figure 6 shows a tri-dimensional graphic, where the x-axis represents the time expressed in hours, the y-axis represents the elevation in the drum from the bottom to the top expressed in feet and the z-axis is the temperature of the coke matrix expressed in degree F. This graphic assumes that the quenching water is injected through the bottoms of the coke drum. At the beginning of the cooling, the coke in the bottoms of the drum will cool faster than the coke in the top of the drum. During the first half hour of cooling, the water will absorb heat from the mass of coke and will vaporize. Initially the generated steam will slighlty raise the temperature of the cooler coke in the top of the drum, which allows for the pitch which didnt have enough residence time to continue reacting. As time progresses, the entire coke matrix will cool down.

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Figure 6: Drum Cooling Dynamics During the first few minutes of the off-line drum steam stripping, a significant amount of heavy hydrocarbon is removed from the drum. At the time of the switch the coke drum is full of solid coke but has a void space of roughly 50%. This void space is filled with reacted and unreacted hydrocarbon. The steam stripping serves to sweep the drum of hydrocarbons remaining in the void space. This will take several minutes due to the porosity of the coke, and during this initial part of the stripping the drum overhead is still lined up to the main fractionator, thus allowing for recovery of the heavy hydrocarbons. After a fixed period (usually between 15 minutes to an hour) the drum is then switched to the blowdown system. Hydrocarbon liquids will still be stripped off from the drum but the quantity of these liquids going to the blowdown system will drop off fairly quickly. However the coke drum will continue to produce light oils and noncondensible gases well into the water quench step. This additional emanation of light hydrocarbons and gas is the result of continued cracking reactions in the coke drum. The yield of light hydrocarbons falls exponentially with the cooling coke but again the porosity of the coke causes the flow of gas to continue exiting the drum until the end of the water quench step. The coker blowdown system is the most difficult section to develop a heat and material balance. The heat and mass balance is a moving target and is in constant change. This makes designing a blowdown system extremely difficult and complex. Most design contractors rely on rules of thumb and past experience when designing a coker blowdown system.

9. DC-SIMTM KBC Technology

KBC has contributed towards uncovering and modelling the complexities of heavy oil thermal dynamics. Once the kinetic model is calibrated, it can be run in predict mode to study the effects of changing operation. In a properly tuned model, a number of key parameters can be modified to predict yields and product qualities. Such key parameters can include feed rate and feed qualities, combined feed ratio, furnace outlet temperature, drum pressure, and product fractionation cut-points. Given these inputs, the model predicts how the unit will behave in terms of yields, product properties, drum fill time, and quench rates. Figure 7 shows a snap shot of the Delayed Coker model and Coker Gas Plant simulation in the Petro-SIMTM environment. The model is tailor made for each refinery configuration and typically includes a reactor model, detailed tray-by tray or Distop fractionation, tube by tube fired heater simulation (to predict the slope of temperature change function of the coke deposited in the tubes), wet gas compressor, and gas plant fractionation.

Figure 7: Delayed Coker Simulation using Petro-SIMTM Petro-SIMTM - is a trade mark of KBC Advanced Technologies Inc.

10. Quotations and Bibliography

Science and technology multiply around us. To an increasing extent they dictate the languages in which we speak and think. Either we use those languages, or we remain mute. - J.G. BALLARD 6

Rio Oil & Gas Expo and Conference 2012 ROMERO, S., ALDESCU, M. Thermal Kinetics- Dynamics in Delayed Coker, Galveston-Coking.com, April/May 2012 Troubleshooting Process Operations, Norman P. Lieberman (Third Edition), Penn Well Publishing Co, 1991 FAVOR, A. Engineering Education Today in History Blog: Burton Patents Thermal Cracking, January 7, 2011. http://www.k-grayengineeringeducation.com/blog/index.php/2011/01/07/engineering-education-today-in-history-blogburton-patents-thermal-cracking-4/ ROMERO, S., SAYLES, S. Coke Yield Estimate for Heavy Aromatic Oil at Comparatively Low Temperatures, Client Report, May 2009