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Upgrading The Bottom of The Barrel
Upgrading The Bottom of The Barrel
Some alternatives to carbon rejection are H2 addition technologies, which include ebullated bed hydrocracking and xed-bed hydrotreating/hydrocracking,
among others.
Residuum properties
The properties of the vacuum residuum in the feed are a key factor in determining which technologies will work best. These key properties include
Conradson Carbon (Concarbon) residue, heavy metals such as nickel (Ni) and vanadium (V) that poison catalysts, the asphaltene content, sulfur and
organic nitrogen. These key properties determine which technologies are feasible and which secondary upgrading technologies can be used to upgrade
the feed into marketable fuels.
Carbon: 83%–87%
H2: 10%–14%
Nitrogen: 0.1%–2%
Oxygen: 0.1%– 1.5%
Sulfur: 0.5%–6%
Heavy metals (e.g., Ni and V) under 10 ppmw.
The market for both the products produced and the byproducts, such as coke, low-BTU fuel gas, low-sulfur fuel oils, paving or roo ng asphalt, etc., is a
strong determining factor in the evaluations. The market pays more for higher conversion process technologies. However, with the right set of economics,
the incremental values of the products can provide su cient economic incentives.
Several options of carbon rejection and H2 addition processes are evaluated here, as well as various combinations of these two basic process types.
Process schematics, operating conditions, yields, catalyst and chemicals, and economics are presented.
Following the primary upgrader, a secondary upgrader that usually co-produces other low-value streams like VGOs will be required. Hydrocracking and
FCC are the most commonly used secondary upgrading processes.
The semi-re ned products are upgraded into environmentally friendly fuels using conventional technologies and well-known re nery processes that are
used for processing the crude. These processes are shared between the conventional section of the re nery and the residual upgrading units to provide
economy of scale.
Using block ow diagram simulators is useful for evaluating the cases. These programs contain databases of the feedstocks and models of the individual
units, and simulate re ned products blending into nished fuels, along with providing utility requirements.
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FIG. 1. A schematic of the delayed coking process.
Within the coke drum, a combination of temperature and time thermally decomposes the residuum feed into a broad mixture of materials from gases to
naphtha, light and heavy gasoils. These drum products are then fed back to the main fractionator, which separates the products into gas, gasoline, light-
coker gasoil and heavy-coker gasoil in a continuous fashion, and recycles the bottom resid product back to the coking drum(s). The coke left behind in the
drum is removed by using high-pressure water. This process is referred to as “decoking” the drum. Coke exiting the bottom of the drum usually goes
through a crusher car to pulverize it into ½-in chunks, which fall into a sluice and are carried to the dewatering area as water slurry. A schematic of the
delayed coking process is shown in FIG. 1.
The solid coke product is sometimes calcined to remove volatile hydrocarbons before being transported to market. Environmental regulations prohibit the
direct combustion of coke unless the combustion includes process facilities to recover hydrogen sulfur oxides and other pollutants. These facilities are
included in the design of the continuous uid coking process. One advantage of this process over the batch-wise delayed coking process is the recovery of
energy from combusting some of the coke product.
Some delayed cokers process special composition feeds (i.e., highly aromatic), and can produce a more valuable, metallurgical grade of coke that is used to
make anodes for the production of aluminum and other chemical () products. The properties of the feedstock determine the applicability.
Typically, the gas produced is treated to remove hydrogen sul de (H2S) and other impurities, then sent into the re nery fuel gas system. The coker naphtha
is sent to the hydrotreater and catalytic reformer, either by itself or with other similar naphthas. The light gasoil (e.g., kerosine/diesel boiling range) can go
to the hydrocracker for secondary upgrading. Typically, the heavy-coker gasoil goes to the FCCU for secondary upgrading.
The economics of a delayed coker depend on the sale price of the coke and the cost of transporting it to market. Coke is typically 20 wt% of the feed, and
coke purchasers generally only pay the transportation cost to their facility.
Visbreaking
This technology is very old, and has become useful only in areas where heavy fuel oils are used for power generation and fuel for ships. It is still used in
some European countries to produce heavy fuel oil for boilers. Like the delayed coker, the visbreaker uses time and temperature to partially decompose the
feed and reduce the viscosity. The primary di erence between coking and visbreaking is that coking produces a solid bottoms product and recovers
essentially all of the oil product. Visbreaking leaves a signi cant amount of oil in the bottoms product. For this reason, coking achieves pro table oil
recoveries in the range of 55%–65%, whereas the less expensive visbreaking process achieves recoveries of approximately 25%–35%.
The coke deposits on the visbreaker’s heater tube walls and in the soaker drum must be periodically removed. This makes visbreaking a semi-continuous
process, meaning that several parallel units are required with one in decoking mode.
The visbreaker produces small amounts of naphtha and gasoil products, as well. The o gas must be amine treated for H2S removal before entering the
re nery fuel system. One potential application for visbreaking would be producing a pumpable oil from the tar sands (bitumen) upgrading process. Most
tar sands deposits are located near the Arctic Circle. Transporting a syncrude composed of products of a crude, vacuum and visbreaker unit into a less
viscous and transportable material has economic potential. Additional diluents may be required for this approach, as asphaltene compounds typically settle
out from the bitumen in piping in cold climates.
Another option for the gasi cation product is to further convert it into syngas [one part carbon monoxide (CO) and two parts H2]. Syngas is the starting
feed for many petrochemical () plant operations, such as an H2 plant.
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The common part of the delayed coker or resid upgrading technology is the reactor-coking vessel. The uid coke recirculates back to the reactor, making
more coke by reacting with the feed. Some of the coke is combusted to supply heat for the coking reactions.
RFCC process
This process is similar to conventional FCC, primarily with enhanced regeneration capacity. The feedstock is limited to an upper, maximum level of metals,
which will poison the catalyst. The Concarbon number and asphaltene content determine the special requirements of the regenerator section. These
carbon-rich compounds form coke on the catalyst, which must be removed during regeneration (burning with air), generating heat. Most of the heat
generated is transferred by uidization back to the uidized reactor, where it is utilized. Steam generation coils can recover some of this heat, as well.
Due to the higher-than-normal heavy metals, the catalyst must be replaced to keep the equilibrium metals content within a tolerable level. The atmospheric
residuum of light crudes, such as West Texas Intermediate (WTI), can be fed to an RFCCU. A simpli ed process ow diagram of an RFCCU is shown in FIG.
2.b In this scheme, the reactor and regenerator are con gured side-by-side. The RFCCU is similar to a gasoil FCCU except that the regenerator must be
designed to remove the higher heat loads resulting from the increased coke formation. Typically, steam coils or another type of steam generation system
are used to remove heat.
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FIG. 2. A schematic of the RFCC process.b
The previously mentioned technologies are the most commonly used upgrading processes in the re ning () industry. In areas where it is environmentally
permitted, vacuum residuum can be manufactured directly in the vacuum unit into No. 6 fuel oil for use in boilers and in marine fuel, as well as into paving
asphalt. The asphalt can be further processed into roo ng asphalt in an air blower, or cut back with solvent for custom road applications.
The semi-re ned products from these upgrading technologies must be further processed to make marketable products. FCC and hydrocracking are used
individually or in combination. The products produced from the secondary residual upgrading processes are then integrated into the re nery upgrading
process units used for the lighter crude/vacuum unit semi-re ned products.
H2 ADDITION TECHNOLOGY
Unlike carbon rejection technology, H2 addition uses catalyst, high pressure and an H2-rich atmosphere to break down large molecules into smaller ones,
and hydrogenate them. Lique ed petroleum gas (LPG) is in the C3–C4 range, gasoline is in the C5–C9 range, kerosine is in the C9–C15 range, and diesel is
in the C15–C20 range. All of these saleable products are blended to the required product speci cations for new, low-sulfur gasoline,1 and new ULSD.2 The
kerosine range material is used primarily for jet fuel and has less stringent environmental requirements. The key properties are ash point, freeze point and
smoke point. Flash point is controlled by the front-end components; freeze point is controlled by the back-end components, and smoke point is controlled
by the aromatics content and back-end components.
In H2 addition processes, H2 saturates the ends where carbon-to-carbon bonds are broken by hydrocracking reactions. H2 also converts sulfur to H2S,
organic nitrogen to ammonia (NH3), and saturates most ole ns and some naphthenes and aromatic compounds. Most of the processes use xed-bed
reactors loaded with di erent catalysts to perform the required functions. Typically, multiple beds are required to limit increases in exothermic temperature
caused by quench H2 injection. Licensors provide their own proprietary catalysts or have catalyst manufacturers produce catalyst to their speci cations.
Some catalysts are generic and available from multiple catalyst vendors.
The design of the reactor must have su cient wall thickness to withstand the high pressures. Typically, the base metal is a low-alloy cobalt/molybdenum
(Co/Mo) or Ni/Mo carbon steel with su cient amounts of Mo, Co or Ni to resist high-temperature corrosive attack. The base wall is then overlaid with
austenitic stainless steel using a special welding procedure to ensure that the overlay does not disband. Since these heavy-wall alloy reactors require
considerable time to fabricate, long lead times are required in the construction schedule.
Most hydroprocessing technologies use recycled H2 to provide su cient partial pressure for the reactions, while suppressing coking reactions. Makeup H2
is added as required to replace the H2 consumed by the reactions.
As previously mentioned, both NH3 and H2S are produced from side reactions. To prevent the deposition (sublimation) of ammonium bisul de (NH4HS)
and chloride crystals in the downstream () equipment, a water wash is included at temperatures where these reactions are predicted to occur. It is
recommended that this injection system be designed to ensure that the wash water is adequately and uniformly distributed to keep these potential solid
deposits dissolved in the wash water. Ultimately, this spent wash water is recovered in one of the separators and is sent to a sour water stripper. For each
mole of NH3 in the reactor e uent, a mole of H2S combines with NH3 to produce a mole of NH4HS. The unreacted H2S is partially absorbed in the spent
wash water.
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FIG. 3. A schematic of a xed-bed hydroprocessing unit.
The main fractionator removes the lighter products, including LPG, gasoline, jet fuel and diesel. The higher-boiling components ow to the FCCU. Due to
new regulations for low-sulfur gasoline and ULSD, additional processing is required to provide a low-sulfur blendstock that can be blended with other fuel
blendstocks.
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FIG. 4. A schematic of a proprietary ebullated-bed process technology.c
Comparison of technologies
A comparison of the various carbon rejection and H2 addition technologies is shown in TABLE 1; however, the table only discusses the relative merits of
these technologies. These upgrading processes must then be integrated into the overall re nery. The three areas that are most a ected and require
debottlenecking include the sulfur recover units (SRUs), H2 production units and utilities (steam, fuel gas, electric power, cooling water circulation, etc.).
(/media/6285/elshout_table1.jpg)
Ultimately, the nal upgrading of the semi-re ned products into fuels is required, which includes cat reforming, isomerization, fuel blending, hydrocracking
and FCC. In the US, heavy fuel oils have nearly disappeared; however, some areas of Eastern Europe still produce fuel oils, such as bunker or No. 6 fuel oil,
for power plants and fuel for ships.
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FIG. 5. A block ow diagram of a fully integrated re nery.
Economic evaluation
Simple, before-tax payout is the means for screening various processing technologies early in the comparison stage of technology selection. Incremental
revenues are divided into the incremental capital cost to determine the number of years to payout for each option. To determine the payout of a processing
unit, subtract the unit’s feed costs from the net product revenues to determine the net product revenues. Then, the incremental cost of utilities, labor,
catalyst and maintenance are subtracted to determine net revenues.
Conducting the evaluation in this manner avoids getting into the economics of the existing units. If the streams entering the new project perimeter are
considered as feedstocks, and the semi-re ned products leaving the “new project” area are considered products, then the economics can be determined
on the upgrading of the products rather than the nal products, which are a blend of existing and new operations. These revenues are based on in-house
price values of the upgraded streams. When the streams leave the project perimeter, the economics can be greatly simpli ed. Using inter-re nery costs for
feeds and products allows the evaluation to be made on a net upgrade basis and not on the whole re nery.
A further step toward achieving the total conversion of the bottom of the barrel to middle distillates is the slurry hydrocracking technology (1). The slurry
process operates in the presence of a catalyst with sub-micronic particles. The catalyst is more stable than the conventional hydrocracking catalyst, and it
can be used in the presence of much heavier feedstocks. After the reaction and the separation sections, the catalyst remains in the residue of the vacuum
distillation unit with the nickel (Ni) and vanadium (V) sul des. Conversion higher than 95% is achieved by recycling the heavier unconverted fraction
through the reactor, so that only this fraction remains in the reactor for a longer residence time.
The innovation of the new slurry technology consists of an oleo-soluble molybdenum octoate dissolved in the feedstock. The mixture is fed to the reactor,
and H2 is supplied through a distributor located at the reactor bottom. Under these conditions, the catalyst precursor is converted to molybdenite, which is
crystalline-layered MoS2, with an average particle size of a few nanometers.
The nano-sized hydrogenation catalysts and an original process scheme allow the complete feedstock conversion to valuable distillates, avoiding the
production of residual byproducts, such as petcoke or heavy fuel oil. The heart of the process is a slurry reactor in which the heavy feed is hydrocracked to
lighter products in the presence of nano-sized, molybdenum-based catalyst.
The feedstock conversion starts with thermal breakage of the C-C bonds and generation of free radicals that are suddenly quenched via H-uptake
reactions, preventing the free radical recombination that could evolve to coke formation. The presence of an active Mo-based catalyst, such as
molybdenum sul de, promotes the H2 activation reaction.
The use of unsupported slurry catalysts is particularly useful in feedstock containing high concentrations of pollutants, particularly metals and asphaltenes.
Contrary to the conventional supported catalysts that are utilized in xed- and ebullated-bed reactors, the dispersed molybdenite is not susceptible to
plugging problems due to the metals and coke deposits on the porous supports.
The upgraded oil withdrawn from the slurry reactor is sent to a separation section to recover gas, naphtha, and middle and vacuum distillates. The
unconverted material, as well as the dispersed catalyst, are recycled back to the reactor and blended with the fresh feed. The recycle stream is
reprocessed to achieve almost total conversion, while a small purge is necessary to eliminate metals buildup.
The process ensures complete metal removal (HDM), excellent Conradson Carbon Residue and sulfur reduction (HDCCR and HDS), and good
denitrogenation (HDN). Another peculiar characteristic of the slurry technology process is the production of a high-quality vacuum gasoil (VGO) with low
sulfur and aromatic content that can be further converted into transportation fuels or used as new marine bunker.
The rst industrial unit started on October 14, 2013 at the Eni’s Re nery in Sannazzaro, demonstrating the possibility of making a correct scale up from
the tests carried out on a pilot and demonstration plant. At the moment 3 licenses have been sold to three di erent oil companies (Total, Sinopec and
Zhoushan); the Maoming plant is currently under construction and will be operational in 2020. As described in a previous article (/news/2017/08/online-
exclusive-sunset-boulevard-for-delayed-coking), EST is currently the best technology for converting the bottom of the barrel, much better than, for
example, the delayed coking technology as it is able to achieve better economic results and lower environmental impacts.
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This technology will be detailed in Giacomo Rispoli’s, Executive Vice President Portfolio Management for Eni, keynote address at IRPC Europe
(http://www.hpirpc.com/events/irpc-europe-2018/event-summary-e656fdfb46434a43b1a d68f3c5e4e7.aspx), which will be held in Milan, Italy in
June.
References:
(1) Refers to EST (Eni Slurry Technology)
(2) Sunset Boulevard of Delayed Coking (/news/2017/08/online-exclusive-sunset-boulevard-for-delayed-coking)
Takeaways
Bottom-of-the-barrel upgrading costs can run in the billions of dollars. Past evaluations have shown that the higher cost of the H2 addition technologies,
when combined with carbon rejection technologies, can show robust payouts. This is primarily due to the increased volumes of more valuable products
that are produced by the hydroprocessing processes. Carbon rejection technologies generally decrease the volume of valuable products, since carbon
rejection reduces the net volume of the nal products.
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A detailed comparison of upgrading technologies is summarized in TABLE 2. A complete evaluation is needed to compare the various technologies. The
necessary steps to select the best upgrading technology include:
REFERENCES
1. Elshout, R. V. and C. S. Bains, “USA motor fuels sulfur levels: Moving up a tier—Part 1:Gasoline sulfur,” Hydrocarbon Engineering, 2005.
2. Elshout, R. V. and C. S. Bains, “Moving Up a Tier—Part 2:Ultra-low sulfur diesel,“ Hydrocarbon Engineering, 2005.
NOTES
a Flexicoking is a proprietary resid upgrading technology from ExxonMobil.
b Refers to Honeywell UOP’s RFCC process.
c Refers to CB&I’s LC-Fining technology.
The Authors
Elshout, R. (/authors/e/energy-systems-engineering/elshout-r) - Energy Systems Engineering, Pasadena, California
Ray Elshout has 30 years of process and project engineering experience with Fluor, Jacobs and Unocal. At present, he is a consultant with Energy Systems
Engineering. His primary experience is in process design, including retro ts, revamps and expansions. Mr. Elshout holds BS and MS degrees from the
University of Michigan.
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Lynn Brown has 40 years of operations and design experience in re ning, petrochemicals, gas processing and production at Worley Parsons, Unocal,
Jacobs and Fluor. Her primary expertise is in operations, instrumentation reliability, and design and revamp of crude units, desulfurizers and distillation
systems.
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