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Upgrading in Alberta

There are three major oil sands deposits in Alberta. The largest is the Athabasca
deposit, which is located in the northeast of the province. The main population centre of
the Athabasca region is Fort McMurray. The second largest oil sands deposit is the Cold
Lake at the south of Athabasca deposit. The main population centre of this region is the
City of Cold Lake. The smallest oil sands deposit is known as Peace River, which is
located in northwest-central Alberta. A fourth deposit called Wabasca is a small area
connected to the Athabasca region.
The oil sands contain 9-13% bitumen, 3-7% water, and 80%85% mineral solids. Of
the solids, 15-30% are fine particles, predominantly clays with less than 44 m in
diameter. The challenge in production is to separate the bitumen not only from the sand
grains but also from the micron and submicron-sized clay particles and water. The
bitumen fills most of the pore volume between the mineral particles, giving a very low
permeability to operate in-situ. A typical reserve has an average grade of 9-12%: above
10% bitumen is considered high grade, while a low grade ore is 6-8%. Ores with lower
grade bitumen are not economic to extract. The distinction between bitumen, extra heavy
oil and heavy oil is rather inaccurate. The Cold Lake, Athabasca, and Peace River
deposits are grouped together as oil sands by legal definition, and combine bitumen
(Athabasca) and heavy oil (Cold Lake) resources. The Orinoco reserves in Venezuela are
classed as extra heavy oils, based on their viscosity, but are otherwise similar to
Athabasca bitumen in their processing characteristics.
The following table compares the typical viscosity of various grades of oils.

Material API
Bitumen and extra heavy oil <10
Heavy oil 10-19
Medium crude oil 19-34
Light crude oil 34-42

The chemical species in bitumen are thought to be heavily degraded by bacterial
action as the alkanes and lighter boiling fractions are absent in bitumen. The remaining
oil has a low concentration of paraffinic groups, and many of these groups are side chains
in larger molecules. The high concentration of sulfur, nitrogen and oxygen which more
complicates the bitumen processing is also a consequence of this ancient bacterial attack.
The following table provides the typical concentration of sulfur, nitrogen and metals in
various oil sands deposits.

Sulfur (wt%) Nitrogen (wt%) Nickel (ppm) Vanadium (ppm)
Athabasca 5.14 0.56 150 290
Cold Lake 5.10 0.45 200 490
Lloydminster 4.69 0.53 140 190
Peace River 7.02 0.63 130 410

The mining operations in Athabasca are unique as the only petroleum mining
operations in the world. The sequence of steps consists of mining, to remove the ore for
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processing, followed by extraction to remove the bitumen from the ore, forth treatment to
clean the bitumen, and then upgrading to process the bitumen. The oil sands deposits in
other regions such as Cold Lake are too deep to be mined, thus in-situ operations to
extract the bitumen and pump it to the surface are practiced in those regions.
The two major approaches to upgrading in Alberta are processing the bitumen to
approach the specifications of conventional light sweet crude, or dilution to meet the
minimum pipeline specifications for viscosity. Transport in common pipelines requires
that the crude oil meets several key specifications such as: gravity >=19 API, viscosity
<= 350 cSt at pipeline temperature (5-38C), solids and water content <=0.5%, vapor
pressure <100 kPa, untreated cracked petroleum = 0%, and no organic chlorides.
Producers of bitumen and heavy oil, by mining or steam injection (in-situ), blend in
natural gas condensate in order to make their crude oil pipelinable. For example, Imperial
Oil produced 112*10
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bbl/d of bitumen at Cold Lake in 2002 and sold 145*10
3
bbl/d of
bitumen/condensate blend with a blending ratio of 0.29*10
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bbl/d of bitumen/condensate.
As the bitumen production is expected to increase fast over the next decade, the demand
for gas condensate diluent will increase and the pipeline transportation becomes very
important and challenging in the following years. Stable transportation of these complex
thick liquids that usually contain some solid particles over long distances is also a
challenge in nature. CFD can greatly contribute in monitoring the pipeline operations
coupled with SCADA systems by predicting the changes in situations such as leakage or
depositions. Enbridge and TransCanada are the major pipeline operators in Alberta.
The refineries that would be accessed by expanding the pipeline networks would be
able to take some fraction of their intake from oil sands sources. The majority of the
refineries in North America are designed to operate with light sweet crude, which can be
processed by fluid catalytic cracking (FCC). This technology is not compatible with the
properties of oil sands products from bitumen, expect as blend with conventional crude
oil. Blending synthetic crude oil with conventional crude oil in these refineries can reduce
the yield of gasoline, and affect the quality of the jet fuel and diesel oil products. These
limitations tend to restrict the fraction of synthetic crude oil to 20-30% of the total feed to
the refinery. Refineries that are equipped with hyrdocracking units, such as Shell
Scotford and Suncor/PetroCAnada Strathcona, can run a higher fraction of synthetic
crude, up to 100% in the case of Shell Scotford.
Upgrading can be considered a subset of refining technology, with shifts to
accommodate the prevalence of non-distillable components in the bitumen. The processes
used in upgrading are drawn from refining of conventional crude oils. The main
differences are that the refinery emphasizes the production of highly purified streams that
meet all the specifications for the consumer use, whereas the upgraders produce an
intermediate stream. Upgraded products must give a naphtha cut which has a nitrogen
content low enough for catalytic reforming, a middle distillate cut which is suitable for
use as a diesel blendstock, and a gas oil cut which can be used in a fluid catalytic cracker.
These downstream uses for the synthetic crude limit the acceptable nitrogen and sulfur
contents, and constrain the cetan number of the mid-distillate. The following table shows
the current upgrading facilities in Western Canada.
The first step in upgrading is recovery of diluent from bitumen in the Diluent
Recovery Unit (DRU) in a distillation process. The diluent is reclaimed and send back to
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bitumen production where it is used again. The bitumen is then sent to various unit
operations to undergo various mild and severe reactions.

Upgraders in Operation Capacity (bbl/d) Products
Suncor, Fort MacMurray
(1967)
350,000 Sweet oilsands blend, sour cracked
bitumen, diluted bitumen, sulfur, coke
Syncrude, Fort
MacMurray (1978)
360,000 Syncrude sweet blend, sulfur
Coop Refinary and
Upgrader, Regina (1992)
80,000 Refinery products
Husky Bi-Provincial,
Lloydminster (1992)
82,000 Sweet synthetic crude, sulfur, coke
Shell Canada, Scotford
(2002)
155,000 Refinery products, sweet and sour
crudes, sulfur
OPTI/Nexen, Long Lake
(2008)
60,000 High quality synthetic crude
CNRL (Horizon project),
Wood Buffalo (2009)
110,000 Range of upgraded products

The reactions used to convert bitumen and heavy oil fractions fall into two main
categories namely thermal reactions (cracking, coking) and catalytic reactions
(hydroprocessing). Thermal reactions are responsible for most of the conversion of the
vacuum residue materials to distillate products. These cracking reactions are often
accompanied by the formation of coke. The catalytic reactions in the presence of
hydrogen give hydrogenated products with lower sulfur and nitrogen content. The
thermal reactions are usually called primary upgrading. The objective of primary
upgrading is to break chemical bonds, giving a lighter product. The main bonds of
interest during primary upgrading are carbon-carbon, carbon-sulfur and carbon-hydrogen.
In the absence of catalyst, the breakage of C-C bonds requires a temperature on the order
of 420C to achieve useful rates. Significant breakage of C-C bonds at lower
temperatures requires very active catalysts which, have not been effective when applied
to residues. Catalytic reactions that are usually called secondary upgrading have three
main outcomes in upgrading of bitumen and heavy oil: hydrogenation of aromatics and
olefins which is particularly valuable in suppressing the coke formation, removal of
metals, mostly vanadium and nickel, from the vacuum residue fraction which produce
feed for the subsequent refinery processing such as fluid catalytic cracking, and removal
of sulfur, nitrogen and oxygen which are called hydrodesulfurization,
hydrodenitrogenation, and hydrodeoxygenation, respectively, when hydrogen and
catalyst are used. Coke forms as a separate phase during thermal cracking of asphaltic
oils, either as particles in the oil or on surfaces, depending on the nature of the coking
process. In coking processes (primary upgrading) this accumulation is normal and part of
the design, whereas in hydroconversion and hydrotreating (secondary upgrading) such
coke formation is highly undesirable.
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The following figure shows an overall schematic for a generic upgrader.

The choice of specific upgrading technologies depends on feed properties, local
market and the type of major products. A more detail description of the unit operations in
upgraders are as follows:

1. Desalting and dewatering using large scale, but conventional technologies.

2. Atmospheric distillation to recover some distillate and remove diluent from
bitumen and heavy oil feed. Vacuum distillation is used to recover more
distillate.

3. Solvent deasphalting to precipitate the asphaltenes using solvents such as
propane. The term asphaltenes describes all materials that are soluble in benzene
or toluene and insoluble when diluted with a large excess of n-alkanes such as n-
pentane or n-heptane. Lower alkanes precipitate more asphaltenes than higher
alkanes. Only OPTI/Nexen that gasifies the asphaltenes use this process to
separate asphaltenes, others send the whole stream to the coking process.

4. Thermal viscosity reduction (visbreaking) is a mild thermal cracking process
which is aimed at reducing the viscosity of the residue or crude oil so that it can
be pumped easily. A 5-10% conversion of atmospheric residue to naphta is
sufficient to reduce the viscosity by five times. The viscosity reduction occurs
due to removal of side chains from the asphaltenes and breaking the bridging
aliphatic linkages that cause high viscosity by entanglement and formation of
ordered structured in liquid phase. All of the reactions in this process occur as the
oil flows through the tubes of the reaction furnace. The severity is controlled by
the flowrate through the furnace and the temperature. The typical temperatures
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are 475-500C at furnace exit and a residence time of 1-3 min. Hydrogen gas can
be present to achieve hydrovisbreaking which gives a higher API product.

5. The coking process divides the feed into light ends, liquid products and solid
coke. Coking process is very efficient for rejecting mineral solids, metals and
sulfur and nitrogen from the feed.
a. In the delayed coking several coke drums operates alternatively in a semi-
batch manner. The hot feed is blown into the drum to form coke and the
cracked vapors exit from the top of the drum. Once a drum is filled in
around 12-14 hr, the feed is directed to the next drum and the filled drum
is discharged and cleaned.
b. Fluid coking is a continuous process and uses a dual fluidized bed with
coke particles as the fluidized particles. The feed is sprayed on the hot
coke particles in the first fluidized bed. The coking occurs at the particle
surfaces and the cracked vapors will leave from the top. The coke particles
will be stripped by steam to remove liquids and passed to the second
fluidized bed. The coke is partially burned here to supply the heat
requirements of the coker.

6. Hydrotreating, also referred to as hydrodesulfurization, uses hydrogen and
catalyst at temperatures below 410C to provide moderate breakage of chemical
bonds. Thermal decomposition is usually minimized in this process. The
objective is removing impurities, such as sulphur, nitrogen and oxygen for the
control of a final product specification (such as naphtha, gasoline, diesel fuel,
kerosene, and fuel oil or for the preparation of feed for further processing
(naphtha reformer feed and FCC feed).

7. Hydroconversion uses hydrogen and catalyst at temperatures higher than 410C
to provide more significant breakage of chemical bonds. The addition of
hydrogen helps to suppress coking, and catalyst facilitates the hydrogenation of
aromatics and sulfur removal.

8. Hydrocracking is a high pressure process that uses a bi-functional catalyst to
perform the cleavage of carbon-carbon linkages, accompanied by saturation of
the fragments to produce lower boiling products. The catalyst is composed of a
metallic part, which promotes hydrogenation, and an acid part, which promotes
cracking. The acid cracking catalyst is only effective at low concentrations of
nitrogen and sulfur, so a hydrotreating stage usually exists before hydrocracking
to reduce sulfur and nitrogen. This process is mostly popular in Europe as FCC
process accounts for 85% of US refinery cracking capacity compared to 15% for
hydrocracking. Hydrocracking units are used by PetroCanada and Shell refineries
near Edmonton.

The well-established process technologies for upgrading are reliable but expensive.
The large capital cost investment in upgrading operations is only attractive at large scales.
Consequently, there has been a tremendous interest in alternate approaches to develop
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low-cost upgrading technologies. Pilot plants for heavy oil processing are difficult to
operate at steady-state, therefore, the claims for new processing technologies can be
difficult to assess. Any upgrading technology involves complex feed and product
mixtures, and multiple reactions that include cracking, hydrogenation, dehydrogenation,
coke formation, and removal of sulfur and nitrogen. Even with complete assay data, it is
very difficult to predict the potential of a process to give sufficient volume yield of high
gravity products. The CFD simulation can prove very useful in assessing different
new/established technologies for oil sands upgrading.
There are other severe constraints that the oil sands and heavy oil industry in Canada
is facing that, without new technology, could jeopardize the expected growth scenario.
The natural gas is currently the fuel of choice for steam generation, upgrading, heat, and
power. Currently, oil sands operations consume 5% of Canadas natural gas supply. With
growth in production and without fuel substitution, it is expected that oil sands operation
will be using approximately 1 billion cubic feet of gas per day which would be the major
part of the Arctic gas expected to come to market over the next 10 years. Furthermore,
there is a significant dependence on water for separation of oil from the sand in surface
mined operations and for in situ steam generation. To produce a barrel of bitumen or
synthetic oil, around 10 barrels of water for mining operations and 3 barrels of water for
in situ operations are required. Although most of the water is recycled, there is still about
20% of potable make-up water that is required that creates concerns over the need for
conservation and sustainability. The amount of energy required to produce a barrel of
synthetic crude oil is about a third of the energy in a barrel of bitumen. This makes the oil
sands operations large single source emitters of greenhouse gases. The need to reduce
CO
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emissions, as concern about climate change grows and reduction targets come into
effect; add considerable additional risks to oil sands investments.

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