Fuel 85 (2006) 1526–1534

[Link]

Mineralogy and phase transition of oil sands coke ash

Heemun Jang *, Thomas H. Etsell
Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Alta., Canada T6G 2G6
Received 26 April 2005; received in revised form 29 November 2005; accepted 12 December 2005
Available online 19 January 2006

Abstract
Coke obtained from Syncrude and Suncor was investigated to characterize the metals and minerals by ashing it at various temperatures.
Samples were collected by high temperature ashing at 100 8C intervals from 400 to 1200 8C. Samples were also obtained from low temperature
ashing (LTA) which gives little effect on the mineral assemblage compared to HTA samples. X-ray diffraction patterns of Suncor and Syncrude
coke ash were analyzed qualitatively and quantitatively to characterize the mineral phases in the sample and their thermal transition behavior. In
Suncor ash, kaolinite, illite, gypsum, anhydrite, microcline, anorthite, hematite, sillimanite and quartz were dominant phases in ash from the LTA
temperature up to 700 8C, and mullite, cristobalite, hercynite, albite, anorthite, pseudobrookite and other iron–titanium oxides were dominant
mineral phases from 700 to 1200 8C. In Syncrude ash, illite, anhydrite, quartz, anorthite, microcline, sillimanite and hematite were dominant up to
700 8C, and hercynite, anorthite, albite, pseudobrookite and other iron–titanium oxides were dominant up to 1200 8C. The higher quantities of Ca,
K and Na, and the lower quantities of V, Fe and Ni in Syncrude ash resulted in higher amorphocity and the different mineral phases.
q 2006 Elsevier Ltd. All rights reserved.

Keywords: Oil sands; Fly ash; Mineralogy

1. Introduction operations would suggest a similar composition of the mineral

matter, Suncor and Syncrude fly ash are quite different in
Oil sands are also known as tar sands and bituminous sands. nature, mainly due to differences in the pretreatment of
They are found throughout the world, but the largest deposit is bitumen and in the ash formation temperature. First, Suncor
in the Athabasca area in northern Alberta, Canada. Suncor uses centrifuging after flotation to increase the purity of
Energy Inc. and Syncrude Canada Ltd operate commercial bitumen by removing more sand grains, whereas Syncrude uses
mining plants in this area for bitumen recovery from the oil flotation as the sole separation process. This difference in
sands. Oil sands are composed of bitumen (10–11 wt%), fine pretreatment results in a higher content of silica in Syncrude
clays, water and quartz grains [1]. Bitumen normally under- ash so that a mineralogical difference in the ash is also
goes separation and upgrading processes. Delayed coking and expected. Second, the difference in ashing temperature
fluid coking are the techniques used by Suncor and Syncrude, significantly affects mineralogy, chemistry and morphology
respectively, to break down the hydrocarbon molecules. A of fly ash. Suncor fly ash is produced when the coke left in the
substantial amount of oil sands coke is produced from these coking reactor as a solid residue is burned in boilers that
upgrading processes of bitumen. Approximately 22% of the generate electricity. The temperature of the boilers is as high as
bitumen is converted into coke in eight Suncor delayed cokers, around 1200 8C. On the other hand, Syncrude fly ash is
whereas around 15% of the bitumen is converted into coke in produced when the coke obtained from its fluid cokers is
two fluid cokers at Syncrude, with two-thirds of the total coke burned in the cokers themselves to maintain the coker
being stockpiled [2]. temperature, which is normally held at around 630 8C [3,4].
Oil sands fly ash is produced, when the coke generated from Mineral constituents of oil sands fly ash and the phase
changes of these minerals on combustion are of scientific and
the upgrading process is burned. However, even though the
commercial interest since a significant amount of metal values
proximity of the production mines of the Suncor and Syncrude
and other mineral matter originating in the oil sands are
concentrated in the fly ash when bitumen undergoes upgrading,
* Corresponding author. Tel.: C1 780 492 6620; fax: C1 780 492 2881. especially coking processes. Mineral composition of the oil
E-mail address: [Link]@[Link] (H. Jang). sands is over 90% quartz with minor amounts of potash
0016-2361/$ - see front matter q 2006 Elsevier Ltd. All rights reserved. feldspar, chert and muscovite [5]. Clay minerals mainly
doi:10.1016/[Link].2005.12.013 include kaolinite (Al2Si2O5(OH)4), illite and a small amount
 H. Jang, T.H. Etsell / Fuel 85 (2006) 1526–1534 1527

of montmorillonite. Chlorite, smectite, kaolinite/illite/vermi- model LTA-302 purchased from LFE Corporation, MA, USA,
culite mixed layers and illite/smectite interstratifications have which were held in an activated oxygen-plasma atmosphere
been also reported [6,7]. The kaolinite to illite ratio in some oil generated by a radio-frequency field [12]. The main advantage
sands samples ranges from 1 to 2 [6,8]. Trace amounts of of using the low temperature asher, or radio-frequency asher, is
inorganic compounds that have been found in oil sands are that the organically bonded minerals can be broken apart
potash feldspar, plagioclase, calcite, siderite, dolomite and without mineral alterations as activated oxygen generated from
pyrite [8,9]. Metal values found in oil sands residues include the radio-frequency oscillator reacts with organic substances in
appreciable amounts of vanadium, titanium and nickel. the coke.
Vanadium is concentrated to between 2.0 and 3.5 wt% (3.6– A combination of scanning electron microscopy (SEM) and
6.2% V2O5) in the fly ash when the coke is burned [10,11]. X-ray diffraction analysis (XRD) was used to characterize the
Significant research has been done on oil sands fly ash to leach mineral phases in the sample. For chemical composition of oil
out these metal values over the last two decades. This research sands fly ash samples in all temperature ranges, SEM/EDX
has enhanced the processability by development of various analyses were performed on a Hitachi S-2700 Scanning
processes including salt roasting in some cases. Microscope Link eXL EDS System. The formation of different
However, very little work has been completed on the phases was identified by a Rigaku X-ray diffractometer
mineral phases and their thermal behavior upon heating so that operating at 40 kV and 110 mA. X-ray data were collected
characteristics of oil sands fly ash have not been, so far, well using Cu Ka radiation in the range between 10 and 908 and
understood. This paper focuses on the mineralogy of oil sands steps of 0.058 2q with a count time of one second per step.
fly ash produced by ashing coke obtained from Suncor and Quantitative analyses on the amorphocity of samples used in
Syncrude. By ashing both Suncor and Syncrude coke at this study were based on the internal standard addition method
different temperatures, evidence of the transformation behavior first proposed by LeRoux, Lennox and Kay [13]. For analyzing
of mineral phases was revealed. Moreover, upon using a low the amorphocity of the ash, zinc oxide was chosen as an
temperature asher (LTA), which can sufficiently remove internal standard. Before X-ray analyses, 10 wt% ZnO was
carbon without changing any mineralogy in the original added into each sample and mixed with ash thoroughly by
coke, the nature of coke was also uncovered. A good means of hand grinding. The results were then collected by
understanding of the mechanisms of mineral phase transition using a traveling copy of Siroquant obtained from Sietronics
during combustion could lead to future improvements and Pty. Ltd, Australia. Quantities of all mineral phases in the
optimization of recovery of metal and mineral values from oil samples obtained over the temperature range of 500–1000 8C
sands ash. As well, the mineralogical knowledge of fly ash were also calculated by this program based on the Rietveld
could be a useful source for acceptable disposal of ash or refinement method [14–17].
successful gasification of coke.
3. Results and discussion
2. Experimental
3.1. Amorphocity of oil sands ash
Coke used in this study was obtained from Suncor and
Syncrude. Table 1 describes the typical data from proximate
Fig. 1 shows the quantities of amorphous materials in oil
and ultimate analysis of both cokes. Cokes were ashed at
sands fly ash treated from 500 to 1000 8C. The quantity of
100 8C intervals from 400 to 1200 8C before analysis. All the
amorphous materials in Suncor ash at 500 8C is 79.9 wt% and
samples were combusted in a muffle furnace until constant
keeps decreasing as temperature increases. At 1000 8C, it falls
weight was achieved, then ash content of each sample was
to around 20 wt% which is consistent with the result of Bruhns
calculated. In order to preserve the original mineral phases of
and Fisher [18]. The formation of mullite originating from
the coke, a low temperature ashing (LTA) technique was also
amorphous aluminosilicates at a relatively low temperature
used. Each coke sample was placed in two sample chambers of
appears to be the major contributor to this decreasing trend.
Table 1 XRD patterns from high temperature Suncor ash samples also
Typical data from proximate and ultimate analysis of oil sands coke (wt%) indicate many crystallites including mullite that are not found
Suncor coke [32] Syncrude coke [21] in low temperature samples.
Proximate
Moisture N/A 0.25
Ash 3.99 4.83
Volatiles 12.48 4.99
Fixed carbon 83.53 89.95
Ultimate
Carbon 84.02 83.74
Hydrogen 3.67 1.77
Sulfur 5.73 6.52
Nitrogen 1.38 2.03
Oxygen 1.21 0.88
Fig. 1. The amorphocity of oil sands fly ash from 500 to 1000 8C.
1528 H. Jang, T.H. Etsell / Fuel 85 (2006) 1526–1534

Compared to Suncor ash, a much higher fraction of The raw patterns from low temperature (up to 600 8C)
amorphous materials remains in Syncrude ash even at high samples have amorphous humps, or diffuse scattering maxima
temperature. Starting with 75.5 wt% at 500 8C, the (DSM), in the background starting at about 158 2q and ending
amorphous fraction is 48.8 wt% at 1000 8C. It is obvious at 358 2q. It is known that the position of the maximum is
that high fractions of Ca, Na and K, and amorphous silica closely related to the amount of Ca in a fly ash sample [19].
found in Syncrude ash interfere with the transformation of Low-calcium fly ashes, such as bituminous coal ashes, have
aluminosilicate glass into crystallites such as mullite. XRD their DSM at lower 2q angles, whereas high Ca samples have
raw patterns of Syncrude ash also indicate its higher their DSM at much higher angles. DSM found in Suncor ash at
amorphocity compared to Suncor ash. lower temperature seems to be close to that of bituminous coal
ash. These amorphous humps are not found in high temperature
3.2. Mineralogy of Suncor ash (700 8C or higher) samples.
The structure of sulfur in petroleum has been well
XRD raw data obtained from Suncor ash treated at different documented due to its environmental importance. Sulfur in
temperatures are shown in Fig. 2. Table 2 summarizes the oil sands is in two main forms. The most common type of sulfur
thermal transition behavior of Suncor fly ash in between low is in aromatic rings, which are difficult to remove. The other
temperature phases and high temperature phases identified, type is in thioethers, which are much easier to remove [20]. In
including unidentified amorphous materials. both cases, a significant amount of the total sulfur is kept in the

Fig. 2. XRD raw patterns of Suncor ash treated from LTA to 1200 8C. Abbreviations used are: K, kaolinite; I, illite; Q, quartz; Mi, microcline; An, anorthite; AH,
anhydrite; G, gypsum; H, hematite; S, sillimanite; M, mullite; P, pseudobrookite; IT, Fe–Ti Oxide; INT, Fe–Ni–Ti oxide; Ab, albite; Hc, hercynite; Ma, mayenite; C,
cristobalite.
 H. Jang, T.H. Etsell / Fuel 85 (2006) 1526–1534 1529

Table 2 amorphous glass. In this study, one spinel group mineral,

Low temperature and high temperature phases identified in Suncor fly ash and hercynite (FeAl2O4), started to form following the decompo-
their transition behavior on heating
sition of illite at 700 8C. Contribution to the formation of
Low temperature phases (!700 8C) High temperature phases (R700 8C) mullite and amorphous glass could also be expected.
Identified by Unidentified Identified by Unidentified Other than crystallites in LTA samples, hematite (Fe2O3),
XRD XRD anorthite (CaAl2Si2O8), sillimanite (Al2SiO5) and anhydrite
Kaolinite Metakaolinite Mullite (CaSO4) are the first mineral phases identified as predominant
Cristobalite minerals in 500 and 600 8C samples. A hydrated calcium
Illite Mullite Aluminosilicates sulfate, gypsum, is identified at LTA samples and up to 600 8C
Hercynite (Ca, K, Na rich)
samples. An intermittent phase, bassanite (CaSO4$1/2H2O),
Gypsum Anorthite
Anhydrite Mayenite which is believed to be dehydrated from the original gypsum at
Microcline Aluminosilicates Microcline slightly higher temperature, was not present in any samples.
(Ca, K, Na rich) Anorthite Some of the gypsum was dehydrated and resulted in the
Albite formation of anhydrite at 500 8C. The peaks of gypsum were
Hematite Hematite
not identified at 700 8C or higher so that the dehydration
Quartz Quartz Amorphous
silica temperature of gypsum found in Suncor ash was confirmed to
Sillimanite Sillimanite be 700 8C. Complete decomposition of anhydrite was also
Aluminosilicates Pseudobrookite found at this temperature.
(Fe, Ti, Ni rich) Fe–Ti–O As anhydrite decomposed, Ca released from anhydrite
Fe–Ni–Ti–O
formed mayenite at 700 8C. Association between anorthite and
mayenite is unknown. Many researchers argue that anorthite
residues, such as asphaltene and coke. While sulfur is believed forms when anhydrite reacts with alumina and silica, whereas
to occur mostly as pyritic sulfur in coal, Furimsky [21] suggests mayenite forms when CaO selectively reacts with alumina
that more than 95% of the sulfur is of organic origin in bitumen [19,23,24]. However, since no free lime is found in lower
and should be retained in the coke due to the prolonged heating temperature Suncor ash, it appears that excess Ca released from
in both Suncor and Syncrude coking processes. Neither iron– anhydrite reacts with alumina to form mayenite.
sulfur related inorganic compounds such as pyrite, marcasite While gypsum and anhydrite disappear at 700 8C, traces
(FeS2), or pyrrhotite, nor iron sulfates were identified in this of anorthite and sillimanite are continuously found up to
study. It is, thus, clear that pyrite or other related compounds 1200 8C. Hematite, on the other hand, appears to have
are not the precursors of hematite found at 500 8C and above. significant distortion in its structure since only one
Crystalline structures identified in LTA samples include characteristic peak is clearly shown at elevated tempera-
clays, gypsum, quartz and microcline. Clays were mostly ture, whereas many other peaks are broad and overlap with
kaolinite and illite. Polytype kaolinite (1 M) was identified others. Partial transformation into amorphous aluminosili-
with its characteristic peaks at 12.457 and 24.9938 2q which cates at the high temperatures is also expected [25]. Along
represent the (0 0 1) and (0 0 2) planes, respectively. These two with hematite, significant amounts of Fe in oil sands fly
peaks were also found at 400 8C, but disappeared in 500 8C ash samples result in the formation of other oxides at
samples. Since, Suncor ash contains only a minor amount of K relatively high temperature (700 8C). These oxides include
(around 2%), the major fraction of the clay should be kaolinite Fe–Ni–Ti oxide (Fe2NiTi3O10) and Fe–Ti oxides (Fe2TiO5
with a minor fraction of illite. However, the X-ray patterns are (pseudobrookite) and Fe2Ti3O9). The characteristic peaks
dominated with illite peaks. This indicates that a large part of of these Fe–Ti and Fe–Ti–Ni oxides are found throughout
kaolinite has already been transformed to metakaolinite, even the samples above 700 8C. The peaks of pseudobrookite
at a temperature lower than 400 8C. It might be postulated are the most intense and abundant among them.
that the structure of kaolinite starts to transform into One of the most important reactions found in Suncor fly ash
metakaolinite at 400 8C, and finally completes its transform- is the formation of mullite, which is first observed at 700 8C
ation by forming the mullite structure at 700 8C. Illite and is predominant up to 1200 8C. The formation of mullite
(K0.7Al2(Si,Al)4O10(OH)2) was identified as the 1 M polytype might be explained by the following three mechanisms. Firstly,
with its characteristic peaks at 4.43d and 2.56d. While the peak since kaolinite has been found at lower temperature, it seems
at 2.56d spacing disappeared at 500 8C, the peak at 4.43d feasible that the presence of mullite is associated with the
spacing was identified up to 600 8C, which probably means that decomposition of metakaolinite. Secondly, it is also possible
illite underwent structural deformation, or thermal expansion for aluminosilicate glass to be crystallized at this temperature
due to loss of water on heating, and completed dehydration at since the characteristic peaks of mullite become more intense
600 8C. at higher temperature indicating that more mullite crystals are
Grim and Bradley [22] state that dehydration of illite causes continuously formed. Finally, many scientists have shown that
formation of either spinel or mullite, or both. These authors dehydration of illite causes the formation of mullite [26]. The
also report that the octahedral sheet of illite lattice, which formation temperature is significantly lower compared to that
normally carries Al, Mn and Fe causes the formation of spinel, of other sources, such as mullite found in coal ash. This may be
and the alkalies and silicas in tetrahedral layers yield an related to the higher quantities of vanadium and iron in the
1530 H. Jang, T.H. Etsell / Fuel 85 (2006) 1526–1534

samples since these elements are believed to enhance clay to Microcline, which is found throughout the temperature
mullite transformations [18,27]. range is believed to be the most stable feldspar during
While quartz is found in the samples for the temperature combustion. The quantity ranges from 2 to 5%, which indicates
ranging from LTA to 800 8C, cristobalite, first found at 700 8C, that it is inactive on heating and quite isolated from other
is the predominant silica mineral at higher temperature. Quartz, chemical reactions. Its quantity slightly increases with
silica glass and the silica discarded from the decomposition of increasing temperature as more K might be introduced into
metakaolinite might be the precursors of cristobalite formation. the feldspar system when aluminosilicate glasses crystallize as
Along with anorthite, albite (NaAlSi 3O8), which is mullite. Ca and Na, released by the same mechanism, form
classified as one of plagioclase feldspar minerals, is identified anorthite and albite, respectively. However, the quantities of
at 700 8C and continues to be present in samples up to 1200 8C. these two plagioclase feldspar minerals start to decrease above
The formation of albite may involves structural change 900 8C. The amount of mayenite is quite small at lower
originating from microcline, since it is known that they have temperature, but the quantity increases at 700–900 8C due to
similar structures, and Na, Ca and K ions are interchangeable the formation of secondary mayenite from the decomposition
without requiring a significant structural alteration [28]. Na and of anhydrite. Mayenite also shows a decreasing trend at 900 8C
K components, which are released from glass or from illite and above.
decomposition at 700 8C, react with microcline to form albite. Mullite, sillimanite, hercynite and pseudobrookite keep
Compared to albite, anorthite first forms at a relatively low increasing in their quantities as temperature goes up to
temperature because Ca is abundant due to the decomposition 1000 8C. As amorphous aluminosilicates continuously crystal-
of gypsum and anhydrite. lize in this temperature range, Al oxides and Si oxides, key
elements of mullite, and hercynite and sillimanite become
abundant enough to form crystalline structures, while all other
3.3. Quantitative analysis on Suncor ash
base elements released from the aluminosilicates form feldspar
structures.
In order to better understand the transition behavior of
mineral phases, Suncor ash samples obtained over the
temperature range of 500–1000 8C were refined using the 3.4. Mineralogy of Syncrude ash
Rietveld method. Table 3 shows the quantities of each mineral
phase (wt%) found in Suncor ash. XRD raw patterns of Syncrude ash obtained from LTA to
Hematite, which is a predominant mineral phase at 500 and 1200 8C are brought together in Fig. 3 for comparison. Table 4
600 8C, slightly decreases in its quantity from 6.7 to 3.3%, summarizes the thermal transition behavior of Suncor fly ash
whereas the amount of other Fe-related minerals such as between low temperature phases and high temperature phases
pseudobrookite (and probably iron–nickel–titanium oxide as identified, including unidentified amorphous materials. The
well) increases up to around 10% as the temperature goes up to amorphous humps are visible here in samples up to 1000 8C
1000 8C. The quantity of quartz is quite unchanged up to indicating that the ash contains a higher quantity of amorphous
800 8C and remains at 1.8–2.6%. This confirms that quartz is materials. The DSM of Syncrude ash centers at approximately
one of the most inactive minerals during combustion. It appears 188 2q, and the shape of the DSM is very sharp compared to
to be true that high temperature quartz crystals are the same that of Suncor which is relatively flat and broad. This is due to
ones found before combustion. Decomposition of quartz is the higher quantity of calcium as mentioned earlier.
completed at 900 8C, and is not related to the formation of Strong peaks of quartz, along with moderate peaks of illite
cristobalite, since the quantity of cristobalite remains the same and anhydrite, are identified in LTA samples. Microcline is
at 800 and 900 8C, and even decreases at higher temperatures. also found in this sample with very low intensity peaks. As in

Table 3
Quantitative analysis of mineral phases in Suncor ash (wt%)

Minerals/temperature (8C) 500 600 700 800 900 1000

Hematite (Fe2O3) 6.7 13.5 2.2 6.0 4.7 3.3
Pseudobrookite (Fe2TiO5) 0.0 0.0 1.4 11.2 7.2 10.7
Hercynite (FeAl2O4) 0.0 0.2 2.8 3.6 6.4 10.7
Cristobalite (SiO2, tetragonal) 0.0 0.0 5.4 11.2 11.4 4.0
Mayenite (Ca12Al14O33) 0.3 0.5 1.8 2.1 3.1 1.5
Microcline (KAlSi3O8) 1.8 1.3 2.6 2.1 3.2 5.3
Mullite (3 Al2O.32 SiO2) 0.0 0.0 13.5 20.1 25.7 30.4
Albite (NaAlSi3O8) 0.0 0.0 1.2 4.0 5.4 0.1
Anhydrite (CaSO4) 4.7 5.6 0.6 0.0 0.0 0.0
Sillimanite (Al2SiO5) 0.2 0.0 6.8 4.0 5.2 8.5
Quartz (SiO2) 2.6 1.9 0.0 1.8 0.0 0.0
Anorthite (CaAl2SiO8) 3.5 5.3 1.6 9.9 8.9 5.8
Amorphous contents 79.9 70.8 60.1 19.2 18.8 19.2
 H. Jang, T.H. Etsell / Fuel 85 (2006) 1526–1534 1531

Fig. 3. XRD raw patterns of Syncrude ash treated from LTA to 1200 8C. Abbreviations used are; I, illite; Q, quartz; Mi, microcline; An, anorthite; AH, anhydrite; H,
hematite; S, sillimanite; P, Pseudobrookite; IT, Fe–Ti oxide; INT, Fe–Ni–Ti oxide; Ab, albite; M, mullite.

Suncor ash, illite (K0.7Al2(Si,Al)4O10(OH)2) identified in Anhydrite, rather than gypsum, is found in LTA samples
Syncrude ash is the 1 M polytype with its characteristic indicating that gypsum is completely dehydrated at this
peaks at 4.43d and 2.56d, and is found up to 700 8C. No temperature. Gypsum has a transition sequence of gypsum–
characteristic peaks of kaolinite are found at low temperature. bassanite–anhydrite, and this transition which accompanies the
As a result, no mullite structure is identified at high loss of water could begin at a temperature above 60 8C [29].
temperature and, as well, no cristobalite structure is found. This transition temperature is highly affected by the presence
The presence of kaolinite was initially anticipated because of alkali or alkaline impurities such as Na2SO4 [30]. Bayat [31]
similarity of mineralogy is expected due to similarity in coking also states that the presence of calcium promotes the
temperature, which is about 580 8C at Suncor and 630 8C at dehydration of gypsum and forms sulfates easily. One could
Syncrude, and the proximity of the production mines. It note that, due to higher concentrations of Ca, Na and K,
appears that the difference in elemental composition of the fly gypsum in Syncrude coke undergoes a phase transition to
ash mainly controls its mineralogy, especially the occurrence anhydrite at a very low temperature on combustion. Compared
of kaolinite. Less volatiles due to slightly higher coking with anhydrite, which completely disappears at 700 8C in
temperature, less Ni, Ti and V, higher silica and higher Ca Suncor ash, anhydrite is found to be present up to 800 8C in
could be the main factors that retard the formation of kaolinite Syncrude ash, which indicates decomposition of anhydrite is
in Syncrude ash. retarded by about 100 8C by elemental effects. The higher
1532 H. Jang, T.H. Etsell / Fuel 85 (2006) 1526–1534

Table 4 Unlike Suncor ash, no mullite structure was identified even

Low temperature and high temperature phases identified in Syncrude fly ash at high temperature. Suspicious peaks at 16.6 and 60.58 2q,
and their transition behavior on heating
which are among the characteristic peaks of mullite were found
Low temperature phases (!7008C) High temperature phases (R7008C) at 900 8C and above, but quantitative analysis was unable to
Identified by Unidentified Identified by Unidentified detect this phase. None of the associated minerals such as
XRD XRD cristobalite were found. Instead, the intensity peaks of albite
Illite Hercynite Aluminosilicates and anorthite become stronger as temperature increases from
(Ca, K, Na rich) 800 to 1000 8C.
Anhydrite Anorthite
Microcline Aluminosilicates Microcline
(Ca, K, Na rich) Anorthite
3.5. Quantitative analysis on Syncrude ash
Albite
Hematite Hematite Table 5 shows the quantities of each mineral phase (wt%)
Quartz Quartz Amorphous found in Syncrude ash. The quantities of sillimanite and hematite
silica are quite consistent (sillimanite, 2.8–4.4%; hematite, 2.8–4.3%),
Sillimanite Sillimanite
Aluminosilicates Pseudobrookite
which indicates these mineral phases are inactive on combustion.
(Fe, Ti, Ni rich) Fe–Ti–O The quantity of sillimanite displays an increasing trend with
Fe–Ni–Ti–O increasing temperature in Syncrude ash. Quartz is in a decreasing
trend and disappeared at 900 8C. Compared with Suncor ash,
quartz in Syncrude ash disappears at a slightly higher
amount of calcium in Syncrude ash may be mainly responsible temperature. The absence of cristobalite along with disappear-
for these elemental effects. ance of quartz indicates again that quartz did not transform into
Weak intensity peaks of sillimanite are found throughout the cristobalite. Instead, quartz appears to transform into amorphous
temperature range. The presence of sillimanite at 400 8C silicates. Mayenite which is regarded, as a second phase
indicates that, among the amorphous materials of fly ash, following the decomposition of anhydrite in Suncor ash is not
aluminum was the easiest component to be crystallized. found in Syncrude ash. The amounts of albite and anorthite are
Reacting with Ca released from either the amorphous matrix significantly increasing at 800 8C as much more alkali elements
or gypsum, continuous crystallization of Al also affects the are released from the amorphous aluminosilicates at this
formation of anorthite identified at 600 8C. The presence of temperature. The quantity of albite decreases when the
microcline, as in the Suncor ash, could also be the precursor of temperature is over 1000 8C, whereas the quantity of anorthite
anorthite formation. continuously increases. The quantity of pseudobrookite also
Hematite is first identified at 500 8C, and the peaks remain increases as temperature increases.
up to 1200 8C. Unlike Suncor ash, the peaks are quite obvious
up to 1000 8C and slowly broadened and overlapped above 3.6. Comparison between Suncor and Syncrude ash
1000 8C. Other Fe-bearing oxides found from 700 to 1200 8C
include pseudobrookite (identified at 800 8C and higher), other Due to the proximity of the actual production mines, some
Fe–Ti oxides (identified at 800 8C and above) and Fe–Ni–Ti mineralogical information obtained from Suncor and Syncrude
oxides (identified at 900 8C and higher). As found in Suncor cokes is quite similar. For both cokes, the main constituents of
ash, the peaks of pseudobrookite are the most intense among fly ash were aluminosilicate minerals and amorphous Fe–Ti–Ni
these mineral phases. Whereas all these mineral phases compounds. Aluminosilicate minerals are mainly associated
containing Fe possibly originate from amorphous Fe–Ni–Ti with the formation of mullite and feldspars, whereas Fe–Ti–Ni
compounds, hercynite found at 800 8C and above appears to compounds lead to the crystallization of hematite, Fe–Ti
contain Fe originating from illite which contains a significant oxides, pseudobrookite and Fe–Ti–Ni oxides. For both cokes,
amount of Fe (normally 1.43% or higher) as an impurity in its no pyritic sulfur is identified supporting the fact that almost all
interlayers. the sulfur in oil sands coke is of organic origin. Hematite and

Table 5
Quantitative analysis of mineral phases in Syncrude ash (wt%)

Minerals\temperature (8C) 500 600 700 800 900 1000

Hematite (Fe2O3) 2.8 2.1 4.3 3.9 4.0 2.9
Pseudobrookite (Fe2TiO5) 0.0 0.0 0.0 3.2 5.9 6.8
Quartz (SiO2) 7.5 16.1 9.4 2.9 0.2 0.7
Cristobalite (SiO2) 0.0 0.0 0.0 0.0 0.0 0.6
Sillimanite (Al2SiO5) 3.0 1.6 3.5 4.4 2.8 3.7
Anorthite (CaAl2SiO8) 4.8 2.2 2.1 13.4 19.5 21.7
Albite (NaAlSi3O8) 0.1 0.0 2.0 14.7 18.0 14.8
Anhydrite (CaSO4) 6.6 3.6 7.9 0.0 0.0 0.0
Amorphous content 75.2 74.4 70.9 57.4 49.5 48.8
 H. Jang, T.H. Etsell / Fuel 85 (2006) 1526–1534 1533

quartz are relatively unchanged, but quartz is altered to 4. Conclusions

amorphous silicates at high temperature (800–900 8C). Anhy-
drite originating from gypsum is decomposed at low Oil sands fly ash obtained from the LTA is revealed to have
temperature (700–800 8C). Anorthite is formed both by significant amounts of amorphous aluminosilicate materials
decomposition of anhydrite and by crystallization from along with minor amounts of illite, kaolinite, calcium sulfate
amorphous aluminosilicates. A minor amount of hercynite is and quartz. Aluminosilicates can be further classified into two
found as a secondary phase of illite decomposition. forms: aluminosilicates enriched in alkaline earth elements and
However, since Suncor and Syncrude employ different aluminosilicates enriched in iron and titanium. The former
upgrading and coking processes, the mineralogy of their aluminosilicates were the precursors of feldspars, mullite and
coke is quite different, as is the mineralogy of fly ash. sillimanite, while the latter were attributed to the crystallization
Chemical analyses reveal that, compared to Suncor ash, of hematite, Fe–Ti oxides and Fe–Ti–Ni oxides. Clays
Syncrude ash is characterized by its high Ca, Na, K and Si contributed to the formation of mullite, cristobalite and
fractions and its low Fe, Ti and V fractions. This elemental hercynite, while quartz was not associated with chemical
difference results in some differences in mineral phases and interactions. Gypsum underwent dehydration resulting in the
their thermal behavior. formation of anhydrite, which also contributed to the formation
of anorthite at a later stage of combustion.
1. Crystalline phases found in Suncor coke are mainly It was found that crystalline phases identified in Suncor
kaolinite, illite, gypsum, microcline and quartz, whereas coke were mainly kaolinite, illite, gypsum, microcline and
illite, microcline, quartz and anhydrite are the main quartz, whereas illite, microcline, quartz and anhydrite were
crystallites in Syncrude coke. Based on the assumption the main crystallites in Syncrude coke. In high temperature
that the same bitumen is treated at both Suncor and (700 8C or higher) fly ashes, mullite, feldspars, cristobalite,
Syncrude, which means the mineral phases should be hercynite, hematite, pseudobrookite, and other iron–titanium
similar, this difference indicates that kaolinite undergoes oxides became the major mineral phases in Suncor samples,
significant structural distortion during fluid coking whereas feldspars, hercynite, hematite, pseudobrookite, and
processes at Syncrude. other iron–titanium oxides were the major mineral phases in
2. Occurrence of mullite is found only in Suncor ash. Syncrude samples. It was also found that minor differences in
Mullite formation found at 700 8C in Suncor ash is not chemical composition between two plants greatly affected the
found in Syncrude ash which has no kaolinite to serve as phase transitions at elevated temperature.
the precursor for mullite formation in its coke samples.
Formation of cristobalite results from the decomposition Acknowledgements
of metakaolinite in Suncor ash, but not in Syncrude ash.
This difference confirms the fact that the amorphous The authors would like to thank Suncor Energy Inc. and
silica-to-cristobalite transformation or quartz-to-cristoba- Syncrude Canada Ltd for providing the coke samples used in
lite transformation is not possible in oil sands fly ash. this study.
The only possible way for cristobalite to form is the
decomposition of metakaolinite.
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