Chemical Engineering Journal xxx (2015) xxx–xxx

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Chemical Engineering Journal

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A comparative study of fixed-bed and dispersed catalytic upgrading

of heavy crude oil using-CAPRI
Abarasi Hart a, Malcolm Greaves b, Joseph Wood a,⇑
a
School of Chemical Engineering, University of Birmingham, Edgbaston, Birmingham B15 2TT, UK
b
IOR Research Group, Department of Chemical Engineering, University of Bath, BA2 7AY, UK

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Fixed-bed and dispersed catalytic

upgrading of heavy oils was studied.
 The extent of upgrading is dispersed
catalyst > fixed-bed > thermal
cracking.
 Fixed-bed produces high middle
distillate fractions than dispersed
catalyst.
 Dispersed catalyst produces more
light distillates compared to fixed-
bed.
 High level of ultrafine particles
dispersion improves catalytic activity.

a r t i c l e i n f o a b s t r a c t

Article history: CAtalytic upgrading PRocess In-situ (CAPRI) incorporated with Toe-to-Heel Air Injection (THAI) for heavy
Available online xxxx oil and bitumen recovery and upgrading was studied for fixed-bed and dispersed catalysts. The extent of
upgrading was evaluated in terms of API gravity, viscosity reduction, impurity removal, and true boiling
Keywords: point (TBP) distribution. The test was carried out using Co-Mo/Al2O3 at temperature of 425 °C, pressure
Heavy oil 20 bar, and residence time of 10 min. The dispersed catalyst was tested in a batch reactor. However, the
Upgrading residence time, catalyst-to-oil (CTO) ratios as well as the Reynolds numbers of both contacting patterns
CAPRI
were kept the same to ensure dynamic similitude. It was found that the produced oil from dispersed
Fixed-bed
Dispersed catalyst
ultrafine Co-Mo/Al2O3 catalyst (dp = 2.6 lm) exhibited superior light oil characteristics and quality than
that produced with the fixed-bed of pelleted Co-Mo/Al2O3 (1.2 mm diameter  2–5 mm length). The API
gravity of the feed oil was 13.8° and the produced oil showed an increase of 5.6° in the fixed bed and 8.7°
with the dispersed catalyst. Unlike the fixed-bed of pelleted Co-Mo/Al2O3 which may suffer from diffu-
sion limitations, rapid deactivation, and channelling effect, the ultrafine particles presented high surface
area to volume ratio, reducing the chances of pore plugging, have more accessible reaction sites per unit
mass, and lead to enhanced cracking of macromolecules. Moreover, the reduction of sulphur of 38.6% and
(Ni + V) content of 85.2% in the produced oil show greater heteroatom removal compared to 29% (sul-
phur) and 45.6% (Ni + V) observed in the product from the fixed-bed.
Ó 2015 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license (http://
creativecommons.org/licenses/by/4.0/).

1. Introduction

Heavy oil and bitumen are viewed as a large potential energy

⇑ Corresponding author. Tel.: +44 (0) 1214145295; fax: +44 (0)1214145324. sources since their total reserve of about 9–13 trillion barrels out-
E-mail address: [email protected] (J. Wood). weighs conventional light crude oil reserves of about 1.02 trillion

http://dx.doi.org/10.1016/j.cej.2015.01.101
1385-8947/Ó 2015 The Authors. Published by Elsevier B.V.
This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).

Please cite this article in press as: A. Hart et al., A comparative study of fixed-bed and dispersed catalytic upgrading of heavy crude oil using-CAPRI, Chem.
Eng. J. (2015), http://dx.doi.org/10.1016/j.cej.2015.01.101
2 A. Hart et al. / Chemical Engineering Journal xxx (2015) xxx–xxx

barrels [1]. Heavy oil and bitumen contain resins and asphaltenes and Pereira-Almao [13] tested trimetallic (Ni–W–Mo) submicronic
which give them the characteristics of high viscosity, high den- catalyst in a batch reactor for dispersed-phase upgrading at 380 °C,
sity/low API gravity, high metals and heteroatom content. Upgrad- a stirring speed of 500 rpm, and reaction time 3–70 h. After
ing therefore improves refineability; reduces metals and upgrading, they found that the produced oil sample (API gravity
heteroatom content as coke precursors such as resins and asphalt- 16° and viscosity at 40 °C, 60 mPa s) was significantly upgraded
enes are converted into valuable liquid products. This can be compared to the Athabasca bitumen (API gravity 9.5° and viscosity
achieved through carbon-rejection and/or hydrogen-addition. 7680 mPa s).
Heavy oil and bitumen are mainly extracted using thermal stimu- The delivery of nano-sized catalyst into the oil-bearing forma-
lation of the reservoir, and to a lesser extent cold production. The tion for in situ catalytic upgrading can be accomplished by inject-
thermal methods include steam injection and on a smaller scale, ing it as a slurry, pneumatically conveying into the MOZ or
In-Situ Combustion (ISC) technologies. The commonly used steam alternatively precipitated in situ using a suitable metal precursors
technologies are Cyclic Steam Stimulation (CSS) and Steam [12,14,15]. The separation challenges can be resolved by inducing
Assisted Gravity Drainage (SAGD). However, the steam-injection magnetic characteristics to the ultrafine particles to enhance mag-
technologies are energy and cost intensive, consume large volumes netic separation [16]. The nano-sized catalyst can be introduced
of water and natural gas for steam generation, and subsequently into the reservoir in two forms namely: (1) as heterogeneous
their thermal efficiency drops with time owing to heat loss to adja- nano-sized catalyst, and (2) as dispersed precursor of water or oil
cent reservoir formation [2]. In-situ combustion includes conven- soluble salts [17,18]. The latter is transformed into active catalyst
tional ISC and Toe-to-Heel Air Injection (THAI). In the latter phase in-situ during the upgrading reactions. In this study, the
process a small portion of the oil in place is oxidised with its com- fixed-bed of pelleted catalyst and once-through dispersed catalyst
bustion front sustained by continuous injection of air through a contacting techniques of the THAI–CAPRI process were evaluated.
vertical well. Over the past 12 years, the THAI process research However, the dispersed catalyst test was carried out in a batch
and subsequent field studies have been carried out in conjunction reactor. The second phase of the study involves optimisation of
with the CAtalytic upgrading PRocess In-situ (CAPRI) in which a the catalyst-to-oil ratio, reaction time and agitation for the dis-
pelleted refinery catalyst is incorporated with the horizontal pro- persed catalyst. A further aim of the research was to identify
duction well to aid in-situ catalytic upgrading as the hot mobilised new concepts, directions and strategies for future studies of
oil flows across the layer of pelleted catalyst [3–6]. This technology THAI–CAPRI using dispersed nano-sized catalyst.
offers the advantage of using in-situ generated energy from the in
situ combustion reactions to mobilise the oil and also catalytically
2. Materials and methods
upgrade it in the reservoir, thereby offering great potential cost
advantages compared to SAGD and CSS which incur the cost of nat-
The heavy oil sample used in this study was supplied by Touch-
ural gas, steam generation and post water treatment. Moreover,
stone Exploration Inc, from the THAI field operation, Kerrobert,
Xia et al. [3] has demonstrated the potential use of regenerated
Saskatchewan, Canada. The feedstock is a blend of oils recovered
industrial hydrodesulphurisation (HDS) catalyst in CAPRI which
from eight wells, with properties summarised in Table 1. [Note:
could reduce the cost of catalyst. Additionally, commercial cata-
the original crude gravity was 10.9° API and increased to 13.8°
lysts are fairly cheap according to Shah et al. [7], it is estimated that
API upon extraction with THAI process].
20 tonnes of new HDS catalyst for 500 m horizontal producer well
Physically, ultrafine or micron sized particles can be prepared
cost about $60–100 k. The payback time is estimated to be only a
mechanically via crushing [19]. Therefore, the pelleted Co-Mo/
few days, based on a production rate of about 800 bbl/d. If THAI/
Al2O3 catalyst was crushed using a Tema laboratory disc mill
CAPRI can achieve 20 API gravity this could potentially add a
model T 750 K (TEMA Machinery Ltd., UK). The size of the catalyst
$20–30/bbl margin of profit over conventional extraction.
particles after pulverization was measured by laser diffraction par-
The down-hole upgrading method investigated and reported by
ticle size analyser (Helos-Rodos T4.1, Sympatec, Germany). The
Shah et al. [7] and Hart et al. [6,8,9] involved the fixed-bed contact-
mean particle size is approximately 2.6 ± 1.08 lm. The tempera-
ing pattern with catalyst incorporated adjacent to the horizontal
ture programmed desorption (TPD) of the fresh Co-Mo/Al2O3 cata-
production well. Findings from the fixed-bed of catalyst studies
lyst was carried out with a Micromeritics AutoChem II 2920
showed that the catalyst rapidly deactivates as a result of deposi-
analyser. This was performed to determine the number and
tion of asphaltenes, coke, metals and heteroatom during the pro-
strength of the acid sites based on the adsorption–desorption of
cess [6,7]. Typically, the duration of the catalyst ranged from
tert-butylamine ((CH3)3CNH2). The catalyst has two acid sites;
only 72–91 h, which is a major drawback of the fixed-bed pattern.
2.86 mmol adsorbed (CH3)3CNH2/g catalyst at 320 °C and
Owing to the high level of metals, heteroatom and asphaltenes in
0.45 mmol adsorbed (CH3)3CNH2/g catalyst at 500 °C, respectively.
heavy oil, dispersed ultrafine catalyst (i.e., submicron and nano-
Detailed properties of the Co-Mo/Al2O3 have been reported
sized particles) upgrading has been found to be more suitable
because it enables a once-through process [10]. Additionally, cata-
Table 1
lyst deactivation rate is a major yardstick for the selection of con-
Heavy feedstock properties.
tacting pattern, and the complications of pre-packing the
horizontal production well with pelleted refinery catalyst and Parameter Value
associated bed plugging with coke are avoided. However, convey- API gravity (°) 13.8
ing the nano-sized catalyst particles to the mobile oil zone (MOZ) Viscosity at 20 °C (mPa s) 1091
during the THAI process is not straightforward. Also, the recovery Density at 15 °C (g cm3) 0.9737
Sulphur (wt.%) 3.52
and re-use of the nano-catalyst after reaction need to be addressed. Nickel (ppm mass) 41
Reducing the particle size from pellets to powders with diameters Vanadium (ppm mass) 108
in the range of microns or even nanometers could potentially Ni + V (ppm mass) 149
shorten the diffusion path length, enhance active site exposure to Asphaltene (wt.%) 10.7
macromolecules and improve mass and heat transfer [11]. The for- ASTM D2887 Distillation, (°C)
mulation of nanoparticulate catalysts is similar to that of conven- IBP – 200 °C 34.6 vol.%
200 – 343 °C 41.4 vol.%
tional pelleted catalysts, derived from soluble precursors or
343 °C – FBP 24.0 vol.%
water-in-oil emulsions containing Mo, W, Co, or Ni [12]. Galarraga

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 A. Hart et al. / Chemical Engineering Journal xxx (2015) xxx–xxx 3

elsewhere [6]. The CAPRI experiments using a fixed-bed of catalyst detailed description of these analytical instruments has been
were carried out in a microreactor built and commissioned at the reported elsewhere [6,8,9].
University of Birmingham. The schematic diagram of the apparatus
and the experimental details can be found in Hart et al. [6]. Process 3. Results and discussion
variables such as temperature, pressure, flow rate, gas:oil ratio and
residence time used in this study were optimised values obtained The quantitative and qualitative data showing the extent of
from previous studies in the fixed-bed CAPRI reactor [7]. upgrading of the heavy oil after thermal cracking, fixed-bed and
For the dispersed ultrafine catalyst experiment, a small stainless dispersed ultrafine particles experiments are presented and dis-
steel custom-designed stirred batch reactor (100 mL capacity) was cussed in the following sections.
used to test the in situ catalytic upgrading. The reactions were car-
ried out at a temperature of 425 °C and 10 min reaction time, as 3.1. Characterisation
determined in previous fixed-bed investigations [6,7]. During the
heating stage to 425 °C, it has been reported that in-situ activation The pelleted and ultrafine Co-Mo/Al2O3 catalyst samples with
of the catalyst did occur as a result of the sulphur content of the the same chemical composition were analysed by the nitrogen
feed oil [10]. The gas atmosphere is nitrogen with initial pressure sorption technique according to ASTM C1274 method, and the
of 20 bar, which increases with the ramp temperature rise and results are presented in Fig. 1 and Table 3, respectively. A character-
the added gas due to cracking reactions to 74–80 bar, decreasing istic type IV hysteresis loop from relative pressure of 0.35–0.9 can
to 21–23 bar upon cooling the reactor to room temperature. The be noticed for both samples, indicating the filling of mesopores.
increased gas pressure is due to thermal expansion of initial gas Though the hysteresis loop is very similar in Fig. 1, the ultrafine
pressure of 20 bar and the additional gas produced from the reac- Co-Mo/Al2O3 produced by crushing the pelleted Co-Mo/Al2O3
tion. This is expected even in reality as a result of in situ combus- shows lower BET surface area and pore volume compared to the
tion which temperature ranges from 450 to 650 °C. Owing to the pelleted counterpart (Table 3). However, the micropore area of
pressures generated the technique is mainly suitable for wells of the ultrafine Co-Mo/Al2O3 increased by 7.6 m2 g1 above the pel-
at least 75 m depth. Some reaction could occur during heat up, leted form, which is due to the loss some of its mesoporosity dur-
which takes about 2 h 15 min to reach the desired reaction temper- ing the crushing process.
ature of 425 °C. Once the desired temperature of 425 °C is reached,
10 min reaction time was allowed to match that of the fixed-bed 3.2. Comparison of upgrading with fixed-bed of pellets vs. dispersed
reactor residence time. The experimental conditions for the ultrafine catalysts
fixed-bed and dispersed ultrafine particles are summarised in
Table 2. In order to evaluate the effect of the ultrafine catalyst, The results of experiments performed in the fixed-bed and the
other experiments were conducted without catalyst as a bench- dispersed ultrafine catalyst tested in a batch reactor at the same
mark and also pelleted catalyst basket was used in batch reactor residence time (10 min), CTO (0.1 g/g) and the same Reynolds
to study the impact of system hydrodynamics. numbers (Re) of 0.2 (calculated using Eqs. (1) and (2)) to ensure
The products of the upgrading reaction consist of liquid (i.e., dynamic similitude are presented in this section.
light oil), gas and coke. The produced gas was analysed using Agi- qms dp
lent gas chromatography (GC). The liquid product (i.e., upgraded Re ðFixed-bedÞ ¼ ð1Þ
lð1  eÞ
oil) was collected; thereafter measurements of viscosity, API grav-
ity, and simulated distillation by GC using ASTM D2887 method
(the calibration mix of the Agilent 6850 N GC used in this study
qND2
Re ðBatchÞ ¼ ð2Þ
contain hydrocarbons from C5–C40 and subsequently the maxi- l
mum oven temperature is 280 °C, therefore cannot account for where, N number of revolution per second (2.3), density of heavy
some macromolecules such as asphaltene outside this carbon oil, q (974 kg m3), velocity of oil in fixed-bed, vs (0.0032 m s1),
range), as well as sulphur and metals content were performed. viscosity of heavy oil, l (1.091 Pa s), porosity of the fixed-bed, e
The asphaltene content before and after the upgrading reactions (0.48), diameter of impeller, D (0.01 m), and equivalent particle
was determined through precipitation using n-C7H16. The pro- diameter, dp (0.035 m).
duced coke was determined using thermogravimetric analyser
(TGA) NETZSCH-Geratebau GmbH, TG 209 F1 IrisÒ. The spent cata- 3.2.1. API increment, viscosity, conversion and products yield
lyst from the fixed-bed after reaction was crushed before the TGA The mass of gas evolved during the upgrading reactions was
analysis. The analysis was carried out with a ramp temperature calculated by subtracting the masses of upgraded oil and solid
increase from 25 to 900 °C under air flow of 50 mL min1. A deposits in the reactor from a known mass of heavy oil fed using
Eqs. (3) and (4) [20]:
Table 2
wi
Experimental conditions. Yield ðwt:%Þ ¼  100 ð3Þ
wFeed
Parameter Fixed-bed Dispersed
pelleted catalyst ultrafine catalyst
Gas ðwt:%Þ ¼ 100  liquid yield ðwt:%Þ  coke yield ðwt:%Þ ð4Þ
Catalyst weight (g) 6 2
Feedstock weight (g) 60 20 where wi is the weight of component i and wFeed is the overall
Catalyst-to-oil (CTO) ratio 0.1 0.1 weight of the feed oil.
Residence time (minutes) 10 10 The expression used to calculate the conversion of heavy hydro-
Reaction temperature (°C) 425 425
carbons (HC) with boiling above 343 °C is given by Eq. (5). The con-
Reynolds number 0.195 0.195
Pressure (bar) 20 20–75 version definition does not take into account carbonaceous
Agitation (rpm) 133 deposits on the catalysts or reactor as unconverted feed.
Oil flow rate (mL min1) 1 ± 0.2
Effect of CTO 0 to 0.1 ð343  CþÞHC in feed  ð343  CÞHC in products
Conversion ¼
Effect of agitation (rpm) 250 to 1000 ð343  CÞHC in feed
Reaction atmosphere N2 N2
ð5Þ

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4 A. Hart et al. / Chemical Engineering Journal xxx (2015) xxx–xxx

run with dispersed ultrafine Co-Mo/Al2O3 produced oil that was

upgraded by 8.7 ± 0.7° API. This represents 2° API above thermal
cracking alone. Abuhesa and Hughes [23] reported similar findings
on catalytic and non-catalytic in situ combustion.
Viscosity is regarded as one of the key factors for crude oil pipe-
line transportation. The viscosity of 1091 mPa s (feed oil) was
reduced to 28.4 mPa s (fixed-bed) and 7 mPa s (dispersed) after
upgrading. This represents respectively 97.4% and 99.4% viscosity
reduction, a 2% increase upon the use of dispersed ultrafine Co-
Mo/c-Al2O3 compared with the pelleted catalyst. Conversely, Wei
et al. [24] reported 98.9% viscosity reduction of Liaohe extra-heavy
oil using nano-nickel catalyst in batch reactor. Using a fixed-bed of
inert glass beads [6], it was found that thermal cracking only pro-
duced an increase in API gravity of 1.7° and 52% viscosity reduc-
tion, at the same conditions as the present study. When using a
catalyst, the reported viscosity reduction could increase the flow
of the oil through the reservoir media, increasing the production
rate as well as improving pipeline transport. However in the cur-
Fig. 1. Nitrogen adsorption–desorption isotherm of pulverised and pellets Co-Mo/ rent work, the effect of dispersed ultrafine catalyst on viscosity
Al2O3. of produced oil seems to be roughly the same as that obtained with
only thermal upgrading. Chemical conversion to lighter compo-
nents could achieve the same or more with the dispersed catalyst
Table 3
The results of nitrogen sorption analysis for pelleted and ultrafine Co-Mo/Al2O3 on promoting hydroconversion as can be seen in the increased con-
basis of weight of catalyst sample. version of heavy fractions.
The difference in hydrodynamics and contacting pattern of
Parameter Pelleted form Ultrafine form
fixed-bed and dispersed catalyst could have contributed signifi-
BET surface area (m2 g1) 217.5 198.2
cantly to the level of upgrading achieved with pelleted and micron
Micropore area (m2 g1) 6.3 13.9
Pore volume (cm3 g1) 0.46 0.43 particles of Co-Mo/Al2O3. To gain further insight, an alternative
contacting technique using a spinning basket with pelleted Co-
Mo/Al2O3 in batch reactor at the same experimental conditions
was carried out. Although, the viscosity of the upgraded oil sam-
The main cause of catalyst deactivation is coke deposit due to ples after thermal cracking, pelleted catalyst basket, and dispersed
cracking of hydrocarbons and macromolecules such as resins and ultrafine catalyst upgrading was approximately the same, its API
asphaltenes [6,7]. The extent of deactivation as a function of spent gravity showed an increase in the order: dispersed ultrafine cata-
catalyst coke content was determined by TGA of the recovered cat- lyst > pelleted catalyst basket > thermal cracking (Table 4). This
alyst after upgrading. Fig. 2 provides the TGA weight loss curves as superiority of ultrafine catalyst over pellets (in basket) can be
a function of ramp temperature increase for the fresh and spent attributed to an increased contact, high surface area to volume
pellets and micro Co-Mo/Al2O3 catalysts recovered after the ratio, and decreased diffusion path length with particle of smaller
upgrading experiments with fixed-bed and batch reactor. The sizes.
weight loss (2.3 wt.%) by the fresh catalyst from 25 to 100 °C is Thermal cracking showed the lowest conversion of heavy frac-
due to loss of moisture. However, for the spent catalyst the weight tions (BP > 343 °C) of 33.1%, whereas the conversion was improved
loss from 25 to 208 °C represents loss due to de-volatilisation of upon using a catalyst to 46.4% (fixed-bed) and 59.7% (dispersed).
residual oil on the catalyst. The weight loss from 208 to 780 °C Though the upgraded oil after thermal cracking in batch showed
therefore represents soft and hard coke burn-off [6,7]. Hence, the high naphtha fractions, however the conversion of 343 °C+ frac-
spent catalyst coke content after upgrading with fixed-bed is tions into low-boiling fraction is low compared to catalytic coun-
32.7 wt.% and ultrafine particles after reaction in batch reactor is terpart in fixed-bed. This is because thermal cracking in batch
53.6 wt.%. The higher coke produced with dispersed ultrafine Co- reactor produced less middle distillates (200–343 °C) compared
Mo/Al2O3 is due to increase reaction as a result of increase surface to fixed-bed of catalyst, due to re-cracking of middle fractions in
area with particle size reduction. the batch reactor pushes the products towards naphtha fractions
Physical properties such as API gravity and viscosity of the (see Section 3.2.2). Additionally, the hydrodynamics difference
crude oil are two measures used in the petroleum industry to between the fixed-bed and stirred batch reactor also contributed.
assess its quality. The extent of upgrading achieved with fixed- The superiority of dispersed ultrafine catalyst over fixed-bed pel-
bed and dispersed micro-particulates of Co-Mo/c-Al2O3 catalyst lets could be because they offer better contact, whereas preferen-
are presented in Table 4. For duplicate runs, the average API incre- tial channelling encountered in fixed-bed will drastically reduce
ment was 8.7 ± 0.7o for dispersed ultrafine catalyst and 5.6 ± 1.8o oil-particle contact. Additionally, dispersed catalysts promote
for the fixed-bed system. The API gravity achieved using ultrafine cracking reactions because of their reduced particle size and large
Co-Mo/c-Al2O3 catalyst was 3o points above that obtained with surface-area-to-volume ratio, decreased diffusion path-length, and
fixed-bed catalyst. Ovalles et al. [21] observed an API gravity effective contact and wetting of the dispersed ultrafine catalyst
increase of 7° and 55% conversion of heavy fractions using dis- compared to the fixed-bed catalyst [25,26]. According to Le Perc-
persed molybdenum catalyst at 410 °C reaction temperature. With hec et al. [26], dispersed nano-catalysts exhibit higher reaction rate
regards to cost, the dispersed catalyst could therefore potentially than their fixed-bed counterpart, because hydrogen generated in
lead to the production of oil with higher added value [22]. situ promotes hydroconversion reactions which help to stabilise
The API gravity of the produced oil was also compared for cat- the free radicals produced during the cracking of heavy oil.
alytic and thermal cracking runs. As can be seen in Table 4, the The material balance presented in Table 4 shows that the
oil produced by non-catalytic route was upgraded by 6.6 ± 0.65° amount of coke produced at 425 °C was 12.95 wt.% (thermal crack-
API, above the original feed oil of 13.8° API. Whilst the catalytic ing only) compared to 12.07 wt.% (pelleted catalyst basket) and

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 A. Hart et al. / Chemical Engineering Journal xxx (2015) xxx–xxx 5

Fig. 2. TGA of fresh and spent pellets and ultrafine Co-Mo/Al2O3 catalyst after reaction in fixed-bed and batch reactors at temperatures of 425 °C, CTO 0.1 (g/g), Reynolds
number 0.2, and residence 10 min under nitrogen atmosphere.

Table 4
Comparison of upgrading level with fixed-bed Co-Mo/Al2O3 pellets, pelleted catalyst basket and dispersed ultrafine Co-Mo/Al2O3 at temperature 425 °C, pressure 20 bar, CTO 0.1,
Stirring speed 133 rpm, and thermal cracking only (in batch). Feed oil (13.8 °API and 1091 mPa s).

Experimental run API increment (o) Viscosity (mPa s) Conversion Coke Gas Liquid
(343 °C+) (%) (wt.% of feed oil) (wt.% of feed oil) (wt.% of feed oil)
Thermal (no catalyst in batch) 6.6 8 33.1 12.95 8.15 78.9
Dispersed ultrafine catalyst (batch) 8.7 7 59.7 7.1 8.05 84.85
Fixed-bed catalyst 5.63 28.4 46.4 1.86 3.34 93.8
Pelleted catalyst basket (batch) 7.41 7.6 48.3 12.07 7.88 80.05

7.1 wt.% (dispersed ultrafine Co-Mo/Al2O3). The corresponding of pelleted catalyst with long diffusion path length leading to pore
liquid yields were 78.9 wt.% (thermal), 80.05 wt.% (pelleted cata- plugging and deactivation [31,32]. As can be seen in Fig. 3, thermal
lyst basket) and 84.85 wt.% (dispersed). Coke formation is a conse- cracking produced the highest residue fraction of 16.6 vol.% (343 °C
quence of precipitation and accumulation of unconverted – FBP) compared to dispersed micron particles, pelleted catalyst
asphaltenes resulting from the decrease of solubility, due to com- basket and fixed-bed of pelleted Co-Mo/Al2O3. The increased
position changes caused by cracking reactions, temperature and low-boiling fractions caused the improvement of API gravity and
hydrogen-abstraction [27,28]. In the case of ultrafine catalyst, their viscosity reported in Table 4, compared to the original feed oil. A
strong affinity with asphaltenes serves to provide the necessary comparison of the yields of the different range of distillates after
active sites for cracking, thereby suppressing polymerisation and upgrading with fixed-bed and dispersed catalysts showed that
condensation reactions to form coke [29]. the light distillate increases from 47.5 vol.% (fixed-bed) to
56.6 vol.% (dispersed). However, the middle distillate decreased
from 39.2 vol.% (fixed) to 33.4 vol.% (dispersed), while the residue
3.2.2. Produced oil true boiling point (TBP) distribution fractions are 13.3 and 10 vol.%, respectively. It can be concluded
Heavy crude oil produces less fuel distillates and more residue that dispersed catalyst upgrading in a batch reactor favours the
fraction when distilled, compared to upgraded oil [6,30]. The liquid production of lighter boiling fractions, whereas a fixed-bed of pel-
product was classified according to the boiling point range after leted catalyst favours the middle distillates fractions. The increased
simulated distillation (SIMDIS) of the samples into the following yield of low-boiling distillates (IBP-200 °C) by 5.5 vol.% after
distillates; gasoline (IBP to 200 °C), middle distillates (200– upgrading with pelleted catalyst basket above 47.5 vol.% (fixed-
343 °C), and residual fraction (BP > 343 °C). In Fig. 3, the yields of bed), re-affirms the effect of hydrodynamics and contacting pat-
the distillate fractions of the distillate are presented for the feed- tern despite keeping the Reynolds number, residence time, tem-
stock and produced oil with dispersed ultrafine catalyst, fixed- perature, and CTO in both dispersed and fixed-bed the same.
bed, pelleted catalyst basket, and thermal cracking upgrading.
It is clear that while the residue fraction decreased from
24 vol.% in the feedstock to 13.3 vol.% and 10 vol.% respectively 3.2.3. Elemental analysis
for the produced oils from fixed-bed and dispersed Co-Mo/Al2O3 The results of the elemental analysis of the samples obtained
catalysts, the gasoline fractions respectively increased from from thermal, fixed-bed and dispersed ultrafine Co-Mo/Al2O3
34.6 vol.% (feedstock) to 45.5 vol.% and 56.6 vol.%. However, for upgrading and also of the feedstock are shown in Table 5. It can
the fixed-bed, more middle distillates (200–343 °C) were produced be seen that the H/C atomic ratio increased after thermal and cat-
compared to dispersed ultrafine Co-Mo/Al2O3. The enhanced gaso- alytic upgrading which supported the earlier notion of increased
line fraction with dispersed catalyst could have occurred since the hydroconversion with the dispersed ultrafine catalyst. However,
heavy molecules are transported to the more readily accessible the thermally upgraded oil sample showed the highest carbon-
active sites of the micron particles faster, unlike in the fixed-bed rejection of 5.16 wt.% and the lowest atomic hydrogen of

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6 A. Hart et al. / Chemical Engineering Journal xxx (2015) xxx–xxx

Fig. 3. Feed and produced oils distillate fractions after upgrading with thermal cracking (batch), pelleted fixed-bed, pelleted catalyst in basket (batch), and dispersed ultrafine
catalyst (batch) of Co-Mo/Al2O3 catalyst at temperature 425 °C, pressure 20 bar, nitrogen gas media, CTO ratio 0.1, stirring speed 133 rpm (batch), 1 mL min1 (fixed-bed), and
residence time 10 min.

Table 5
Micro elemental analysis of samples obtained from thermal, fixed-bed, and dispersed ultrafine Co-Mo/Al2O3 upgrading at temperature of 425 °C, pressure of 20 bar, stirring speed
133 rpm, CTO 0.1, and residence of 10 min under nitrogen atmosphere (basis of weight of oil fed).

Samples C (wt.%) H (wt.%) N (wt.%) H/C (wt.%) Carbon rejection (wt.%)

Feedstock 88.82 10.17 0.57 0.114
Produced oil (Thermal) 83.66 10.06 0.50 0.120 5.16
Produced oil (Fixed-bed) 87.01 11.49 0.44 0.132 1.81
Produced oil (ultrafine Co-Mo/Al2O3) 86.85 10.75 0.45 0.124 1.97

10.06 wt.%. Notably, the amount of carbon-rejected by thermal measurable reduction in sulphur and metals compared with the
upgrading is approximately 3 times that of catalytic upgrading. produced oil after thermal cracking alone. As can be seen in Table 6,
This confirms the mass balance presented in Table 4 and that the ultrafine particles of Co-Mo/Al2O3 led to greater reductions of
upgrading by thermal cracking is due to carbon-rejection. As a con- each component than the fixed-bed pelleted catalyst counterpart.
sequence, the incorporation of a catalyst improved the H/C ratio The produced oil after upgrading with ultrafine particles of Co-
and suppressed carbon formation (see Tables 4 and 5). Mo/Al2O3 has sulphur and metals (Ni + V) contents of 2.16 wt.%
It has been reported by Klerk et al. [33] that an increase in H/C of feed oil and 22 ppm, respectively. This signifies respectively
ratio indicates a decrease in naphthenic and aromatic content rel- 38.6% and 85.2% reduction of sulphur and (Ni + V) content of the
ative to the feed oil. The poly-form of these could have an adverse produced oil relative to the feedstock after upgrading. While the
impact on the H/C, API gravity and viscosity because of their high produced oil from fixed-bed of pelleted Co-Mo/Al2O3 has sulphur
density and carbon content. and metals (Ni + V) content of 2.50 wt.% of feed oil and 81 ppm,
respectively relative to 3.52 wt.% and 149 ppm (feed oil). This repre-
3.2.4. Asphaltenes, sulphur and metals removals sents 29% and 45.6% reduction of sulphur and (Ni + V) content after
The asphaltene content of a crude oil confers high viscosity and upgrading with fixed-bed of pelleted Co-Mo/Al2O3. This shows
low API gravity. The presence of heteroatoms (e.g., N, S, etc.) and therefore that the use of ultrafine particles of Co-Mo/Al2O3 further
metalloporphyrins of nickel, vanadium, iron, etc. are known to decreased the sulphur and (Ni + V) content by 9.6% and 39.6% com-
impact on downstream refining processes and catalysts. In Table 6, pared to that obtained from their pelleted fixed-bed counterpart.
the asphaltene, metals and sulphur contents before and after Pelleted catalysts are relatively large with limited surface area
upgrading, via thermal cracking, fixed-bed of pelleted Co-Mo/ compared to ultrafine catalyst, so the accessibility to active sites
Al2O3 and dispersed ultrafine Co-Mo/Al2O3 catalysts are presented. and interaction with many C–S bonds will be more limited. How-
Clearly, the asphaltene content after upgrading decreased for all ever, ultrafine catalyst have a large surface-to-volume ratio, easy
samples. However, a more significant decrease was recorded after access to active sites, more particles per unit volume, and therefore
upgrading with dispersed ultrafine Co-Mo/Al2O3 compared to ther- the interaction with molecules and C–S bonds will be increased
mal cracking and fixed-bed of pelleted catalyst. Based on the corre- also [34]. Also, some of the sulphur in the heavy oil was removed
lation between asphaltene content with the viscosity and API as a result of catalyst sulfidation during upgrading and coke depo-
gravity of the produced oil, it is clear that the result presented in sition. Clearly, the cleavage of large carbon chains, removal of sul-
Table 6 is consistent with viscosity and API gravity presented in phur, metals and yield of distillable is greater than their pelleted
Table 4. counterpart. It is important to note that the rejected sulphur and
The produced oil after upgrading with ultrafine particles of metals during upgrading reactions are associated with deposited
Co-Mo/Al2O3 dispersed for in situ catalytic upgrading showed coke. This in reality will be left behind in the oil reservoir during

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 A. Hart et al. / Chemical Engineering Journal xxx (2015) xxx–xxx 7

Table 6
Asphaltene, metals and sulphur content before and after upgrading with fixed-bed, thermal cracking and dispersed ultrafine Co-Mo/Al2O3 at 425 °C, nitrogen reaction medium,
10 min residence, 0.1 CTO, and 0.195 Reynolds number.

Impurities THAI produced oil Fixed-bed catalyst Thermal cracking Dispersed ultrafine Co-Mo/Al2O3
Asphaltenes (wt.% of feed oil) 10.4 4.88 3.79 2.32
Aluminium (ppm mass) 2 2 <1 <1
Boron (ppm mass) 6 3 4 2
Iron (ppm mass) 5 <1 <1 <1
Nickel (ppm mass) 41 24 8 7
Vanadium (ppm mass) 108 57 16 15
Ni + V (ppm mass) 149 81 24 22
Sulphur (wt.% of feed oil) 3.52 2.50 2.08 2.16
⁄
Sulphur and metals content was performed by Intertek Laboratories Sunbury Technology Centre, UK, using ICP-OES (Inductively Coupled Plasma Optical Emission
Spectrometry).

the in situ catalytic upgrading and the coke subsequently support- Table 8
ing in situ combustion of the THAI process. Produced gas composition for fixed-bed, thermal cracking and dispersed ultrafine Co-
Mo/Al2O3 catalyst in batch at temperature 425 °C, pressure 20 bar, nitrogen gas
media, catalysts-to-oil ratio 0.1, stirring speed 133 rpm, and residence time 10 min.
3.2.5. Produced gas composition (On the basis of amount heavy oil fed into the reactor).
The produced gas is a major by-product of the upgrading pro- Dispersed Fixed-bed Thermal cracking
cess. This was determined using RGA and the results are presented Gas (wt.% of feed oil) (wt.% of feed oil) (wt.% of feed oil)
in Table 7 on the basis on volume of gas analysed (Table 8 on the
n(C1-C5) 6.265 2.425 6.436
basis of heavy oil fed into the reactor). The THAI-CAPRI process i(C4-C5) 0.533 0.445 0.746
achieves heavy oil upgrading mainly by carbon-rejection, dehydro- Olefin (C2-C4) 0.798 0.280 0.751
genation, and hydrogen-transfer reactions. From Table 7, while 2.4 CO2 0.332 0.037 0.080
CO 0.00913 0.01562 0.05039
vol.% (0.137 wt.% of feed oil) hydrogen was produced from fixed-
H2S 0.00225 0.00040 0.00025
bed catalytic CAPRI, 1.7 vol.% (0.111 wt.% of feed oil) was produced H2 0.111 0.137 0.0858
from the dispersed ultrafine catalyst counterpart and 1.5 vol.%
(0.0858 wt.% of feed oil) from thermal cracking in batch reactor.
This difference in hydrogen can be attributed to the immediate
hydrogen, methyl and ethyl radicals from the gas phase to cracked
release of the produced gas from the gas–liquid separator in the
hydrocarbon fragments in the liquid phase forming a stable mole-
fixed-bed, which was not the case with the dispersed ultrafine cat-
cule. The latter releases a large amount of gas from the promoted
alyst. The presence of hydrogen in the gas moreover promotes
carbon-rejection to balance the elemental hydrogen and carbon
hydroconversion of the heavy oil fragments into smaller and stable
between the upgraded oil, produced gas, and coke deposit (see
molecules, if the partial pressure of hydrogen is high enough. This
Tables 4 and 5 for thermal upgrading alone).
hydrogen-transfer reaction could moderate generated free radicals
The light hydrocarbon gases C1–C5 produced with dispersed
and decrease coke formation, which explains the low yield of coke
catalyst in the autoclave were higher than that of the fixed-bed.
with ultrafine catalyst compared with the thermal cracking exper-
This affirmed the increased rate of reaction with ultrafine catalyst.
iment in batch reactor.
Hashemi et al. [35] found that in addition to low-boiling fractions
The amount of light hydrocarbons gases n(C1–C5) produced
being produced, the produced gases generated by in situ upgrading
from thermal upgrading was higher than that from catalytic
could contribute towards viscosity reduction via miscible displace-
upgrading (Tables 7 and 8). This observation is in agreement with
ment and subsequently enhance oil recovery. It is worth mention-
the results of normal alkane gases detected in the off-gas during
ing that the produced H2S using dispersed ultrafine Co-Mo/Al2O3
thermal upgrading of blend of vacuum residues in a batch reactor
was 4.8 and 8 times more than that produced by fixed-bed process
by Sawarkar and co-workers [27]. This is because thermal cracking
and thermal upgrading respectively (see Table 7). This corresponds
proceeds through a free radical mechanism with methyl and ethyl
to the trend in produced oil sulphur content reduction after
being the smallest hydrocarbon radicals generated by arbitrary
upgrading reaction presented in Table 6.
splits of the hydrocarbon chains while catalytic cracking of the
hydrocarbon chains in the oil proceeds in a systematic fashion of
carbonium ion intermediates and beta-scission. Also, the presence 3.3. Effect of catalyst-to-oil (CTO)
of catalyst promotes the incorporation of materials such as active
In Fig. 4, the effect of CTO on the mass balance of gas, light oil
and coke yields after reaction at a temperature of 425 °C, agitation
Table 7 of 500 rpm and 10 min reaction time is presented. Clearly, while
Produced gas composition for fixed-bed, thermal cracking and dispersed ultrafine Co-
the yield of coke and gas decreases, the yield of light oil increases
Mo/Al2O3 catalyst in batch at temperature 425 °C, pressure 20 bar, nitrogen gas
media, catalysts-to-oil ratio 0.1, stirring speed 133 rpm, and residence time 10 min. with increasing CTO. During the experiment, the change in compo-
(On the basis of volume of gas analysed). sition, temperature and pressure cause the precipitation of
asphaltenes as their aliphatic side chains are cracked.
Gas Dispersed Fixed-bed Thermal cracking
(vol.%) (vol.%) (vol.%) However, in thermal cracking (non-catalytic) the asphaltenes
readily aggregate thereby leading to high coke formation and less
n(C1-C5) 7.68 3.63 10.1
i(C4-C5) 0.31 0.29 0.45
light oil for the experiment without catalyst, at 0 CTO (see
Olefin (C2-C4) 0.59 0.24 0.39 Fig. 4). Whilst in the catalytic slurry environment the asphaltenes
CO2 0.23 0.03 0.1 readily diffuse to the active sites of the catalyst particles and are
CO 0.01 0.02 0.1 cracked into light components with hydrogen-transfer helping to
H2S 0.002 0.0004 0.0003
stabilise coke precursors, thereby causing less coke formation. This
H2 1.7 2.4 1.5
is believed to improve the yield of light oil with increasing CTO.

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8 A. Hart et al. / Chemical Engineering Journal xxx (2015) xxx–xxx

Fig. 4. Effect of CTO on gas, coke and liquid yields after upgrading using ultrafine Co-Mo/Al2O3 at 425 °C, 500 rpm, and 10 min reaction time.

The yield of liquid product in Fig. 4 increases with CTO, which is as well as pipeline transport to refineries. A similar trend with cat-
consistent with findings of Ortiz-Moreno et al. [10], who reported alyst loading was observed and reported by Ortiz-Moreno et al.
a similar observation with vacuum residue being transformed to [10]. The observed narrow trend can be attributed to the increase
valuable light oil product as catalyst loading increases. Thus, as in catalyst active sites per unit mass and more contact with
the catalyst loading falls below 0.02 (g/g), thermal cracking increasing CTO.
upgrading effect could have been dominant. However, increasing
the catalyst loading decreases the thermal cracking effect as the
3.3.2. Effect of catalyst-to-oil on TBP distribution
catalytic reaction becomes dominant, resulting in the decreased
In Fig. 6, the amount of the different distillate fractions before
yield of coke.
and after upgrading using dispersed ultrafine Co-Mo/Al2O3 as a
The reaction temperature of 425 °C applied here has already
function of CTO is shown. The three major reactions occurring in
been shown to lead to high production of coke and gas with low
the slurry upgrading media at 425 °C are: (a) free-radical formation
yield of liquid product [6]. Despite this limitation, the metal con-
from C–C bonds cleavage, (b) hydrogen-transfer reactions (i.e.,
taminants in the feed are deposited on the fine particles as metal
hydrogen-abstraction by C–H bond scissions and hydrogen-addi-
sulphides during the reaction, the aggregate could act as supple-
tion capping free-radicals), and (c) condensation and polymerisa-
mentary catalyst material such as micrometallic-coke [18]. There-
tion reactions between free-radicals.
fore, increasing catalyst loading suppresses asphaltenes
It is noteworthy that compared to the feed oil, the produced oils
precipitation and moderates the polymerisation and condensation
are lighter as CTO increases. Generally, the light fractions are
of coke precursors.
formed at the expense of the heavy fractions, resulting in gas and
coke formation. Thus, increasing CTO leads to decreased coke for-
3.3.1. Effect of catalyst-to-oil on API gravity and viscosity mation (mainly caused by thermal cracking effect). It can also be
The high macromolecular weight components of the heavy oil seen that using low CTO does not alter the level of upgrading sig-
confer low API gravity and high viscosity to the feedstock. The nificantly compared to thermal cracking, whereas high CTO (0.1 g/
change in API gravity and the viscosity of the produced oils after g) increases the conversion of heavy fractions (BP > 343 °C).
upgrading at 425 °C, agitation at 500 rpm, and 10 min reaction Though liquid yield and API gravity show similar trends, the
time with CTO in the range 0–0.1 (g/g) are presented in Fig. 5. decrease in liquid and residue fraction (BP > 343 °C) relative to
As CTO increases, the API gravity of the produced oil increases the feed oil indicates that gas and coke are produced at their
and an opposite trend of viscosity decrease were also observed expense. From Fig. 6, the fraction of the feedstock displaying high-
after reaction. The increase in CTO from 0 to 0.02 (g/g) has a much est conversion was the residue fraction (BP > 343 °C), with residue
bigger effect on change in API gravity and viscosity of the produced fractions after upgrading in the range 18 to 7.4 vol.% with
oil than increase of catalyst from 0.02 to 0.1 (g/g). Considering a increasing CTO from 0 to 0.1 respectively. A comparison of the
trade-off between amount of catalyst used in the reaction and API gravity, viscosity, and yield of distillates with gas, liquid and
API gravity of produced oil, it was observed that at CTO (0.1 g/g) coke products obtained after upgrading with CTO in the range of
the produced oil has 27° API compared to 24° API at CTO (0.02 g/ 0–0.1, showed that an optimum CTO of 0.02 is more economical.
g), however given the relatively small difference in API the effect It can be seen that secondary cracking of middle-distillates
at 0.02 g/g is more economical with only one fifth of the amount (200–343 °C) into low-boiling fractions (IBP-200 °C) increases as
of catalyst from the higher loading of 0.1 g/g. However, thermally the CTO increases in addition to the conversion of heavy fractions
upgraded oil showed the lowest change in API gravity and highest (> 343 °C). The decline in the residue and middle distillate fractions
viscosity at the same conditions. with increasing CTO indicates that their conversion contributed to
The viscosity of the produced oil decreased significantly as the the increase of low-boiling fractions (IBP-200 °C). The improved
CTO increased from 0 to 0.01, but only marginally decreased with physical properties (i.e., viscosity and API gravity) of the produced
further increase of CTO from 0.01 to 0.1 g/g. This reduction of vis- oil after upgrading are a reflection of this observation. Compared
cosity of the heavy feedstock will enhance fluidity for production with the mass balance presented in Fig. 4, it was shown that

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 A. Hart et al. / Chemical Engineering Journal xxx (2015) xxx–xxx 9

Fig. 5. Effect of CTO on API gravity and viscosity of the produced oil after upgrading using ultrafine Co-Mo/Al2O3 at 425 °C, 500 rpm, and 10 min reaction time.

Fig. 6. Effect of CTO on the yield of different distillate fractions of the produced oils after upgrading using ultrafine Co-Mo/Al2O3 at 425 °C, 500 rpm, and 10 min reaction time.

increasing CTO improved the conversion of heavy fractions into therefore thought to be the result of cleavage reactions of the mac-
valuable liquid product. Therefore, the produced oil containing sig- romolecules into smaller fragments of lower molecular weight,
nificant amounts of IBP-200 °C fractions also corresponded to the which increased with agitation.
maximum decrease in viscosity. Evidence of cleavage of heavy molecules can also be seen in the
simulated distillation of the samples before and after upgrading
3.4. Effect of agitation (Fig. 8). On average, the extent of viscosity reduction is 99.4% of
the original heavy oil. Li et al. [34] found 96% viscosity reduction
In Fig. 7, the effect of agitation on the API gravity and viscosity after upgrading of Xinjiang oilfield heavy oil using carbon nanocat-
of the produced oils after reaction using ultrafine Co-Mo/Al2O3 at alyst. Clearly, the results showed that fine particulate catalyst activ-
425 °C, nitrogen reaction medium, 0.02 CTO, and 10 min reaction ity and performance are controlled by the degree of dispersion in
time is presented. The API gravity of the produced upgraded oils addition to simply the catalyst-to-oil ratio and catalyst composi-
increased from 7.4 to 9.8° points as the agitation increased from tion. An increase in agitation causes improved particle dispersion
250 to 1000 rpm. It was noted that the level of upgrading achieved within the reaction medium, which would reduce the mass transfer
at agitation speed 250 rpm is only 1° API higher than that obtained barrier between the solid–liquid–gas. At low agitation, the cracking
after the thermal cracking experiment. Conversely, the viscosity of rate could be limited by the extent of contact and the transfer of
the produced oil decreased from 8.1 to 4.8 mPa s, as the agitation large molecules to the dispersed catalyst. However, the produced
increased from 250 to 1000 rpm, relative to the 1091 mPa s (feed- oil reached an optimum API gravity and viscosity at 500 rpm.
stock). It is well known that high viscosity of the heavy feedstock The amount of the distillate fractions of the feed and produced
can be attributed to their high content of macromolecular weight oils after reactions at varying agitations from 250 to 1000 rpm are
species such as resins and asphaltenes. The reduced viscosity is presented in Fig. 8. Compared to the feedstock, the low-boiling

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10 A. Hart et al. / Chemical Engineering Journal xxx (2015) xxx–xxx

fractions (IBP-200 °C) in the produced oil after reaction increased by

25–32 vol.% as the agitation increased from 250 to 1000 rpm, with
500 rpm giving a maximum of 32.7 vol.% increase. However, a mir-
ror trend can be observed for the middle distillate (200–343 °C)
which decreased by 10–15 vol.% as the agitation increases from
250 to 1000 rpm relative to 41.4 vol.% (feedstock). A similar trend
can be noticed with the residue fractions (BP > 343 °C). This showed
that significant portion of the middle distillates and residue frac-
tions in the feedstock has been converted to low-boiling fraction
after reaction. However, low yield of IBP-200 °C fractions and con-
version of residue fractions was observed at 250 rpm (see Fig. 8).
Also, from 500 rpm and above the level of agitation has an insignif-
icant effect upon the conversion of heavy molecules even though the
extent of dispersion and the transfer of molecules have increased.

3.5. Effect of reaction time

Fig. 7. Effect of agitation on produced oil API gravity and viscosity at 425 °C,
nitrogen reaction medium, 0.02 CTO, and 10 min reaction time.
Fig. 9 shows the effect of reaction time on the level of upgrading
using dispersed ultrafine Co-Mo/Al2O3 catalyst at 425 °C, initial

Fig. 8. Effect of agitation on distillate fractions before and after upgrading at 425 °C, nitrogen reaction medium, 0.02 CTO, and 10 min reaction time.

Fig. 9. Effect of reaction on API gravity and viscosity of produced oil at 425 °C, initial pressure 20 bar (N2), CTO 0.02 (g/g), and 500 rpm agitation.

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 A. Hart et al. / Chemical Engineering Journal xxx (2015) xxx–xxx 11

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Please cite this article in press as: A. Hart et al., A comparative study of fixed-bed and dispersed catalytic upgrading of heavy crude oil using-CAPRI, Chem.
Eng. J. (2015), http://dx.doi.org/10.1016/j.cej.2015.01.101