SPE 84863
Liaohe Extra-Heavy Crude Oil Underground Aquathermolytic Treatments Using
Catalyst and Hydrogen Donors under Steam Injection Conditions
L.G. Zhong, Y.J. Liu SPE, H.F. Fan/Daqing Petroleum Institute and S.J. Jiang/Liaohe Oil Field
Copyright 2003, Society of Petroleum Engineers Inc.
This paper was prepared for presentation at the SPE International Improved Oil Recovery
Conference in Asia Pacific held in Kuala Lumpur, Malaysia, 20–21 October 2003.
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Abstract
The aquathermolysis of Liaohe heavy oil is described which
involves the addition of catalyst and hydrogen donors under
steam injection conditions. The laboratory aquathermolytic
experiments were carried out with the heavy oil, water,
catalysts, and hydrogen donors at different temperature
(160~260℃) and reaction time (24~240 hours). It was found
that the metal species could catalyze the aquathermolytic
reactions of Liaohe extra-heavy oil, for example, Fe(II) led to
near 60% decrease in viscosity of treated oil at 240℃ till 72
hours. However, using catalyst and hydrogen donor (tetralin),
more decrease (up to 90%) in viscosity was observed, it
indicated the synergetic effect of hydrogen donor and catalyst
on aquathermolysis. Average molecular weight, element and
SARA analysis showed the same synergetic effect. A cheaper
hydrogen donor almost as effective as tetralin was developed
from coal tar. The field aquathermolytic testing using catalyst
and hydrogen donor were carried out at five Liaohe extra-
heavy oil wells, as a result, the oil recovery was improved and
treated oil upgraded greatly.
Introduction
Heavy oil is an important hydrocarbon resource that is nearly
three times the conventional oil in the world. The major
difficulty in the production of heavy oil is the high viscosity.
Thermal recovery techniques, such as steam injection, are
effective in temporarily lowering the oil viscosity by heating.
At the same time the field evidence and laboratory research
results indicates that in the presence of water vapor, a
chemical reduction in oil viscosity, or visbreaking [1], often
accompanies these thermal processes owing to the cracking of
the oil [2]. That means some chemical reactions took place,
which are named aquathermolysis [3, 4].
In recent years research on aquathermolysis of heavy oil
under steam injections has been carried out. The results of
heavy oil aquathermolysis with the transition metal catalyst
were introduced by Hyne et al [3, 4]. The laboratory
experimental results indicated obvious reduction in viscosity
and asphaltene contents, increase in saturated and aromatic
hydrocarbon, and generation of some gases such as carbon
oxide, hydrogen, methane, and so on.
Hyne et al. suggested that heavy oils appeared to undergo
competitive chemical transformations that affect viscosity in
opposite ways during aquathermolysis. Once reactive species
have been generated by aquathermolytic cleavage of sensitive
sites such as the carbon-sulphur bond, either they can
polymerize and thus raise the viscosity or initiate a series of
further reactions that result in the generation of products (e.g.
saturates) which can reduce viscosity even in relatively small
amounts. The primarily reason for polymerizing is the
connecting between active freeradicals formed by aqua-
thermolysis, which can even create much larger moleculars
[5]. Cesar Ovalles et al. haved presented that adding hydrogen
donors could prevent the freeradicals from polymerization
under the conditions of steam injection, three-fold viscosity
reduction and, approximately, 8% decrease in the asphaltene
content with respect to the original crude were observed [6].
In this paper, with Liaohe extra-heavy oil, the aquathermo-
lysis using catalyst and hydrogen donors, respectively or
together, is investigated under steam injection condition. In
addition, a hydrogen donor developed from coal tar is also
involved. In the end, the field aquathermolytic testing using
catalyst and hydrogen donor is introduced.
Experimental Part
Materials
The heavy oil used was sampled from the Shuguang region in
Liaohe Oilfield and its properties are listed in the Untreated
colume of Table 1. Chemicals and solvents were obtained
from some chemical companies in Harbin and Beijing and
used as received. Water was distilled and de-ionized
before experiments.
Analysis of oils
The treated oils were measured in terms of viscosity, average
molecular weight, elementary and SARA analysis.
Viscosity determination
Oil viscosities were measured using a Haake viscometer,
model RV-III, at 80℃. Approximately 20g oil was placed in
the sample cup and allowed to equilibrate to the measure
2 SPE 84863
temperature, and the measurement was made according to
procedures specified by the manufacturer.
Sulfur determination
Sulfur content was measured by X-ray fluorescence
accord-ing to GB/T 17606.
SARA analysis
SARA analysis was conducted by the techniques described
in reference 7.
Elemental analysis
Elemental analysis, C, H and N analysis, were carried out
by YANACO MT-3 elemental analyzer.
Average molecular weight
Average molecular weight was determined by gel permea-
tion chromatography (GPC), using a Knauer Vapor Pressure
Osmometer K-7000.
Apparatus
Aquathermolytic experiments were carried out in a hastelloy
500-ml reactor equipped with a magnetic stirrer, a heating
mantle and a temperature controller. In a typical experiment,
the reactor was filled with oil, water, catalyst, and hydrogen
donor with a proper weight ratio, respectively. The experi-
mental scheme in this paper is shown in Table 2.
The reactor was heated at 5~8 ℃ /min to 160~260 ℃ ,
generating a final pressure of approximately 10~25MPa.
Laboratory experiments were carried out in the reactor at
different temperatures (160~260 ℃ ) and reaction times
(24~240 hours). Oil, water, catalyst and the hydrogen donor
were added to the reactor together. After the experiment the
reactor was cooled to room temperature and reaction mixture
was removed from the reactor, and continuously distilled at
about 300℃ in order to remove water and hydrogen donor
from the reacted oil. The upgraded oils observed
were analyzed.
Results and Discussions
Experiments with metal species
Using the above reactor, the experiments in which Liaohe
heavy oil was reacted with steam adding a variety of aqueous
metal species were carried out at 240℃ over 72 hours as run
group 1 suggested in Table 2. These conditions produced in
the reactor are thought to occur in field steam injection
projects. The effect of metal species on the viscosity of Liaohe
heavy oil is shown in Fig 1. Fe(II), Co(II), Mo(II), Ni(II) and
Al(III) showed the largest decreases, up to 60% decrease for
Fe(II). It indicates that these metal species can catalyze the
aquathermolysis of Liaohe heavy oil.
The effect of adding aqueous Fe species to steam is of
some interest because iron is cheaper, consequently, a series of
experiments with varying Fe(II) concentrations were carried
out at 240℃ for 72 hours (see Table 2). It shows that the
concentration of Fe(II) have a marked effect on the viscosity
of the reacted oil such that the value of 96Pa·s obtained using
0.02M Fe(II) decrease to a minimum of 90Pa · s at 0.08M
Fe(II). Higher Fe(II) concentration shows a increasing trend in
viscosity. Consequently, Fe(II) at 0.02M was chosen as the
catalyst to be investigated further with hydrogen donor in
this paper.
Experiments with metal species and hydrogen donor
To investigate the effect of metal species and hydrogen donor
on the aquathermolysis, tetralin (THN) was chosen as a
hydrogen donor. As far as the higher price of tetralin was
concerned, a hydrogen donor which comprises of some
components to supply hydrogen was developed from coal tar.
Many experiments were carried out in the reactor adding
0.02M Fe(II) and 10ml hydrogen donor, respectively and
together, and other conditions just as run group 1~4 in Table 2
suggested. The viscosity of reacted oil is shown in Figure 1.
Only adding THN led to less than 40% decrease in viscosity
from 220 Pa·s untreated to 142 Pa·s for 24 hours and 130.8
Pa·s for 168 hours. The viscosity of oil treated adding Fe(II)
is decreased larger with the reaction time, up to 60% for 240
hours, but after 72 hours the reduction trend is wake. The
results using Fe(II) and THN/hydrogen donor developed
shows the similar trend as Fe(II), but a much larger decrease
in viscosity is observed, for example, up to 90% decrease in
viscosity for THN, and 85% decrease for hydrogen donor
developed. As anticipated, it indicates the synergetic effect of
hydrogen donor and catalyst on heavy oil aquathermolysis
under steam injection conditions. At the same time, it could be
seen that the decrease in the viscosity by adding hydrogen
donor developed is close to THN. It shows that the hydrogen
donor developed is almost as effective as tetralin for aqua-
thermolysis of Liaohe heavy oil. These results show the
potential of aquathermolytic process using the catalyst, e.g.
Fe(II) and hydrogen donor developed to improve Liaohe
extra-heavy oil recovery under steam injection conditions.
The principles maybe proved reasonable, that is, the
catalyst may lead to cleavage of some components of heavy
oil by aquathermolysis, at the same time, the freeradicals by
cleaving are connected with hydrogen, and some bonds of the
components are broken nonreversibly. Of cause, the principles
should be investigated further.
The viscosity decreasing with reaction time is shown in
Figure 3. For 72 hours, lower values of viscosity were
observed in comparison with the 24 hours experiment for all
the reactions using catalyst and hydrogen donor, respectively
or together.
In order to investigate the effect of temperature on the
aquathermolysis reactions, experiments at different tempera-
tures (160~260 ℃ , which are typical in oil field) were
conducted for 72 hours as scheme in Table 2 suggested. The
results are shown in Figure 4. When the temperature increase
from 160℃ to 260℃, the viscosity reduced from 168 Pa·s to
a much lower value of 76Pa·s for Fe(II), 203.2 to 132.4 for
THN, 143 to 22.9 for Fe(II) and THN, 162 to 39.6 for Fe(II)
and hydrogen donor developed. It could be found that higher
temperature would enhance the aquathermolysis. But the
highest in-situ temperature for steam injection is 240℃ or so,
usually lower.
Additionally, the effect of volume of hydrogen donors on
the aquathermolysis was investigated. The results of
experiments with Fe(II) and varying volume of THN or
hydrogen donor developed are shown in Figure 5. It is found
that more hydrogen donor conduces to larger decrease in
viscosity, up to 90% reduction was obtained adding 15 ml
THN, and 85% adding 15ml hydrogen donor developed.
SPE 84863
Volume more than 15 ml does not show larger reduction in
viscosity. It suggests that some proportion of hydrogen donor
to oil would be sufficient for the aquathermolysis of Liaohe
extra-heavy oil.
The properties of oil treated with catalyst and/or hydrogen
donor at 240 ℃ for 72 hours are listed in Table 3. The
viscosity reduction has been discussed above. Average
molecular weight, element analysis and SARA determination
indicates that adding catalyst Fe(II) and/or hydrogen donors
conduces the composition change of the oil, and the experi-
ments with Fe(II) and hydrogen donor had a much great effect
on the composition of the oil than experiments using them
respectively. It is similar to the effect on viscosity.
It could be found that average molecular weight of oil was
decreased after the aquathermolysis treatment, and the H/C
increased. It should be noted that the sulfur content was
decreased greatly by adding Fe(II) and hydrogen donors.
Fe(II) alone resulted in 1/3 decrease in sulfur content (0.96%
to 0.63%). Although hydrogen donors alone have no obvious
effect, the combination of Fe(II) and hydrogen donor had
much larger effect on sulfur content decreese, up to 2/3
reduction (0.96% to 0.32% for THN, and to 0.35% for
hydrogen donor developed). At the same time, the nitrogen
content of the treated oil shows a little change. As J. B. Hyne
and P. D. Clark suggested that the cleavage of C-S bonds and
other bonds should result in observable macroscopic changes
in the oil, and the active H radical from H2O and hydrogen
donors terminates the freeradicals produced by the cleavage,
the combination leads to the change of composition and
viscosity of oil.
SARA analysis of oils gave a similar picture in that the
content of resin and asphaltene was lowered after treatment
with Fe(II) and/or hydrogen donor. Accordingly, the content
of saturated and aromatic hydrocarbons was increased. Adding
Fe(II) alone led to 4% decrease in asphaltene content, 3%
decrease in resin, 4% increase in saturated hydrocarbon, and
3% increase in aromatic hydrocarbon were obtained, THN
alone all 1% or so, respectively, however, adding Fe(II) and
hydrogen donors, up to 9%, 7%, 10%, and 6% respectively.
Field Testing
The field testing of aquathermolysis using catalyst and
hydrogen donor was carried out in Liaohe Oilfield in 2001.
Five steam injecting extra-heavy oil wells have been treated
by aquathermolysis using catalyst (Fe) and hydrogen donor
developed (see Table 3). Specially, well C is the well from
which the oil used in the laboratory research was sampled.
Some steam had been injected to warm-up the reservoir in
advance and then the catalyst was injected at 0.02kmol per ton
steam and developed hydrogen donor at 0.1m3 per ton steam,
together or apart. The production performance of the wells is
listed in Table 3, it shows that up to 80% (from 660 to 133Pa·
s for well A, also measured at 80℃) viscosity decrease was
obtained, at the same time, production for each of the 5 steam
injection wells was significantly increased in that the
accumulative total increased oil amounted to 4139 tons, an
average of 828 tons, the recovery of the extra-heavy oil was
obviously improved.
3
In addition, the properties of treated oil sampled from well
C when it had produced for 14 days, are listed in Table 4. It
shows that the field treatment had a similar upgrading effect
on Liaohe extra-heavy oil as far as chemical components are
concerned. It could be found that the aquathermolysis using
catalyst and hydrogen donor is feasible for Liaohe extra-heavy
crude oil.
Conclusions
1. It could be found that the metal catalyst could accelerate
the aquathermolysis of Liaohe heavy oil under steam
injection conditions. The aquathermolytic reactions in the
presence of catalyst, e.g. Fe(II) led to near 60% decrease
in viscosity of oil treated for 72 hours compared with the
original crude oil.
2. The experiments adding water and hydrogen donor, e.g.
tetralin shows less than 40% viscosity reduction approxi-
mately.
3. Using catalyst and hydrogen donor, a further decrease
(up to 90% for tetralin) in viscosity was observed. It
indicates the synergetic effect of hydrogen donor and
catalyst on Liaohe extra-heavy oil aquathermolysis.
4. Average molecular weight of oil was decreased after the
aquathermolysis treatment, by adding Fe(II) and hydro-
gen donors, and the H/C increased. At the same time, the
sulfur content was decreased greatly and the combination
of Fe(II) and hydrogen donor conduced much larger
effect on sulfur content decrease. The content of resin
and asphaltene was lowered using Fe(II) and/or hydrogen
donors, accordingly, the content of saturated and
aromatic hydrocarbons was increased.
5. A hydrogen donor developed was cheaper, whereas
effective close to the tetralin for aquathermolysis of
Liaohe extra-heavy oil.
6. The aquathermolysis of Liaohe extra-heavy oil using
catalyst and hydrogen donors was enhanced by extanding
reaction time or increasing reaction temperature.
7. The field testing of aquathermolysis using catalyst and
hydrogen donor was carried out at five Liaohe extra-
heavy oil wells, as a result, the oil recovery was
improved and treated oil upgraded greatly.
Acknowledgements
Financial supports from China National Petroleum Corpora-
tion (CNPC) and Heilongjiang S&T Bureau for the comple-
tion of this research are greatfully acknowledged.
References
1. W. R. Shu, K. J. Hartman, “Thermal Visbreaking of Heavy Oil
during Steam Recovery Processes”. SPE Reservoir Engineering,
September 474-482 (1986).
2. H. H. Xu, N. E. Okazawa, R. G. Moore, et al., “In Situ Upgrading
of Heavy Oil”, Journal of Canadian Petroleum Technology, Vol.
40, No. 8 August 45-53 (2001).
3. G. Brons, M. Siskin, “Bitumen Chemical Changes during
Aquathermolytic Treatments of Cold Lake Tar Sands”, Fuel,
Vol. 73, No 2 183-191 (1994).
4. P. D. Clark, J. B. Hyne, “Steam-Oil Chemical Reactions:
Mechanisms for the Aquathermolysis of Heavy Oils”, AOSTRA
Journal of Research, Vol.1, 15-20 (1984).
4 SPE 84863

5. J. B. Hyne, “Aquathermolysis- A Synopsis of Work on the 7. P. D. Clark, R. A. Clarke, J. B. Hyne, and K. L. Lesage, “Studies
Chemical Reaction between Water and Heavy Oil Sands During on the Effect of Metal Species on Oil Sands Undergoing Steam
Simulated Steam Stimulation”, AOSTRA Synopsis Report Treatments”, AOSTRA Journal of Research, Vol. 6, No. 1 53-
No.50, 1986. 64(1990).
6. C. Ovalles, C. Vallejos, et al., “Heavy oil Downhole Upgrading
Process using Hydrogen Donors under Steam Injection
Conditions”, SPE 69692 1-6 (2001).

Table 1. The properties of oil untreated and treated with catalyst and/or hydrogen donor

Fe(II)+Hydrogen
Analytical item Untreated Fe(II) Tetralin Fe(II)+Tetralin
donor developed
Viscosity at 80°C, Pa·s 220 96 136.5 28.5 43.8
Average molecular weight 790 638 690 446 467
Element Analysis
C, % 86.8 83.7 84.4 80.7 83.9
H, % 11.0 14.7 13.7 14.7 14.7
S, % 0.96 0.63 0.90 0.32 0.35
N, % 0.80 0.76 0.78 0.73 0.75
SARA
Saturated hydrocarbon, % 17.4 21.6 18.2 27.0 25.3
Aromatic hydrocarbon, % 19.2 22.2 20.6 25.5 24.2
Resin, % 43.9 40.8 42.8 37.0 39.2
Asphaltene, % 19.5 15.4 18.4 10.5 11.3

a: The viscosity and the followings were measured at 80°C.

Table 2. The experimental scheme for aquathermolysis of the Liaohe Extra-Heavy oil

Reaction temperature Reaction time

Run Group Reactants
°C hours

a 24, 48, 72, 120, 168,

1 100g Crude Oil+ 100g water+ 0.02M Catalyst
240
100g Crude Oil+ 100g water+ 5/ 10/ 15/ 20ml
2 24, 72, 168
Hydrogen donor 160, 180, 200, 220,
100g Crude Oil+ 100g water+ 0.02M Catalyst+ 240, 260 24, 48, 72, 120, 168,
3
5/ 10/ 15/ 20ml Hydrogen donor 240
100g Crude Oil+ 100g water+ 0.02M Catalyst+
4 24, 48, 72, 168
5/ 10/ 15/ 20ml Developed Hydrogen donor

a: Fe(II) were experimented at different concentrations 0.001, 0.005, 0.01, 0.02, 0.04, 0.08, 0.1 and 0.2M at 240°C for 72 hours.

Table 3. The field experiments for aquathermolysis of the five Liaohe extra-heavy oil wells

a
Number Viscosity at 80°C Steam injection Injection style of the catalyst Viscosity of oil treated Increased oil Incresed water
of wells Pa•s Cycle and hydrogen donor Pa•s tons tons

A 660 3 Together 133 617 185

B 347 4 Together 87 1437 838

C 220 3 Together 54 1041 708

D 400 5 Apart 102 642 845

E 230 3 Apart 80 402 968

a: Sampled when the well had produced for 14 days.

SPE 84863 5

Table 4. Analysis of properties of Well A treated by aquathermolysis

Analytical item Untreated Laboratory treated Field treated

Viscosity at 80°C,Pa·s 220 43.8 54
Element Analysis
C, % 86.8 83.9 85.8
H, % 11.0 14.7 12.4
S, % 0.96 0.35 0.63
N, % 0.80 0.75 0.70
SARA
Saturated hydrocarbon, % 17.4 25.3 21.8
Aromatic hydrocarbon, % 19.2 24.2 23.7
Resin, % 43.9 39.2 40.4
Asphaltene, % 19.5 11.3 14.1

250
Viscosity(Pa·s，at 80℃)

200

150

100

50

0
ed

II)

II)
)

II)

I)

I)

II)
(II

(II

i(I

(II
o(

o(

n(

u(
at

Fe

Zn

Al
C

C
M

M
re
nt
U

Figure1. The effect of metal species on the viscosity of Liaohe extra-heavy oil
(240°C, 72hours, 0.02M metal species)

220
Viscosity(Pa·s，at 80℃)

180

140

100

60
0 0.05 0.1 0.15 0.2
Fe(II) concentration(M)

Figure 2. The effect of Fe(II) concentration on viscosity

6 SPE 84863