SPE 106180

A Study on Catalytic Aquathermolysis of Heavy Crude Oil During Steam Stimulation

Shoubin Wen, Yujian Zhao, Yongjian Liu, SPE, and Shaobin Hu, Daqing Petroleum Inst.

Copyright 2007, Society of Petroleum Engineers

study, a new oil-soluble catalyst - Molybdenum Oleate – was
This paper was prepared for presentation at the 2007 SPE International Symposium on Oilfield prepared, which is more effective than inorganic catalyst for
Chemistry held in Houston, Texas, U.S.A., 28 February–2 March 2007.
the aquathermalysis reaction of heavy crude oil. This
This paper was selected for presentation by an SPE Program Committee following review of
information contained in an abstract submitted by the author(s). Contents of the paper, as
advantage was confirmed by laboratory and field experiments.
presented, have not been reviewed by the Society of Petroleum Engineers and are subject to
correction by the author(s). The material, as presented, does not necessarily reflect any
position of the Society of Petroleum Engineers, its officers, or members. Papers presented at Laboratory Experiment
SPE meetings are subject to publication review by Editorial Committees of the Society of
Petroleum Engineers. Electronic reproduction, distribution, or storage of any part of this paper Preparation of oil-soluble catalyst. MoO3 was put into
for commercial purposes without the written consent of the Society of Petroleum Engineers is
prohibited. Permission to reproduce in print is restricted to an abstract of not more than distilled water firstly. Then put quantitative oileic acid into the
300 words; illustrations may not be copied. The abstract must contain conspicuous solution and keep the mixture boiling for half an hour. Finally,
acknowledgment of where and by whom the paper was presented. Write Librarian, SPE, P.O.
Box 833836, Richardson, Texas 75083-3836 U.S.A., fax 01-972-952-9435. separating the organic and aqueous phase after the mixture is
cooled. The molybdenum oleate exists in the organic phase.
Abstract The Mo content in the organic metal compounds is 24.9%.
The aquathermolysis of Liaohe heavy crude oil during Properties of heavy oil samples. The heavy oil samples
steam stimulation was studied by using molybdenum oleate as used in this study were taken from Qi40 block (1#) and Qi108
oil-soluble catalyst for the reaction in this paper. The block (2#) in Liaohe oil field. The properties and composition
laboratory experiment shows that viscosity-reduction ratio of of the samples are given in table 1.
heavy oil is over 90% at 240°C, 24hr, with 0.5wt% catalyst Experiment process. In the aquathermolytic process, 75g
solution. The field test that applied aquathermolytic heavy oil sample, 0.4g catalyst and 25g water were put into
technology in puff-and-huff operation was carried out in Qi-40 the autoclave (internal volume 125mL), and then the system
and Qi-108 blocks of Liaohe oilfield. As a result, significant was heated to 240°C kept for 24h. At the end of heating
viscosity reduction and production increase were obtained. period, the autoclave was cooled slowly to room temperature.
Further filed test indicated that the cycle decline rate of heavy Element analysis. The elements in heavy oil were
oil production in puff-and-huff operation was improved by determined by Carle Erba EA1108 model element analysis
aquathermolytic technology. instrument, 3-4 mg sample was used for auto sampling.
Oil compositions analysis. The compositions of oil
samples were determined by high performance liquid
Introduction
chromatographic (HPLC) analysis of deasphaltened oil. The
The researches continue to be aimed at developing
asphaltene were removed by precipitation with addition of 40-
alternative methods for heavy oils production because of the
volume excess dry hexane to the solution of oil in
anticipated shortfall in supplies of high quality crude oil in
dichlormethane.
China. Heavy oil accounts for a large proportion in the proved
The HPLC analysis was carried out on a semi-preparative
oil reservoirs. Heavy oil reservoirs account for 15% of the
basis using a Whatman Magnum-9, 10μsilica column and
total oil reservoirs in China[1]. It is difficulty to produce heavy
ultraviolet (UV) and refractive index (RI) detectors in series.
oils by conventional methods because of their high viscosity.
The silica column was activated previously by overnight
Nowadays, steam stimulation is the most effective way to
flushing (2 ml/min) with dry hexane. The saturate and
produce heavy oil in the world. Steam can reduce the viscosity
aromatic fractions were obtained by elution with hexane, and
of heavy oil and enable the heavy oil to flow through the
the resins were obtained by back-flushing the column with
porous media in reservoir. The oil production can start after
tetrahydrofuran (distilled from LIAlH4) after the collection of
injection of steam and soaking periods.
the aromatic fraction. These fractions were quantified
Many researched results show that the injected steam can
gravimetrically after removal of solvent.
not only reduce the viscosity of heavy oil, but also react with
Viscosity Determinations. Viscosities were determined
some components in the heavy oil and the reservoir minerals,
using a rotary viscometer (Haake RV-550, made in Germen).
thereby, leading to the heavy oil properties and compositions
For the measurement a SV2 senor system was used.
changed [2,3]. Hyne et al. described all of the reaction between
Approximately 2g oil sample was placed in the sample cup
steam, heavy oil and minerals as “ aquathermalysis”.[4]
and allow to equilibrate to 50°C over 20 min. then the
The catalysts usually applied in aquathermalysis are not oil-
measurement was made according to procedures specified by
soluble. It is mean that the catalysts and the heavy oil cannot
the manufacturer.
fully mix up, so the catalytic effect is relatively low. In this
2 SPE 106180

Gases analysis. Hydrocarbon gases, CO2 and H2S were molecular weights of heavy oil and alsphaltene are shown in
determined by a Carle Series S AGC 3975X chromatograph, Table 5. The results indicate that the light components
in which there are series of columns set up by Carle for increase and the heavy components decrease after the catalytic
refinery gas analysis; H2 was analyzed on a Hewlett-Park aquathermalysis reaction. The catalytic effect of the organic
5700A gas chromatograph using 5Å molecular sieve and mental compounds is obvious.
Poropak Q column in series with thermal conductivity Composition changes of heavy oil. The composition
detection. changes of heavy oil samples are given in Table 6. It is very
Average molecular weight measurement. The average clear seen that the saturate and aromatic increased, the resin
molecular weights of the heavy oil samples and asphaltene and asphaltene decreased when the oil soluble catalyst was
before and after the reaction were measured using benzene as added into the reaction system. The results indicate that some
solvent by VPO method. cyclic hydrocarbons were converted into aromatics. Some
normal and iso-alkyl side chains, which are at the edge of the
Results and Discussion condensed aromatic core in the resin and asphaltene
Effects of the oil soluble catalyst on the viscosity of heavy molecules, were broke off from the condensed aromatic, and
oil. According to the procedure, the reacted heavy oil samples then converted into alkyl hydrocarbon. The alkyl chains,
were collected after the reaction and the viscosities were which link two condensed aromatics in the large molecular
measured. The viscosity reduction ratio was calculated structures of the resin and asphaltene may also be broken off.
according following equation: Δμ=(μ0–μ)/ μ0×100%, where The generation of some low molecular weight components
Δμ is the present of the viscosity reduction ratio(%), μ0 is the will dramatically reduce the viscosity of the heavy oil.
original viscosity (Pa•s,50°C) of sample and μ is the Reaction temperature. As well known, the higher the
viscosity(Pa•s,50°C) of the sample after the reaction. The temperature, the better effective of aquathermolysis reaction
effects of the oil soluble catalyst on the physical characters of has. The temperature 240°C is usually adopted in the
heavy oil are given in Table 2. The amount of catalyst added literatures, which is close to the situation in the reservoir
is relatively lower compared with 5wt% reported by other during steam injection[8,9].
researches [11~13] because the amount of Mo accounts for
24.9wt% in the organic compound. It means that oil soluble Field Test
catalyst is more effective due to its homogeneous catalysis. Reservoir characteristics. The experimental wells are
Too much transition metal in the heavy oil during located in the Qi-40 and Qi-108 blocks of Liaohe oil fields.
aquathermolysis reaction is not beneficial to the viscosity The reservoir lithology is a mixture of sand, clay and gravel
reduction[5-7]. The aquathermolysis takes place under the that is mostly pebbly sandstone. The rock has a high
catalysis of the oil soluble organic metal compounds and the percentage of matrixes with high montmorillonite content. The
viscosity of the heavy oil decreases about 90%. It is reservoir has good connectivity and its connective coefficient
advantageous for heavy oil to migrate in porous reservoir. is 0.85. Reservoir porosity is 23-30% with 15 to 20µm pore
Gas Production. The amounts of gases produced in the throat radii. Reservoir permeabilities are between 1.2 and 2.0
reaction were measured according to the gases analysis dacies.
procedure. The results are shown in Table 3. A large amount Operating procedures in the field test. Firstly, a little
of CO2, H2S, and light hydrocarbon gases were produced after part of steam was injected into the well to preheat the
heavy oil samples undergone aquathermalysis reaction under reservoir. Then the catalytic solution was injected into the
240°C. When catalyst is added in the reaction system, the well. Surplus steam was injected according to design
sample produces more gases because the catalyst can lead to parameter. Finally, start producing after a 7-10 days shut-in.
some pyrolysis occurred in lower temperature. This is The production from the test wells before and after the catalyst
consistent with earlier results from other researchers. C2-C7 injection were shown in Table 7.
and H2S mainly come from the decomposition of the Test result. Table 7 shows that the production of heavy
components containing S in the heavy oil. CO2 may partly oil was obviously improved after the catalyst injection. From
attribute to the aquathermalysis, the decarbonxylation of table 8, it is clear that the oil compositions were changed after
carbonxylic derivatives and the decomposition of humic the aquathermolytic treatment. It shows that the viscosity
compounds in the heavy oil, partly come from water-gas decrease by 78.2% (measured at 50°C) in field test, at the
reaction in the present of CO and steam. C2-C7 light
same time, hydrogen in the heavy oil increased significantly.
hydrocarbons can act as solvents to reduce the viscosity of the
The results indicate that the oxygen, sulfur and nitrogen
heavy oil. CO2 can reduce the viscosity of heavy oil and
content decreased. This is because the aquathermolysis usually
improve the flow ability in oil reservoir.
occurs in the heteroatom compounds in heavy oil. The oil has
Elementary analysis of heavy oil. The elementary analysis
more saturate and aromatic components, which are lighter, and
results are given in Table 4. It shows that the ratio of
less resin and asphaltene components, which are heavier. The
hydrogen to carbon is increased and the amount of heter-
comparison of heavy oil production in Qi40-23-35 oil well
atoms in the sample is decreased when undergoing
before and after catalyst injection was shown in figure 1. It
aquathermalysis. The results indicate the organic metal
indicates that aquathermolytic technology is effective to
compounds have a good catalytic effect on heavy oil, which
improve heavy oil production. The cycle decline rate of heavy
can upgrade the heavy oil under steam stimulation.
oil production in puff- and-huff operation was improved
Average molecular weight changes. The average
obviously.
SPE 106180 3

Conclusion 2. Clark, P. D. Clarke, R. A. and Hyne, J. B. et al.: “Studies on the

Effect of Metal Species on Oil Sands Undergoing Steam
1. The oil soluble Molybdenum Oleate is an effective catalyst
Treatment”, AOSTRO J. Res. (1990, Vol.6, No.1) 53-62.
for aquathermolysis because it can fully mix with heavy oil. 3. Clark, P. D. and Hyne, J. B.: “Steam-Oil Chemical Reactions:
The amount of catalyst put into the reaction system is Principles for the Aquathermolysis of Heavy Oils”, AOSTRO J.
relatively lower compared with earlier literatures and the Res. (1984, Vol.1) 15-18.
method of preparation is simple. 4. Hyne, J. B.: “Aquathermolysis-A Synopsis of Work on the
2. It could be found that the oil soluble catalyst(Molybdenum Chmical Reaction between Water and Heavy Oil Sands During
Oleate) could promote the aquathermolysis of the heavy oil Simulated Steam Stimulation”, AOSTRA Synopsis Report (1986,
from Qi40 and Qi-108 blocks in Liaohe oilfield during steam No.50).
stimulation. Using this catalyst, the viscosity of heavy oil 5. Kenneth, A. G.: “Influence of Thermal Processing on the
Properties of Cold Lake Asphaltene: 2. Effect of Steam Treatment
samples was decreased by 90% in laboratory and 78.2% in
During Oil Recovery ”, Fuel. (1983, Vol.62, No.2 ) 370-372.
field test. At the same time, the compositions of heavy oil 6. Clark, P. D. Hyne, J. B. and Tyrer, J. D.: “Chemistry of Organo
were changed obviously. Sulfur Compound Type Occurring in Heavy Oil Sands: 1. High
3. For the viscosity reduction and composition change of Temperature Hydrolysis and Thermolysis of Therahydro-
heavy oil, the flowability of heavy oil was enhanced. So the Thiophene in Relation to Steam Stimulation Processes ”, Fuel.
cycle production of heavy oil increased significantly. (1983, Vol.62, No.5 ) 959-962.
7. Patel et al.: “Catalytic Process for Upgrading of Light
Acknowledgements Hydrocarbons by Treatment of Heavy Hydrocarbons with
Water”, US Patent: US4743357. 1988.05.10, pp: 20.
The authors thank the financial supports from ministry of 8. Vallejos et al.: “Process for Down-hole Upgrading of Extra Heavy
science and technology of China (fund No. 2005CCA06200) Crude Oil”, US Patent: US5891829. 1999.04.06, pp: 8.
and education department of Heilongjiang province (fund No. 9. Thomas, J. C. and Santa, M.: “ Process for Recovering
10551z0002). Hydrocarbon”, US Patent: US4846274. 1989.07.11, pp: 11.

References
1. Zheng, F. G.: “The Distribution and Geo-Chemical Characteristics
of Chinese Heavy Oil”, Petroleum Industry Press of China. (Jun.
1999) 1-10.

Table 1. The properties and composition of the heavy oil

Analysis item 1# 2#
Viscosity/Pa•s, at50°C 12.4 12.0
Specific gravity/g•cm-1, at20°C 1.014 1.031
Water/wt% 12.8 9.85
Ash/wt% 0.049 0.052
C 85.80 84.62
H 11.80 12.01
Elemental
O 1.26 1.30
composition/wt%
S 0.40 0.57
N 0.72 0.68
Saturate 27.4 23.1
SARA Aromatic 31.5 27.9
composition/wt% Resin 34.3 42.1
Asphaltene 6.8 6.9

Table 2. The effects of oil soluble catalyst on the physical character of heavy oil *
viscosity reduction Specific gravity/g•cm-
Reaction System water, % 1
ratio, % , at20°C
# # # # #
1 2 1 2 1 2#
crude oil + water + catalyst1 59.7 62.2 0.0 0.0 0.9732 0.9495
crude oil + water + catalyst2 91.1 93.2 55.9 61.2 0.9885 0.9686
*note: T = 240°C, t = 24h, Catalyst = 0.5wt%, Water = 30wt%, catalyst1 is inorganic, catalyst2 is Molybdenum Oleate
4 SPE 106180

Table 3. The Amounts of gases produced in the reaction (μmol / 100 g heavy oil)
H2 CH4 C2 C3-C7 CO2 H2S
1# 2# 1# 2# 1# 2# 1# 2# 1# 2# 1# 2#
crude oil + water 122 158 358 369 41 44 167 178 224 235 2.8 3.1
crude oil + water
173 201 459 468 48 51 204 210 309 320 3.9 4.4
+ catalyst
Note: T = 240°C, t = 24h, Catalyst = 0.5wt%, Water = 30wt%

Table 4. The element changes in the oil samples

H/C O/C S/C N/C
1# 2# 1# 2# 1# 2# 1# 2#
dehydrated oil before reaction 1.54 1.55 0.015 0.014 0.06 0.06 0.04 0.04
dehydrated oil after reaction 1.57 1.59 0.012 0.011 0.02 0.02 0.03 0.02

Table 5. The average molecular weight changes

Heavy oil asphaltene
1# 2# 1# 2#
dehydrated oil before reaction 648 546 4157 3529
dehydrated oil after reaction 385 324 2742 2085

Table 6. SARA composition changes in heavy oil

Saturate aromatic resin asphaltene
1# 2# 1# 2# 1# 2# 1# 2#
Before reaction 27.4 23.1 31.5 27.9 34.3 42.1 6.8 6.9
After reaction 34.3 32.7 35.7 37.4 25.0 25.1 5.0 4.8

Table 7. Field test results of aquathermolytic technology

Depth Steam Steam Prior cycle production Catalytic cycle production Improved
Well No. /thickness of injected, injection recovery,
oil belt, m tons cycle Time, days Oil, tons Time, days Oil, tons tons
Qi40-23-35 819.8/14.2 1700 7th 204 758.4 189 1023 264.6
Qi40-17-24 767.9/22.0 2200 9th 165 499.7 173 834 334.3
Qi40-3-211 1023.4/8.1 1940 5th 199 635.9 207 986.9 351.0
Qi40-15-23 712.7/20.4 2109 7th 397 1011.2 360 1123.6 112.4
Qi108-23-15 1277/16.8 2100 6th 141 788 144 1022 234
Qi108-3-17 1146/26.9 2821 2th 122 1184 128 969 -115
Qi108-22-04 1094/20.2 1975 6th 210 612.7 191 870.9 258.2
Qi108-8-20 1172/12.0 2570 9th 165 668.4 169 857.9 189.5
Note: The improved oil recovery does not consider the decrease expected in a subsequent cycle.
SPE 106180 5

Table 8. Analysis of oil sampled from Qi40-23-35 well

Analysis item untreated Treated*
Viscosity/Pa•s, at50°C 12.4 2.7
Viscosity reduction ratio, % 78.2
C 85.80 83.90
H 11.80 13.31
Elemental
O 1.26 1.12
composition/wt%
S 0.40 0.14
N 0.72 0.64
Saturate 27.4 32.0
SARA Aromatic 31.5 34.1
composition/wt% Resin 34.3 28.4
Asphaltene 6.8 5.5
*:sampled when the well had produced for 5 days.

1600
Cycle Production,tons

1200

800

400

0
1 2 3 4 5 6 7 8 9
Cycl es

cycle 1-6: no catalyst. cycle 7-9: have catalyst.

Figure 1. Cycle production of Qi40-23-35 oil well in puff-and-huff operation