2002 International Conference on Heavy Organic Depositions

ASPHALTENE PRECIPITATES IN OIL PRODUCTION WELLS

Wolfram Kleinitz*
Simon Ivar Andersen**
* Preussag Energie GmbH, Waldstrasse 39, 49803 Lingen, Germany
** Technical University of Denmark, Dept. of Chem. Eng., Bygning 229,
2800 Lyngby, Denmark

ABSTRACT
At the beginning of production in a southern German oil field, flow blockage was
observed during the initial stage of production from the oil wells. The hindrance
was caused by the precipitation of asphaltenes in the proximity of the borehole and
in the tubings. The precipitates were of solid, "dry" consistency and resulted in
total damage to flow.
On the basis of residue samples from the wells, a number of physical and chemical
analyses were performed, and the results were compared with those from studies on
other asphaltenic precipitates. Among other items, the fraction of aromatic compounds in the organic scales from operations definitely differed from the data published in the literature.
In order to dissolve the precipitates and thus eliminate the damage, various organic
solvents and industrial solvent mixtures were examined. The kinetics of the dissolution process in operational samples is described and discussed in detail. The laboratory results were subsequently applied in preparing a stimulation concept which
takes into account the specific asphaltene problems in this field. The stimulation
measures were implemented several times in two wells. Eruptive production was
subsequently resumed in these wells.

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2002 International Conference on Heavy Organic Depositions

The production from the wells was adjusted in such a way that the conditions for
asphaltene deposition are effectively suppressed for several years. The long-term
success of the treatment was also supported by modifying the production strategy.
The process of optimising production is also explained and discussed in detail from
a reservoir engineering standpoint.

INTRODUCTION
Asphaltene precipitates in crude oil are difficult to detect as such during the production history of a well. This situation is illustrated for the example of a Bavarian
oil field where the precipitation of asphaltenes resulted in production stoppage.
The oil field considered here was Germanys southernmost reservoir for many
years (Boigk, 1981) with a production depth of about 4400 m. Consortial shares in
the reservoir were held by RWE-DEA, MEEG, BEB and Preussag Energie, with
Preussag Energie as operator. The three production wells were drilled in 1967 to
1980 with different drilling fluid systems: clay/water; clay/water/chalk; oil based
mud. With a net thickness of about 11 m for the producing zone (Eocene Basis
sandstone), values of about 10 per cent for the porosity, and 30 to 110 mD for the
permeability were determined from core analyses. As indicated by (Volz, 1984),
the Eocene Basis sandstone is mineralogically characterised by the following parameters: quartz: 50 to 60 per cent; quartzitic residues: 20 to 30 per cent; carbonate
residues: 10 per cent, feldspar: 10 per cent.
At a reservoir temperature of about 120 C, PVT analyses yielded an ave rage gasoil ratio of 150 : 1 at a bubble point pressure of about 255 bar (Kerekes et al.,
1983).
The flowing production rate for dry oil from well 1 was 150 to 250 m/d for about
seven years, but the wet oil production declined significantly with the first occurrence of water in the produced liquid. Even after the installation of an electrical
submersible pump (ESP) and removal of the gravel pack for avoiding fines, no
appreciable increase in production could be achieved. After a total of 19 years, well
1 was shut-in for economic reasons. No significant difficulties were experienced
during production, with the exception of frequent scraping of the risers. This was
attributed to "paraffin deposits", since the pour point of degassed oil was about
21 C (Kerekes et al., 1983).
In contrast, the use of a electrical submersible pump was necessary from the very
beginning for production from well 2. Initially, about 90 m/d of dry oil was produced, (PI = 0.75 m/[bard]), whereas the value had decreased to 20 m/d with a PI
value of 0,1 m/(bard) after a production period of 1.5 years. Lowering of the

2002 International Conference on Heavy Organic Depositions

liquid level (ESP) resulted in significant flow problems in well 2. After a casing
collapse, repair with a liner, and removal of the entire gravel pack, this well also
failed to exhibit any improvement in production behaviour. Because of the flow
problems, the production proceeded by means of a small volume ESP and intermittent pumping.
Operations at well 3 did not begin until 1981. At a dry oil production rate of
35 m/d, flowing production continued for about 1,5 years. After installation of the
ESP for enhancing production, only intermittent production was possible. Similarly
to that from production well 2, the productivity index (PI) was about 0.8 m/(bard)
at the beginning (1981) and decreased rapidly to about 0.1 m/(bard) during the
period of discontinuous production.
As a result of the significant decline in production from the wells, various causes
were first analysed, and the following possibilities were thereby discussed:
drilling fluid, oil quality, blockage by fines, permeability variation in the pay zone,
and forming of a gas block.
The composition of the drilling fluid varied from well to well, and the unfavourable
effects were initially most serious with the use of the oil-based drilling fluid.
No problems were evident from the physical properties of the crude oil, since the
viscosity of the oil was 0.5 mPas at the bubble point, and the associated density
was 0.65 g/cm under reservoir conditions.
The porosity / permeability distribution for various oil fields in the vicinity with
production from the same formation indicated no significant decline in production.
In the oil field considered here, however, the average hydraulic pore diameter
ranges between 0.55 m (well 1) to 0.35 m (well 3).
On the basis of the PVT analyses, a gas deficit of about 0.5 106 m (Vn ) was obtained for wells 2 and 3 with respect to the quantity of oil produced in each case.
Nevertheless, none of the possibilities investigated proved to be an unambiguous
cause of the decline in production.

ASPHALTENE DEPOSITS
In the course of sampling from well 3 (Fig. 1) with a bailer, a dry, coke-like residue
with an ash content of 0.42 per cent and the composition indicated in table 1 was
found at a depth of about 3850 m.

2002 International Conference on Heavy Organic Depositions

100 m

Fig.1: SEM - picture of the bailer sample from well 3

Table 1: Composition of the bailer sample (well 3) with respect to the colloidal
structure groups
Composition
m-%

Molar mass*
g/mol

Degassed oil

Bailer sample

91.5

27.5

333

Petroleum resins+

6.6

1.4

1410

Asphaltenes +

1.9

71.1

3455

Dispersants +

* VPO at 37 C in benzene

Bailer sample

+ Method given by (Neumann et al., 1967)

In correspondence with the characteristic data for the bailer sample, the residue
consisted predominantly of asphaltenes with low contents of petroleum resins
(Kleinitz et al., 1991). The determination of the molar mass by vapour pressure
osmometry (VPO) should be viewed critically because of the aggregate mass
measurements. However, a conspicuous feature is the low asphaltene content in the
degassed oil in comparison with the composition of the bailer sample.

2002 International Conference on Heavy Organic Depositions

The elemental analysis of asphaltenes from the bailer sample with a sulphur content of 0.32 % (w/w) indicated a aromaticity (atomic H/C) of 1.03. 1 H and 13 C nmr
analysis confirmed the presence of aromatic structures. The asphaltene fraction had
a very low solubility even in chloroform at 50 C which affected the quality of the
nmr analysis. The resins was as expected less aromatic (H/C = 1.69) and contained
less heteroatoms.
On the basis of an estimated material balance with due consideration of asphaltene
deposits in the tubing above the pump (SSD) and in the wellbore zone, as well as
the quantity of dry oil produced, a content of 20 to 30 ppm was obtained for the
asphaltene precipitates. The values are in the same range as those from the Ula
field in Norway (Thawer et al., 1990).
SOLUBILITY BEHAVIOUR OF THE ASPHALTENE DEPOSITS
The development of an effective stimulation concept for the two production wells
was of special economic importance at that time (1982/83). In parallel with the
determination of the chemical structure in the asphaltene deposits, the solubility
behaviour of the unpurified operational residues was analysed. Defined solvents as
well as industrial solution mixtures were analysed as a function of the temperature
of the solutions.
Experimental procedure
The deposits in the risers of well 3 were compressed into an aluminium capsule
(2 bar) in such a way that only one side was available as a defined surface
(7.3 cm). For protecting the substance against falling out during the dissolution
process, a thin net was fastened over the solution surface.
The compressed material hangs freely in the solvent (300 ml) under a balance; the
solvent is thereby maintained at a constant temperature. The dissolution proceeds
with free convection. At specified time intervals the weight of the test specimen is
recorded. The change in mass is determined at solvent temperatures of 20, 40, and
65 C over a period of about 4 h.
As a result of swelling, the sample mass initially increases decidedly, and this is
followed by the solution process per se. This period was employed for the evaluation. The subsequent nonuniform shape of the dissolution surface gives rise to a
quasistatic mass variation, which is not considered.
Dissolution behaviour
In figure 2, the dissolution behaviour is illustrated for the example of the aspha ltene sample in R-methylnaphthalene at various temperatures.

Asphaltene in g

2002 International Conference on Heavy Organic Depositions

12
20 C

11

40 C

10

9
8

R - Methylnaphthaline

65 C
6
0

50

100

150

200

250

300

Time in min.
0

Time in h

Figure 2: Dissolution behaviour of the asphaltene sample (well 3) in R-methylnaphthalene with free convection
The GC analysis yields the following chemical composition for the R-methylnaphthalene: naphthalene, 3 %; 2-methylnaphthalene, 45 %; 1-methylnaphthalene,
30 %; diphenyl, 8 %; dimethylnaphthalene, 10 %; higher-boiling components, 4 %.
For a water content of 0.1 per cent, the density (20 C) of the mixture is
1.005 g/ml.
A comparison of the physical data for the various solvents is presented in table 2.
In addition, the one-dimensional solvent parameter given by Hildebrand is also
indicated. If it is assumed as a model that the highest dissolution rate occurs when
the Hildebrand parameter is the same for the residue and solvent, this parameter for
the asphaltenes of this well must have a value of about 22 MPa 0,5 as have also been
observed for other asphaltene systems (Andersen & Speight 1992; Cimino et al,
1995).
The data presented in table 2 indicate that 2,4 dimethylpyridine is the best solvent
for the asphaltene residues at 65 C. The Basen, 140/160, exhibit a dissolution rate
which is lower by a factor of 0.67. This mixed product consists of 95 per cent alkyl
pyridines, that is, -/-picoline and 2-ethylpyridine, 65 %; -picoline, 8 %;
2,6-lutidine, 21 %; 2,3-2,4-2,5-lutidine, 5 %; and pyridine, 1 %. Nitrogenous heterocyclic compounds such as pyridine dissolve the asphaltene residues from well 3
better than PAH and other aromatic compounds (Waschl II B/1).

2002 International Conference on Heavy Organic Depositions

Table 2: Physical data and dissolution rate for the solvents under investigation
and the precipitate from well 3

Solvent

Benzene
Xylene
DEA-Sol 99
Solv-ESSO
R-Methylnaphthalin
Waschl II B/1+

Molar mass Boiling point

Beginning

Density
20 C

Dissolution rate
Asphaltenes
well 3
65 C
mg/(cm2 s)

Hildebrandparameter
MPa0,5

g/mol

g/ml

78
106
121
149
144
150

80
135
158
218
238
244

0.879
0.862
0.872
0.982
1.005
1.038

7 10-3
8 10-3
20 10-3
22 10-3
13 10-3
41 10-3

18.8
18.0
18.4
19.7
20.3
20.8

115
133
158

0.982
0.940
0.930

63 10-3
76 10-3
112 10-3

21.9
19.8
22.2

Pyridine
79
Basen 140/160+
100
2,4 Dimethylpyri109
dine
+
Trade name Rtgers-VfT AG, D-47138

Duisburg

DEA-Sol 99 and Solv-ESSO are aromatic fractions with a low benzene content,
whereas a GC-analysis indicates the following composition for Waschl IIB/1:
naphthalene, 7 %; 2-methylnaphthalene, 16 %; 1-methylnaphthalene, 14 %; dimethylnaphthalene, 15 %; fluorenes, 18 %; acenaphthenes, 8 %. The remainder
consists of diphenyls, anthracenes, and diphenyl oxides. The mixture exhibited the
highest dissolution rate among pyridine-free products.
In comparison, the dissolution rate for the asphaltene residue under convective test
conditions for 2,4-dimethylpyridine at 20 C is less than the value for halite (NaCl)
in water by a factor of 70.

Other solution effects

In the course of solvent selection, the presence of sealing materials, packings, and
lubricants in the well and in the feed system at the surface also had to be
considered, since these materials can be attacked by the chemical system.
The following materials were tested for their swelling behaviour at 40 and 65 C
after 24, 48, and 72 h:
O-ring material:
Packing material:

91 Q 1234 H; 91 QV 1237 H
91 Q V 84; 91 V 3904

2002 International Conference on Heavy Organic Depositions

The following solvents were employed for determining the swelling behaviour:
xylene, Waschl II B/1, Waschl II B/1 + 20 % EGMME, Waschl II B/1 + 20 %
EGMBE, bases 140/160, and 2,4-dimethylpyridine. The results after a comparable
period at 65 C are presented in table 3.
Table 3: Swelling behaviour of packing and O-ring materials in various solvents
after 72 h at 65 C in vol-%.
Packings
Type

O-ring
Type

91 V 84

91 V 3904

Xylene
Waschl II B/1
II B/1 + 20 % EGMME
II B/1 + 20 % EGMBE

+ 2.06
+ 1.68
+ 1.81
+ 1.06

+ 2.28
+ 2.77
+ 2.69
+ 2.28

2,4-dimethylpyridine
Bases 140/160

+ 2.40
+ 2.59

+ 2.77
+ 2.47

91 Q 1234 H
+
+
+
+

QV 1237 H

6.8
3.8
9.8
4.1

+ 6.9
+ 1.7
+ 10.9
+ 3.3

+ 63.9
+ 56.1

+ 82.9
+ 54.4

Packing material 91 V 84 exhibits the highest resistance toward the solvent mixture
of Waschl II B/1 and EGMME or EGMBE. Even in comparison with O-ring material 91 Q 1234 H, the combination with EGMME exhibits a higher aggressivity in
the mixture than Waschl II B/1 alone and with EGMBE, for instance. The pyr idine products are suitable for use only if higher swelling resistance is achieved.
On the basis of the various investigations and economical reasons, the following
stimulation liquid was selected for operational application: Waschl II B/1,
etheneglycol mono- methylether (EGMME), condensate (BTX fraction over 5 %).

STIMULATION
In conjunction with the selection of the solvent for dissolving the asphaltenes in the
gravel and wellbore zones, a concept for treatment has been developed in parallel.
Special emphasis was thereby placed on the treatment volume, the time required
for action by the solvent mixture, and the optimal production period until repetition
of the treatment.
On the basis of pressure build-up measurements, more extensive reservoir damage
by asphaltenes had been expected in both wells. For instance, the bottom-hole pressure in well 2 had attained a value of 340 bar during the flowing phase after a shutin time of about 100 h, whereas the 100 h value was only 260 bar after application
of the ESP. Furthermore, analyses of pressure coning around well 2 indicated that
the pressure fell below the bubble point of the crude oil at least temporarily by

2002 International Conference on Heavy Organic Depositions

about 50 bar as a result of production. On the basis of this evaluation, it must be

assumed that the damage extended to a radius of at least 10 m around the well.
The stimulation volume for well 2 was specified to match this radius; this
corresponds to a total treatment volume of 310 m for the solvent mixture (aromatic
solvent Waschoel II B/1 and condensate). For this severely damaged well, a calculated specific volume of 15.5 m/m is obtained, if the gross thickness is taken as
basis.
The initial treatment was performed at constant injection rate of the solvent in the
order indicated in table 4.
Table 4: Stimulation sequence at well 2

Treatment volumes
Slug Interval
O1
1a
1b
2
3
4
5
6
7a
7b
O2

Aromatic
m

Condensate
m

PI
Sum
m

II

m/(bar d)
0.15

25
25
60
10
70
10
30
10
70

25
50
110
120
190
200
230
240
310

0.29
0.40
0.39
0.29
0.40
0.47
0.33
0.41
0.26
0.38

The productivity index was 0.15 m/(bar d) before stimulation, whereas a PI value
of 0.38 m/(bar d) resulted after resumption of operation. Moreover, the flowing
production of dry oil from the well ranged from 20 to 30 m/d. The total stimulation time can be subdivided into an injection period of about 5 d and an precipitates
dissolving period of 30 to 40 d. For facilitating the start of production, the final
slug of aromatic solvent Waschoel II B/1 was displaced by condensate into the
zone immediately surrounding the well. As a result, the low-density condensate
was present in the tubing, and lifting proceeded with only small quantities of gas.

2002 International Conference on Heavy Organic Depositions

Slug volume in m

1. Stimulation

2. Stimulation

20

20

20

10

10

10

0
0

Injec. index in m/(bar x d)

3. Stimulation

20

40

60

0
0

20

20

1.16 PI

1.00

1.00

0.89 PI 1.00

0.75

0.75

0.75

0.50

0.50

0.50

0.25

0.25

0.26 PI 0.25

0.09 PI

20

40

60

20

0.86 PI

0.19 PI

20

Cum. treatment volume in m

Figure 3: Sug subdivision, injectivity and productivity indices for different stimulation in well 3
Subsequently, and for comparison, well 3 was initially stimulated with only 70 m
of solvent (10 m aromatic solvent II B1 and 60 m condensate). The specific
treatment volume was 3.5 m/m, as referred to the gross thickness. The slug
volumes and the associated subdivision (condensate, aromatic solvent II B1) are
indicated in figure 3.
With the initial aromatic slug treatment, flowing production also resumed from
well 3. This demonstrates that precipitate deposits in the reservoir zone can be dissolved by aromatic multicomponent solvents.
For the production strategy, however, the decisive factor is the control or adjustment of the dry oil flow rate in correspondence with the flowing pressure during
regular operation (Andersen, 1990). For this purpose, the flowing pressure must
always assume a value which exceeds the bubble point pressure (PB) of 255 bar by
10 to 15 bar. In figure 4 the variation of the bottom-hole flow pressure is plotted for
the period between two stimulations.
From the figure 4, it is evident that precipitates occur solely as a result of the pressure draw-down in the pay rock and cause a decrease in bottom-hole pressure and
production rate. At a quasiconstant bottom-hole flow pressure of about 280 bar, the
production rate declines from 36 m/d to a final value of 10 m/d. The significant

2002 International Conference on Heavy Organic Depositions

Pressure in bar

decrease in productivity index is manifested by the deposition of asphaltenes in the

zone surrounding the wellbore.
350
10.84
325
1
300
5

4
275

10.85

PB
250

225
0

10

15

20

25

30

35

40

Production rate in m/d

2000

1500

1000
ESP - Production

Oil production in m/mon.

Figure 4: Variation of the bottom-hole flow pressure and production rate between
two treatments, as well as the productivity index determined during this
period

500

after Stimulation

0
1980

Figure 5:

1982

1984

Production rate of well 3

1986

1988

1990

1992
Years

2002 International Conference on Heavy Organic Depositions

After matching of the production rate to the bottom-hole flow conditions, the
flowing production rate of dry oil from both wells was 20 to 35 m/d over a period
of several years. Figure 5 shows the production rate over a period of several years.

CONCLUSIONS
During the early stage of production from a Bavarian dry oil well, deposition of
precipitates was observed in the vicinity of the wellbore and in the tubing. The organic scale was a dry coke-like material consisting of more than 70 per cent asphaltenes.
With the use of these samples, dissolution tests were performed with pure and industrial solvents with free convection. With reference to a measuring temperature
of 65 C, 2,4-dimethylpyridine exhibited the highest dissolution rate of about
110 10 -3 mg/(cm s). With due consideration of the swelling behaviour of industrial installation materials underground and at the surface when exposed to this
heteroaromatic compound, a complex polyaromatic system was employed. This
mixture of polycyclic aromatic compounds, which is a product of bituminous coal
distillation, yielded a dissolution rate of about 40 10-3 mg/(cm s) for the aspha ltenes.
Larger treatment volumes (20 to 300 m) of a mixture of BTX-charged condensate
and Waschl II/B1 were repeatedly injected as demanded by the formation damage.
The shut-in period was about 4 weeks. Flowing production subsequently occurred
from all wells.
The production strategy was varied in such a manner that the pressure did not fall
below the bubble point during operation. That is, production was conducted at quasiconstant bottom-hole flow pressure rather than at constant rate. The borehole
stimulations were repeated approximately every twelve months on the basis of the
PI development.
After stoppage of production from the wells for practical purposes because of asphaltene precipitation, significant flowing production was achieved for several
years with the application of appropriate solvent stimulation and modified production strategy.

2002 International Conference on Heavy Organic Depositions

REFERENCES
Andersen, S.I. 1990. Association of Petroleum Asphaltenes and Related Molecules;
Ph. D. Thesis (Editor). Techn. Uni. Denmark, Dept. Phys. Chem.

Andersen, S.I., Speight, J.G. 1992. Asphaltene Precipitation and Incipient Flocculation in Mixed Solvents. Preprints Am. Chem. Soc. Div. Fuel 37 (3) 1335

Boigk, H. 1981. Erdl und Erdlgas in der Bundesrepublik Deutschland. F. Enke

Verlag, Stuttgart

Cimino, R., Correra, S., Del Bianco, A., Lockhart, T.P. 1995. Solubility and Phase
Behavior of Asphaltenes in Hydrocarbon Media; (in Asphaltenes - Fundamentals
and Applications; Eds. E.Y. Sheu and O.C.-Mullins) Plenum Press, 97

Kerekes, F., Kleinitz, W., Trieloff, H.J. April 1983. Provisions against deposits of
paraffins in oil and gas production. Erdl und Erdgas., p. 110 - 118

Kleinitz, W., Andersen, S.I., Birdi, K.S. 1991. Identification of low concentration
aromatics in solid petroleum precipitates. Symposium Chemistry of Bitumen,
Rome

Neumann, H.J., Rahimian, I., Taghizadeh, D. 1967. Zur analytischen Bestimmung

der sogenannten Asphaltene. Brennstoff-Chemie; 48

Thawer, R., Nicoll, D., Dick, G. Nov. 1990. Asphaltene Deposition in Production
Facilities. SPE-Prod. Eng.

Volz, H., Andreae, H.H. 1984. Einsatz von Chemikalien zur Verbesserung der Produktivitt bzw. Injektivitt von lbohrungen. Erdlchemikalien Symposium
Clausthal-Zellerfeld, 26 pages

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