Fuel 86 (2007) 1409–1416

www.fuelfirst.com

Flow improver additives for gas condensate

Ana Erceg Kuzmić, Marko Radošević, Grozdana Bogdanić, Radivoje Vuković *

INA-INDUSTRIJA NAFTE d.d., Research and Development Sector, 10002 Zagreb, Lovinčićeva bb, P.O. Box 555, Croatia

Received 24 July 2006; received in revised form 22 November 2006; accepted 24 November 2006
Available online 28 December 2006

Abstract

This paper describes synthesis and evaluation of polymeric additives for improving the flow properties of gas condensate. The addi-
tives were prepared by the free-radical initiated polymerization of methacryl esters with styrene and acrylic or methacrylic acid. Poly-
merization was performed by initiator azo-bis isobutyronitrile in toluene or xylene at 80 °C. The influence of additives structure,
composition and molar weight, as well as gas condensate properties on its flow properties was studied. Gas condensate samples from
the fields of Kalinovac, Stari Gradac and Molve located in the northern Croatia were used for evaluation of the prepared additives.
It was found that the additives efficiency was considerably influenced by their properties and by condensate n-paraffin content and
distribution.
Ó 2006 Elsevier Ltd. All rights reserved.

Keywords: Gas condensate; Flow improver; Polymeric additives

1. Introduction therefore the problems concerning paraffin deposition in

Natural gas condensate is a by-product of natural gas.
Hydrocarbon fractions, which are liquid at standard temper-
ature and pressure, can if sufficiently light, become gaseous
at high pressures of natural gas fields. When the gas is
removed from the field and pressure reduced, some of the
heavier fractions condense depending on the pressure. The
liquid condensate can be refined like light crude oil. The con-
densate composition generally depends on the production
field. Since the beginning of the 80s in the last century,
INA-INDUSTRIJA NAFTE d.d., Zagreb, Croatia has
been producing gas condensate from the fields of Molve,
Kalinovac and Stari Gradac (St Gradac) situated in north-
ern Croatia. The condensate samples differ in properties
including distribution of n-paraffin content (up to C37).
The absence of heavier fractions (especially resins and
asphaltenes) facilitates an unhindered paraffin crystalliza-
tion causing gelling of condensate in installation facilities.
Such behaviour is also characteristic of paraffinic crude oil,
*
Corresponding author. Tel.: +385 1 238 16 45; fax: +385 1 238 12 28.
E-mail address: radivoje.vukovic@ina.hr (R. Vuković).
condensate and crude oil are usually treated in the same
way. A separate treatment of condensate is also described
in the literature [1–5]. It is well known that the presence of
long-chain normal paraffin in crude oil and derivatives, as
well as in gas condensate is responsible for the precipitation
at near-ambient temperature that affects the bulk stream,
characteristics, and influences the flow properties. In order
to counteract the problems caused by n-paraffin deposition,
several options are available, namely various mechanical,
thermal and chemical means [6,7]. In most cases, paraffin
problems can be resolved efficiently and economically with
chemical products [8]. Paraffin precipitation may be treated
chemically with solvents, dispersants and inhibitors (crystal
modifiers, crystal distorters, wax modifiers). A preferred
option would be to use wax modifier additives, commonly
known as pour point depressants (PPDs), which are
designed to improve cost- effectively the cold-flow properties
of crude oil, gas condensate and derivatives. These com-
pounds do not dissolve, disperse or remove paraffin that
has already been deposited. They are applied in either con-
tinuous or squeeze-type treatment to restrict the crystal size
and shape of precipitated paraffin, and help prevent

0016-2361/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2006.11.033
1410 A.E. Kuzmić et al. / Fuel 86 (2007) 1409–1416

re-agglomeration of paraffin crystals [8,9]. All PPDs are Table 2

structured so that a part of the molecule is similar to paraffin Distribution of n-paraffin fractions in the gas condensate samples Molve 1,
Molve 2, Kalinovac, St Gradac 1 and St Gradac 2; SIM DIS analysis
wax crystals, which provide nucleation sites and co-crystal-
lize with the paraffin wax crystals. The other part of the Fraction Gas condensate sample, weight %
structure, dissimilar to wax crystals, blocks the extensive Molve 1 Molve 2 Kalinovac St Gradac 1 St Gradac 2
growth of wax matrices. Thus, it enables the bulk stream C5 0.79 0.69 2.56 1.87 1.69
to persist as a fluid at lower temperatures and, consequently, C6 1.53 1.09 3.05 2.60 2.37
to remain pumpable, pourable and filterable. C7 2.52 1.87 3.49 3.22 3.03
C8 3.32 2.77 3.63 3.53 3.48
There are many polymeric compounds exhibiting such C9 3.53 3.40 3.41 3.43 3.60
properties. Particular examples of the chemicals used in C10 3.39 3.88 3.08 3.27 3.67
practice include: ethylene–vinyl acetate copolymers, vinyl C11 3.29 3.86 3.06 3.25 3.58
acetate-a-olefin copolymers, alkyl esters of styrene–maleic C12 2.85 3.45 2.70 2.92 3.16
anhydride copolymers, poly alkyl-acrylates, poly alkyl- C13 2.56 3.14 2.47 2.74 2.88
C14 2.41 2.94 2.27 2.56 2.65
methacrylates, and alkyl esters of unsaturated carboxylic C15 2.26 2.62 2.05 2.41 2.48
acids, and a-olefin copolymers [9–16]. C16 1.89 2.18 1.81 2.13 2.06
In this paper, the synthesis of efficient flow improver C17 1.63 1.86 1.49 1.74 1.75
additives for gas condensate of different properties is C18 1.44 1.64 1.27 1.51 1.51
described on the basis of octadecyl methacrylate copoly- C19 1.28 1.50 1.11 1.32 1.33
C20 1.08 1.25 0.92 1.11 1.11
mers with styrene and acrylic or methacrylic acid, as well C21 0.95 1.09 0.78 0.99 1.00
as on the terpolymerization of these monomers in toluene C22 0.80 0.92 0.63 0.81 0.82
or xylene. C23 0.71 0.82 0.55 0.72 0.74
C24 0.59 0.68 0.44 0.59 0.60
C25 0.49 0.60 0.39 0.53 0.51
2. Experimental C26 0.45 0.51 0.33 0.45 0.47
C27 0.38 0.42 0.28 0.39 0.41
2.1. Materials C28 0.34 0.36 0.24 0.34 0.35
C29 0.28 0.29 0.20 0.29 0.29
C30 0.23 0.21 0.14 0.26 0.25
Monomers: acrylic acid (AA), >99%, Fluka; methacrylic C31 0.16 0.09 0.11 0.21 0.18
acid (MAA), >99%, Fluka; dodecyl methacrylate (DDMA), C32 0.11 0.12 0.09 0.13 0.14
polymerization grade, Rohm and Haas; octadecyl methac- C33 0.08 0.08 0.05 0.10 0.10
rylate (ODMA), polymerization grade, Rohm and Haas; C34 0.05 0.05 0.05 0.07 0.08
C35 0.04 0.03 0.04 0.06 0.05
styrene (St), >99.5%, Fluka. C36 0.04 0.02 0.03 0.04 0.04
Solvents: toluene, >99.5%, Fluka; xylene, isomers mix- C37 0.03 0.02 0.04 0.04
ture, Fluka.
Initiators: azo-bis isobutyronitrile (AIBN), AKZO
Chemie.
NMR Bruker Avance 300, at room temperature, in CDCl3
Gas condensate samples from the fields of Molve,
with TMS as internal standard.
Kalinovac, Stari Gradac (INA-INDUSTRIJA NAFTE
Molar weights based on calibration with monodispersed
d.d., Zagreb) the properties of which and n-paraffin distri-
polystyrene standards (Polymer Laboratories) were deter-
bution are listed in Tables 1 and 2.
mined by GPC (Varian HPLC, Model 8500) using a set
of 4-l styrogel columns with THF as solvent, at room
2.2. Measurements temperature.
Testing of flow improver additives was carried out by
The average number of carbon atoms in methacrylic measurements of pour point (ASTM D 97), Linetronic
esters and additive compositions were obtained from FT Oil Lab Apparatus.

Table 1
Characteristics of the gas condensate samples Molve 1, Molve 2, Kalinovac, St Gradac 1 and St Gradac 2
Property Method Gas condensate sample
Molve 1 Molve 2 Kalinovac St Gradac 1 St Gradac 2
3
d 15
Specific gravity, 4 (kg/m ) ASTM D-4052/91 784.6 786.5 765.0 776.6 772.2
API degree Calculated 48.8 48.3 53.4 53.2 51.7
Pour point (°C) ASTM D-97/93 15 15 3 3 9
Dynamic viscosity, 40 °C (mm2/s) ASTM D-446/95 1.29 1.13 1.12 1.42 1.41
Refractive index, n20
D ASTM D-542 1.4460 1.4409 1.4381 1.4448 1.4364
Average molar weight, M m Estimated 165 158 155 175 173
 A.E. Kuzmić et al. / Fuel 86 (2007) 1409–1416
Viscosity and flow curves (rheograms) were measured by
means of the Haake RV20/CV100 rotating viscosimeter.
Paraffin distribution in gas condensate samples by a
modified SIM DIS analysis, ASTM D 2887 method, was
performed by means of GC Varian Star 3400cx apparatus.
2.3. Preparation of additive compounds
The additive compounds were prepared by free-radical
initiated homopolymerization of dodecyl methacrylate
(DDMA) or octadecyl methacrylate (ODMA), and copoly-
merization of ODMA with styrene (St) and/or acrylic acid
(AA), and methacrylic acid (MAA) using azo-bis isobuty-
ronitrile (AIBN) in toluene or xylene. The desired quantity
of comonomers and initiator in solvent were charged into a
polymerization reactor equipped with a mechanical stirrer
and condenser. The reaction vessel was heated through
the thermostated oil bath. The system was protected by
nitrogen atmosphere.
Polymerization was performed out at 80 °C and the
reaction was running for 5 h. Once the polymerization
was completed, the resulting product was cooled to the
room temperature and used as additive without any further
treatment. This procedure was applied to preparation of
polymeric additives with different properties which were
evaluated as favourable flow improvers for gas condensate
samples.
The ultimate polymer was isolated from the reaction
mixture using methanol as precipitating solvent. Repeated
processes of dissolution in toluene and precipitating using
methanol ensure complete removal of unreacted monomer.
The polymer was finally dried under vacuum at 60 °C. The
1
H NMR spectrum indicates the absence of unreacted
monomer in the synthesized polymers. The conversion
was determined gravimetrically.
3. Results and discussion
Besides the additives composition, also the influence of
molar weight, initiator concentration and monomer–sol-
vent ratio were studied. The additives effect on the pour
point and rheological properties of different gas condensate
samples was investigated, too.
3.1. The influence of additive composition on gas condensate
pour point
Structures of the prepared polymers are presented in
Fig. 1.
The structural determination of the polymer was carried
out by recording the 1H NMR spectra using CDCl3 as sol-
vent and TMS as internal standard. The peak assignments
for the polymers are as follows: (a) octadecil methacrylate
polymer, d: 3.9 ppm, –OCH2– groups; 1.2 ppm, –CH2–
groups of the side chain; 0.9 ppm, and –CH3 groups of
the side chain; (b) styrene polymer, d: 6.9–7.2 ppm,
–C6H5 groups; 1.1–2.4 ppm, –CH2–CH– groups; (c) acrylic
1411
Fig. 1. Structural representation of (a) homopolymer of DDMA, ODMA;
(b) copolymer of ODMA–St; (c) copolymer of ODMA–MAA (AA) and
(d) terpolymer of ODMA–St–MAA (AA).
acid polymer, d: 2.5 –2.3 ppm, –CH–COO– groups;
1.5–2.1 ppm, –CH2– groups and (d) methacrylic acid poly-
mer, d: 1.4–2.1 ppm, –CH2– and –CH3 groups.
Polymerization conditions, conversion, polymeric addi-
tive compositions, molar weight of additive, and pour
point of the untreated gas condensate and that treated with
200 ppm of prepared additive, including one commercial
additive, Nalco 5353, are shown in Table 3.
The influence of poly(ODMA-co-St) additives concen-
tration on the pour point of gas condensate samples Molve
1, Kalinovac and St Gradac 1 is presented in Table 4.
Several important conclusions can be drawn from the
results shown in Table 3. Primarily, it is evident that poly-
meric additives obtained by homopolymerization of meth-
acrylic esters (DDMA and ODMA) are not efficient for the
pour point depression of the investigated gas condensate
samples, independently of their properties. Furthermore,
it is obvious that poly(ODMA-co-St) additives of different
composition and molar weight exhibit pour point depres-
sion when added to the gas condensate samples Molve 2,
Kalinovac, St Gradac 1 and St Gradac 2 (properties of
which are shown in Tables 1 and 2). On the other hand,
these additives are not efficient for the pour point depres-
sion of the Molve 1 gas condensate sample. The same
results, regarding the behavior of the poly(ODMA-co-St)
additives, were obtained with various additive concentra-
tions for the gas condensate samples Molve 1, Kalinovac
and St Gradac 1 (Table 4). Thus, a possible solution for
overcoming this problem could be preparation of the poly-
meric additives with higher polar properties. It was done by
the copolymerization of ODMA with a functional mono-
mer, acrylic or methacrylic acid. As it can be seen from
Table 3, copolymer of ODMA with AA (MAA), contain-
ing only 0.05 mol fraction of acid in the comonomer feed,
 1412
Table 3
The influence of additive composition and molar weight on the pour point of the gas condensate samples Molve 1 (M1), Molve 2 (M2), Kalinovac (K), Stari Gradac 1 (SG1) and Stari Gradac 2 (SG2);
additive concentration 200 ppm
Sample code Monomer composition in feed and in polymer ( ), mole fraction Conv. (%) Molar weight (g mol 10 3) Pour point (°C)
Gas condensate sample
DDMA ODMA St AA MAA Mw Mn M1 M2 K SG1 SG2
1a 1 (1) – – – – 97 147.4 57.7 15 12 6 6 6
2b 1 (1) – – – – 97 110.9 43.6 15 6 3 6 3

A.E. Kuzmić et al. / Fuel 86 (2007) 1409–1416

3c – 1 (1) – – – 98 128.2 39.3 12 9 3 3 3
4d – 1 (1) – – – 97.5 150.4 47.5 12 9 3 3 3
5 – 0.95 (0.93) 0.05 (0.07) – – 97 102.7 42.6 12 6 18 18 3
6 – 0.93 (0.92) 0.07 (0.08) – – 98 118.5 55.9 15 3 21 24 6
7 – 0.91 (0.90) 0.09 (0.10) – – 97.5 117.2 55.9 15 3 18 15 3
8 – 0.84 (0.81) 0.16 (0.19) – – 97 106.5 56.8 12 6 21 18 6
9 – 0.82 (0.80) 0.18 (0.20) – – 98.4 97.7 52.8 15 6 18 15 3
10 – 0.79 (0.79) 0.21 (0.21) – – 96.5 101.6 49.3 15 6 24 18 6
11 – 0.91 (0.90) 0.09 (0.10) – – 98 92.6 42.5 15 6 24 18 6
12 – 0.91 (0.91) 0.09 (0.09) – – 98 125.8 49.3 15 3 27 18 6
13 – 0.95 (0.96) – 0.05 (0.04) – 97 143.3 44.9 3 6 15 12 3
14 – 0.95 (0.96) – – 0.05 (0.04) 98 132.3 45.0 3 6 15 6 3
15 – 0.91 (0.93) 0.05 (0.03) 0.04 (0.04) – 98 135.2 115.2 3 6 18 6 3
16 – 0.91 (0.92) 0.05 (0.04) – 0.04 (0.04) 97.5 145.2 51.6 3 3 18 6 3

Commercial additive Nalco Co 5353 30.6 18.1 6 3 3 3 6

Untreated gas condensate 15 15 3 3 9

Polymerization conditions. Temperature 80 °C; initiator AIBN, concentration 0.5 wt% except for the samples 11 (0.6 wt%) and 12 (0.4 wt%); solvent (toluene)–monomer ratio = 64:36; polymerization
time 300 min; DDMA – dodecyl methacrylate.
a
C average in alkyl chain, 12.6.
b
C average, 11.3, 1H NMR. ODMA – octadecyl methacrylate.
c
C average, 18.2.
d
C average, 16.6. In other samples ODMA C average 18.2 was used, 1H NMR. St – styrene; AA – acrylic acid; MAA – methacrylic acid.
 A.E. Kuzmić et al. / Fuel 86 (2007) 1409–1416 1413

can be successfully used as pour point depressant in all gas

Polymerization conditions. Temperature 80 °C; initiator AIBN, concentration 0.5 wt% except for the samples 11 (0.6 wt%); solvent (toluene)–monomer ratio = 64:36; polymerization time 300 min;
18
18
24
18
300
condensate samples regardless of their properties. The ter-
polymer of ODMA–St–AA exhibits also a satisfactory

15
18
18
18
St Gradac 1

200
influence on the pour point depression of all the investi-
gated gas condensate samples (Table 3). Based on those
results, copolymers of ODMA with AA and terpolymers

10
10
11
13
100
of ODMA–St–AA of different composition were prepared
and evaluated as pour point depressants of gas condensate

18
24
21
21
200
samples.

13 3.2. Influence of the poly(ODMA-co-AA) and

12
15
10
100
Kalinovac

poly(ODMA–St–AA) additives composition on the gas

condensate pour point
11
8

9
9
Additive concentration (ppm)
50

Copolymers of ODMA with AA and terpolymers of

The influence of poly(ODMA-co-St) additives concentration on the pour point of the gas condensate samples Molve 1, Kalinovac and St Gradac 1

ODMA–St–AA of various compositions were prepared

400
13
13
13
13

and evaluated as good pour point depressants of gas con-

Pour point (°C)

Gas condensate

densate samples. Polymerization conditions of the addi-

200

tives preparation, conversion, additive compositions and

15
15
12
15
Molve 1

influence on the gas condensate pour point are presented

in Table 5. The results clearly show that the prepared addi-
100
13
13
13
13

tives are efficient pour point depressants of gas condensate

samples in a wide range of copolymer and terpolymer
Molar weight (g mol 10 3)

compositions and with various gas condensate sample

characteristics.
55.9
42.5
56.8
49.3
Mn

The results obtained by the study of additives influence

on the rheological properties of some gas condensate sam-
ples are presented in continuation of this work.
117.2

106.5
101.6
92.6

3.3. Influence of the poly(ODMA-co-AA) and

Mw

poly(ODMA–St–AA) additives on the rheological behavior

of gas condensate samples
Conv.

97.5

96.5
(%)

It is known that waxy-paraffinic crude oils, as well as gas

98
97

condensate exhibit a high pour point and possess the non-

Newtonian flow properties at the temperature equal to or
lower than the pour point, due to wax crystallization and
gel formation of their heterogeneous matrix. Thus, a yield
Monomer composition in feed and in copolymer ( ),

stress rises and increase of viscosity occurs. The rheological

properties cease to be constant and viscosity varies as a
(0.10)
(0.10)
(0.19)
(0.21)

function of shear rate [7,17]. The strength of the generated

gel depends on the temperature and cooling rate of the con-
0.09
0.09
0.16
0.21

densate. The lower cooling rate means the higher gel

St

strength and viscosity. It is important to ascertain whether

ODMA – octadecyl methacrylate; St – styrene.

cooling occurs under static or dynamic conditions. A low

cooling rate under static conditions results in pronouncedly
unfavourable flow properties for the particular oil/conden-
sate, because paraffin has all thermodynamic prerequisites
for generating a solid crystal structure. This means that
mole fraction

undisturbed transportation of fluid with increased wax

(0.90)
(0.90)
(0.81)
(0.79)
ODMA

content requires a modification of flow properties. In this

0.91
0.91
0.84
0.79

study, the additives influence on the rheological behaviour

of gas condensate was established by measurements of vis-
cosity and rheograms (shear rate/shear stress) of the origi-
Sample code

nal gas condensate and gas condensate treated with

Table 4

selected additives (using the rotating viscosimetry method).

11

10
7

The influence of poly(ODMA-co-AA), comonomer molar

 1414
Table 5
The influence of poly(ODMA-co-AA) and poly(ODMA–St–AA) additive composition on the pour point of gas condensate samples Molve 1 (M1), Molve 2 (M2), Kalinovac (K), Stari Gradac 1 (SG1)
and Stari Gradac 2 (SG2)
Sample code Monomer composition in feed and in polymer ( ), mole fraction Solvent–monomer ratio Conv. (%) Molar weight (g mol 10 3) Pour point (°C)
Gas condensate

A.E. Kuzmić et al. / Fuel 86 (2007) 1409–1416

ODMA St AA Mw Mn M1 M2 K SG1 SG2
13 0.95 (0.96) – 0.05 (0.04) 64:36a 97 143.3 44.4 3 6 15 12 3
17 0.95 (0.95) – 0.05 (0.05) 64:36 97 156.6 57.5 0 6 6 12 3
18 0.83 (0.85) – 0.17 (0.15) 60:40 97.5 102.1 38.4 6 6 6 6 3
19 0.83 (0.85) – 0.17 (0.15) 70:30 98 81.0 35.1 3 3 3 3 3
20 0.83 (0.86) – 0.17 (0.14) 50:50 99 124.9 49.3 6 3 16 12 6
21 0.62 (0.68) – 0.38 (0.32) 80:20 97 70.3 29.2 3 3 0 3 3
22 0.56 (0.65) – 0.44 (0.35) 80:20 97.5 78.3 26.8 6 3 0 3 3
15 0.91 (0.92) 0.05 (0.04) 0.04 (0.04) 64:36a 97 135.2 45.2 3 6 9 6 3
23 0.87 (0.89) 0.05 (0.04) 0.08 (0.07) 64:36a 97.5 127.2 53.2 6 9 9 6 3
24 0.79 (0.82) 0.05 (0.04) 0.16 (0.14) 64:36a 97 131.7 44.0 6 9 9 6 3
25 0.79 (0.83) 0.05 (0.05) 0.16 (0.12) 50:50a 98 113.0 48.5 6 9 6 3 6
26 0.79 (0.83) 0.05 (0.05) 0.16 (0.12) 50:50 98 109.5 41.1 6 9 6 3 6
27 0.79 (0.83) 0.05 (0.04) 0.16 (0.13) 60:40 97 79.9 35.8 3 9 9 6 3
28 0.79 (0.81) 0.05 (0.05) 0.16 (0.14) 70:30 97 69.2 33.6 0 3 3 3 3

Commercial additive Nalco Co 5353 30.6 18.1 6 3 3 3 6

Untreated gas condensate 15 15 3 3 9

Polymerization conditions. Temperature 80 °C; initiator AIBN, concentration 0.5 wt%; polymerization time 300 min.
a
Toluene; in other samples xylene; ODMA – octadecyl methacrylate; St – styrene; AA – acrylic acid.
 A.E. Kuzmić et al. / Fuel 86 (2007) 1409–1416 1415

ratio in the feed 0.83–0.17 (Table 5, sample 20), and

Untreated Molve 2
poly(ODMA–St–AA), comonomer molar ratio in the feed 0.5
Molve 2 + additive 20
0.79–0.05–0.16 (Table 5, sample 27) on the viscosity/shear Molve 2 + additive 27
rate curves of gas condensate samples Molve 2 and St Gra-
0.4
dac 2 (Tables 1 and 2) are shown in Figs. 2 and 3.

Shear stress, τ (Pa)

Flow curves of the untreated gas condensate samples
τ 0 = 0.24
suggest the non-Newtonian fluid properties. It was found 0.3
that the additives reduced the viscosity of both condensate
samples to about the same extent and that a decrease was
significant at low shear rates. Graphic presentation of shear 0.2
τ 0 = 0.10
rate/shear stress curves of the same gas condensate samples
are shown in Figs. 4 and 5. 0.1
From the rheological data shown in Figs. 4 and 5, it is
obvious that additives reduce the shear stress with mini- τ 0 = 0.05
mum yield values (s0), which are different for the gas con- 0.0
0 5 10 15 20
densate samples Molve 2 and St Gradac 2. The yield value
Shear rate, γ (s-1)

Fig. 4. Shear stress versus shear rate for the gas condensate Molve 2,
100
untreated and treated with 200 ppm of additives at 5 °C.

Untreated Molve 2
Molve 2 + additive 20 1.0
75 Molve 2 + additive 27 Untreated St Gradac 2
St Gradac 2 + additive 20
Viscosity, η (mPas)

St Gradac 2 + additive 27
0.8
50
Shear stress, τ (Pa)

0.6

25
τ0 = 0.29
0.4

0 τ0 = 0.01
0.2
0 5 10 15 20 τ0 = 0.02
Shear rate, γ (s-1)

Fig. 2. Viscosity versus shear rate for the gas condensate Molve 2, 0.0
0 5 10 15 20
untreated and treated with 200 ppm of additives at 5 °C.
Shear rate, γ (s-1)

Fig. 5. Shear stress versus shear rate for the gas condensate St Gradac 2,
100 untreated and treated with 200 ppm of additives at 5 °C.
Untreated St Gradac 2
St Gradac 2 + additive 20
St Gradac 2 + additive 27 in both condensate samples containing additives is lower in
75 comparison with the untreated samples.
Viscosity, η (mPas)

4. Conclusions
50
Gas condensate flow improver additives were prepared
by the free-radical initiated polymerization of octadecyl
25
methacrylate with styrene and/or (meth)acrylic acid in aro-
matic solvents using azo-bis isobutyronitrile as initiator.
The evaluation of additives was carried out by their appli-
cation to the gas condensate samples of various character-
0 istics (gas condensate fields, INA-INDUSTRIJA NAFTE,
0 5 10 15 20 Croatia). The additive efficiency depends on their composi-
Shear rate, γ (s-1)
tion, molar weight and gas condensate properties. The
Fig. 3. Viscosity versus shear rate for the gas condensate St Gradac 2, influence of poly(octadecyl methacrylate-co-styrene) on
untreated and treated with 200 ppm of additives at 5 °C. the pour point is highly dependent on gas condensate
1416 A.E. Kuzmić et al. / Fuel 86 (2007) 1409–1416
characteristics. On the other hand, copolymers of octadecyl
methacrylate with acrylic acid and terpolymers of octa-
decyl methacrylate with styrene and acrylic acid are very
efficient flow improvers regardless of gas condensate prop-
erties. From the obtained rheological data it is obvious that
additives reduce the shear stress with minimum yield value
which is lower in comparison with the untreated conden-
sate samples.
Acknowledgement
The authors gratefully acknowledge the Ministry of
Science, Education and Sports of the Republic of Croatia
for its support.
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