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Demulsification of Crude Oil Emulsion Using

Polyamidoamine Dendrimers

Jun Wang , Cui‐Qin Li , Jie Li & Jin‐Zong Yang

To cite this article: Jun Wang , Cui‐Qin Li , Jie Li & Jin‐Zong Yang (2007) Demulsification of
Crude Oil Emulsion Using Polyamidoamine Dendrimers, Separation Science and Technology, 42:9,
2111-2120, DOI: 10.1080/01496390701241857

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Separation Science and Technology, 42: 2111–2120, 2007
Copyright # Taylor & Francis Group, LLC
ISSN 0149-6395 print/1520-5754 online
DOI: 10.1080/01496390701241857

Demulsification of Crude Oil Emulsion

Using Polyamidoamine Dendrimers

Jun Wang
The State Key Laboratory of Fine Chemical, Dalian University of
Technology, Dalian, P. R. China and College of Chemistry and Chemical
Engineering, Daqing Petroleum Institute, Daqing, Heilongjiang,
P. R. China

Cui-Qin Li and Jie Li

College of Chemistry and Chemical Engineering, Daqing Petroleum
Institute, Daqing, Heilongjiang, P. R. China

Jin-Zong Yang
The State Key Laboratory of Fine Chemical, Dalian University of
Technology, Dalian, P. R. China

Abstract: Six dendrimers with the same polyamidoamine (PAMAM) basic structure
but different terminals/generations were synthesized by divergent method. The dendri-
mers were studied by surface tension measurement at the air-water interface. The
demulsification performance for oil/water (O/W) simulated crude oil emulsion and
crude oil extract directly from field was investigated. The experimental results
indicate that the three dendrimers terminated with ester groups were insufficient demul-
sifiers for crude oil emulsion. However, the three dendrimers terminated with amine
groups exhibited excellent demulsification performance for O/W emulsions. As demu-
lisifers, amine based dendrimers were superior to the commercial polyether ones
(SP-169 and BP-169). The possible mechanisms for the nanocontainer effects of the
dendrimers, through either surface adsorption or internal encapsulation, were
discussed.

Keywords: Dendrimers, oil-in-water emulsions, demulsifications, produced fluid

Received 27 January 2006, Accepted 17 January 2007

Address correspondence to Jun Wang, The State Key Laboratory of Fine
Chemicals, Dalian University of Technology, Dalian 11601, P. R. China. Fax: þ86-
0459-6504325; E-mail: [email protected]

2111
2112 J. Wang et al.

INTRODUCTION

Dendrimers are well-defined macromolecules that have a specific size, shape,

and chemical functionality. Structurally they are regularly branched from a
central core, and a large number of terminal groups surround this core to
form a relatively empty interior. This new type of functional macromolecules
was simultaneously developed by Tomalia and Newkome in the middle of the
1980s (1, 2). Upto the present, dendrimers have been broadly studied for drug
delivery (3, 4), catalysis (5, 6), etc. For all these applications, dendrimers are
considered as nanometer sized containers, with the relatively empty interior as
the cage and the crowded terminal groups as the steric wall. Sometimes,
molecules can be adsorbed onto the surface of dendrimers due to the large
number of terminal groups on a dendrimer. The latter effect has also been con-
sidered one type of nano-container effect (7). These structural features are also
called “dendrimer box” (8) in some special cases, referring to small guest
molecules being encapsulated/adsorbed into/onto the dendrimer. This
report intends to explore the possibilities of using these nanocontainers with
special structures for demulsification.
Oil field emulsions can be formed during either waterflood or steam-
flood techniques when oil and water mix in the reservoir, at the
wellbore, or in surface facilities. Demulsification is an essential industrial
process, mainly used for removing water from crude oil. Because of the
inevitable complex composition of crude oil and the existence of water,
crude oil most likely exists in the form of emulsion with oil emulsified
in the water phase. Whether they are created unintentionally or deliberately,
emulsions eventually must be destroyed to separate the oil and water
phases. Among different methods of demulsification, chemical demulsifi-
cation is one of the most effective and simplest of methods. The efficiency
of demulsification process is largely dependent on the performance of the
demulsifier (9).
The solubilization mechanism is one common demulsificaiton mechan-
isms. It typically means that natural surfactants are dissolved into the bulk
phases of demulsifier (10). Encouraged by the excellent performance of
dendrimers as nanocontainers for drug delivery, catalysis, etc., we
reasoned that dendrimers with properly designed structures might also be
used as efficient demulsifiers. They can dissolve/adsorb the natural surfac-
tants into/onto the nanocontainers rapidly, and lead to the destruction of
emulsion.
Polyamidoamine (PAMAM), the simplest dendrimers, were chosen to
study the demulsification for simulated emulsion. The interior of the dendri-
mers was designed to be polar but hydrophobic, which should match the prop-
erties of a typical surfactant. The outer surface provided by the terminal
groups of the dendrimers was varied between charged and uncharged (but
still polar). The size of the dendrimers was altered from generation 1 (G1),
generation 2 (G2), to generation 3 (G3). Experimental results reveal that the
Demulsification of Crude Oil Emulsion 2113

structure of the terminal groups plays a determining role for the targeted
demulsification. Efficient demulsification only occurs for amine-terminated
dendrimers. In addition, demulsificaiton becomes more efficient as the
generation number of dendrimers increases. The results seem to be consistent
with the solubilization mechanism of the surfactants onto the surface of the
amine-terminated dendrimers through ionic interactions with the negatively
charged surfactants although encapsulation of surfactants into dendrimers
cannot be completed ruled out.

EXPERIMENTAL

Synthesis of Dendrimers

Ethylenediamine, methyl acrylate, and methanol are analytical reagents from

the Shenyang Dongxing Reagent Factory (China).

Synthesis of G1 ester: Ethylenediamine(9.0 g, 0.15 mol) was dissolved in 30 g

of methanol, then methyl acrylate (103.2 g, 1.20 mol) was added into the
flask. The mixture was stirred 24 hours at 258C. The solvent and the
unreacted methyl acrylate were removed under reduced pressures. A
light-yellow liquid G1 ester was obtained.
Synthesis of G1 amine: G1 ester (20.2 g, 0.05 mol) was dissolved in 60 g of
methanol, then ethylenediamine (72 g, 1.20 mol) was added into the
flask. The mixture was stirred for 24 hours at 258C. The solvent and
unreacted ethylenediamine were removed under reduced pressures. A
light-yellow thick liquid G1 amine was obtained.

According to a chemical reaction equation, the above unit reaction was

repeated the G2 ester, G2 amine, G3 ester, and G3 amine were obtained
respectively (11).
The above dendrimers were studied in literature. To conform to the struc-
tures, 1H NMR spectra were recorded for the six dendrimers discussed above
using a Varian NOVA 400 MHz NMR spectrophotometer. CDCl3 was used as
the solvent. Experimental results (Table 1) indicate that the NMR spectra
of the purified dendrimers completely matched those reported by reference
(10).

Preparation of Simulated Emulsion

The surfactant polyoxyethylenenonyl phenol ether (OP-7) and sodium

dodecyl benzene sulfonate (ABS) are of industrial purity, purchased from
the Tianjin Auxiliary Manufactory and Shanghai Auxiliary Manufactory
2114 J. Wang et al.

Table 1. Hydrogen-1 chemical shift of six dendrimers synthesized

Generation Chemical shift assignments d/ppm

G1 ester
(a) 2.50 (b) 2.77 (c) 2.44 (d) 3.67
G1 amine
(a) 2.47 (b) 2.70 (c) 2.36 (d) 3.26 (e) 2.78 (f) 1.96
G2 ester
(a) 2.50 (b) 2.77 (c) 2.36 (d) 3.27 (e) 2.55 (f) 2.77 (g) 2.44 (h)
3.67
G2 amine
(a) 2.43 (b) 2.68 (c) 2.52 (d) 3.21 (e) 2.74 (f) 2.80 (g) 2.36 (h)
3.27 (i) 2.74 (j) 1.55
G3 ester
(a) 2.51 (b) 2.82 (c) 2.37 (d) 3.28 (e) 2.56 (f) 2.78 (g) 2.34 (h)
3.28 (i) 2.56 (j) 2.78 (k) 2.45 (l) 3.68
G3 amine
(a) 2.44 (b) 2.68 (c) 2.34 (d) 3.25 (e) 2.78 (f) 2.68 (g) 2.34 (h)
3.25 (i) 2.78 (j) 2.68 (k) 2.34 (l) 3.25 (m) 2.79 (n) 1.65
a
Hydrogen is in order from core to outside.

(China), respectively. The crude oil was provided by Daqing Oil Field
(China). The molecular structures of surfactants are shown below:

The mixture of 5.0 g of crude oil, 0.1 g of polyoxyethylenenonyl

phenol ether (OP-7), 0.1 g of sodium dodecyl benzene sulfonate (ABS), and
94.8 g of water were separately added into the conical flask, the mixture
was stirred by a mulser at 5000 rpm. Subsequently, the oil phase was
separated, and the simulated crude 1.70% O/W emulsion in the lower layer
was collected. This emulsion was found to be stable within the experimental
timeframe.

Demulsification for Simulated Crude Oil Emulsion

The demulsification experiments were performed by using the standard bottle-

test. The simulated crude oil emulsion and dendrimers were added into the test
bottle, the mixture were well mixed by a hand shaking motion for 200 times at
Demulsification of Crude Oil Emulsion 2115

a frequency of 2 times/sec. The demulsification ratio was evaluated by demul-

sifiction ratio (X), which was calculated using the equation,

Xð%Þ ¼ ðC0
CÞ=C0  100% ð1Þ

Here, C and C0 are respectively the oil concentration in the water phase before
and after demulsificaiton, which were measured using absorption methods.

Demulsification for the Produced Fluid

The O/W produced fluid (extracted from oil well) used in this study was
provided by Daqing Oil Field (China), and the demulsifier SP-169 and BP-
169 were purchased from Xian petroleum chemical industry Auxiliary Man-
ufactory (China). The molecular structure of SP-169 and BP-169 are shown
below:

RESULTS AND DISCUSSION

The structures of the dendrimers used are shown in Fig. 1. As pointed above, a
dendrimer is an organic molecule which regularly branches out from the core
(1). The number of branching points from the core to a terminal group deter-
mines the generation number of the dendrimer. For instance, a G3 dendrimer
means it has three branching points from the core to a terminal group.
For the dendrimer shown in Fig. 1, each generation has two related den-
drimers, one terminated with amine groups and the other terminated with ester
groups. The interior of the two dendrimers for each generation is the same.
Therefore, the solubility of the targeted surfactants in the interior pore of
the dendrimers should be similar. Although the terminal groups were varied
between amines and esters, all dendrimers in Fig 1 were found to be soluble
in water, indicating the hydrophilic nature of these dendrimers.
However, the properties of the dendrimers in Fig. 1 as potential surfac-
tants were found to be substantially different. As shown in (Fig. 2, top), the
amine terminated dendrimers possessed very high surface free energy,
between 69 and 70 mN/m, which is very close to that of water. This result
indicates that all amine terminated dendrimers in Fig. 1, no matter what gen-
eration it is, cannot reduce the surface tension of air-water interface. Conse-
quently, they do not behave like surfactants, at least for air-water interface.
2116 J. Wang et al.

Figure 1. Structures of the dendrimers to be studied.

Figure 2. Surface free energy of different dendrimers. Top: amine terminated dendri-
mers. (B) G1; (†) G2; (O) G3. Bottom:ester terminated dendrimers. (P) G1; (V) G2;
(R) G3.
Demulsification of Crude Oil Emulsion 2117

A different situation was observed for ester terminated dendrimers

(Fig. 2, bottom). All these three dendrimers possessed significantly lower
surface free energy in comparison to pure water (about 72.5 mN/m at 208C).
This means that these ester based dendrimers can behave like surfactants for
the air-water interface although they are not ideal ones in comparison to
common surfactants.
All ester based dendrimers did not show any sign of demulsification.
Under the same conditions, amine based dendrimers with different generation
numbers demonstrate excellent performance for demulsification of crude oil
emulsion in water (Fig. 3).
For the following experiments, both types of dendrimers were tested sim-
ultaneously. Since ester based ones did not show any demulsificaiton, only the
data for amine based ones will be discussed in detail below.
Although the concentration of the amine based dendrimers was low
(50 mg/L), all three dendrimers showed significant demulsification effects
(Fig. 3). Each curve can be approximated to an exponential function. The
demulsification ratio, increases substantially from G1, to G2, and G3.
The concentration of the amine based dendrimers affects the demulsifica-
tion efficiency significantly (Fig. 4). When the concentration of the G3 amine
dendrimers was 100 mg/L (equivalent to 0.01%), which is still very low,
about 60% of the oil was separated in 10 minutes. In one hour, about 80%
of the oil was separated. In addition, the oil-water interface was very neat
and the water phase was clear, indicating that they are excellent demulsifiers
for this emulsion.
Amine based dendrimers worked as excellent demulsifiers not only for the
simulated crude oil emulsion but also for the crude oil extract from Daqing oil
field. As shown in Table 2, when the concentration of the G3 amine dendrimers

Figure 3. Demulsification ratio (see definition in the experimental section) of amine

based dendrimers at 308C. (B) G1; (†) G2; (O) G3.
2118 J. Wang et al.

Figure 4. Concentration dependence of demulsification using G3 amine dendrimers

at 308C. (P) 30 mg/L; (B) 50 mg/L; (P) 70 mg/L; (†) 100 mg/L

was 30 mg/L, about 90% of the oil was separated in 60 minutes. In addition, the
oil-water interface was very distinct or clear. Comparing with the commercial
polyether demulsifier, the concentration of G3 amine dendrimers had signifi-
cantly better performance although the concentration of the G3 dendrimers
was about 1/3 of that for commercial ones. In fact, the demulsification of
amine-based G3 dendrimers compared favorably with that of the commercial
demulsifiers when its concentration was 1/5 of that for the commercial ones.
The results shown above are encouraging for using dendirmers as demul-
sifiers. At this point, it is unlikely to completely clarify the mechanisms.
However, the results may shine some light on the demulsificaiton mechanisms
using dendrimers, which should at least provide some hints for the future
design of dendrimer based demulsifiers.
The dendrimers may act as “nano-containers” which dissolves the
existing surfactants in the emulsion inside their interior as they often do in

Table 2. The demulsiflcation of dendrimer for produced fluid

Concentration/ Demulsification Demulsification Interfacial

Demulsifier mg/L temperature/8C ratio/% state

G3 amine 10 45 78.1 Distinct

G3 amine 20 45 84.6 Distinct
G3 amine 30 45 90.6 Clear
SP-169 100 45 81.5 Distinct
BP-169 100 45 78.8 Distinct
Demulsification of Crude Oil Emulsion 2119

other cases, such as for drug delivery (12, 13). On the other hand, the amine
terminal groups will be positively charged in water unless the pH of the bulk
aqueous solution is significantly basic, namely above pH ¼ 10. In our
simulated oil-water emulsions, the solution was more or less neutral.
Therefore, the surface charge for amine based dendrimers should interact
with the surfactant strongly (14). It should be pointed out that the amine
groups in the interior of both types of dendrimers should also be positively
charged. However, for electrostatic interactions, the strong steric hinders
should make these interior positive charge centers less reachable.
The emulsion should become unstable if either of the above two processes
occurred, encapsulation or adsorption. In our measurement, the single droplet
method, a droplet of emulsion stabilized with a monolayer of surfactants came
into a bulk solution of water with or without demulsification reagents. If the
surfactants could be quickly captured by the demulsificaiton reagents in the
bulk water solution, the emulsion droplet shall break down and merge into
the bulk oil phase on the top of the water phase.
The first process, encapsulation of surfactants into dendrimers, would
be relatively slow but efficient as the amine based dendrimers do not
behave like surfactants, indicated by the results in Fig. 2. The second
process, surface adsorption, should occur very fast. However, the resulting
dendrimer-surfactant complex might still behave like a surfactant, as the
dendrimer part is hydrophilic and the surfactants are hydrophobic. As a
result, the demulsificaiton by the surface adsorption process occurred
through drastically decreasing the total surface area of stabilization offered
by the original surfactants.
The difference in saturation of the demulsification ratio (the plateau values
in Fig. 3) with differently sized dendrimers could be explained using either of
the processes. A larger dendrimer should have a higher solubilization power for
the existing surfactants in the emulsion because of its larger interior nano-cage.
On the other hand, a large dendrimer would adsorb more surfactants onto its
surface, which should provide a better reduction of the total stabilization
area as discussed above. For the same reasons, the concentration effects of den-
drimers (Fig. 4) could also be explained through both the processes.
One evidence, however, seems to support the surface adsorption hypoth-
esis. As shown in Fig. 3, a significant demulsificaiton effect was observed even
for G1 amine based dendirmers. This dendrimer is not large in size in compari-
son to the surfactants and does not show much cage effects in literature. The
difference between ester based dendrimersis and amine based ones, on the
other hand, does not conflict with either hypothesis.

CONCLUSIONS

Amine based dendrimers were found to be efficient for demulsification of oil-

water emulsion by acting as nano-containers for the surfactants presented in
2120 J. Wang et al.

the emulsion, through either surface adsorption or internal encapsulation of

the surfactants. The dendrimers terminated with amine exhibited excellent
demulsification performance for O/W crude oil emulsion. As demulisifer,
they were superior to the commercial polyether ones (SP-169 and BP-169).
The high demulsification efficiency illustrated here implies that dendrimers
with proper structures have a great potential for oil extraction from today’s
dominating raw oil products, oil-water emulsions.

ACKNOWLEDGEMENTS

We thank CNPC(China National Petroleum Corporation), and Daqing Oilfield

Company Ltd. for financial support.

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