Fuel 257 (2019) 115881

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Full Length Article

Size exclusion chromatography reveals a key parameter of demulsifiers for T

enhanced water separation from crude oil emulsions
Saroj K. Pandaa, , Murtala A. Mohammeda, Arnaud Cadixb, Mohammed Alaboalirata,
⁎

Claire Poix-Davaineb, Eric Duranc

a
Saudi Aramco, Research & Development Center, Dhahran 31311, Saudi Arabia
b
Solvay, R&I Centre Paris, Aubervilliers 93308, France
c
Solvay, Long Beach Site, LongBeach, CA 90810, USA

GRAPHICAL ABSTRACT

ARTICLE INFO ABSTRACT

Keywords: Demulsifier is used in gas oil separation plants for the separation of water from crude oil emulsion. One of the
Demulsifier important parameters for the enhancement of performance is the optimization of demulsifier formulation with
Emulsion respect to oil composition and produced water chemistry. The consistency in the quality of the formulation is
Crude oil essential to obtain the best separation of water throughout the production period of crude oil. The industry
Size exclusion chromatography
accepted method to optimize formulations is the bottle test method. However, this method remains laborious,
Bottle test
time-consuming, imprecise, and requires access to fresh crude oil, which is not convenient from a practical
Water separation
viewpoint. Instead, routine physical and chemical properties are monitored to ensure the consistency of the
demulsifier quality. It was, however, observed that there was a significant influence on the performance of a
demulsifier from different batches with very close physical and chemical properties. Therefore, we developed a
method using size exclusion chromatography to determine the molecular weight distribution of demulsifier base
material, in this case, alkoxylated alkylphenol-formaldehyde resin. It was found that all the samples contained
two well-separated species with one low molecular weight of about 2700 g/mol and other one with high mo-
lecular weight of about 15000 g/mol. The variation in the content of low and high molecular weight species was

⁎
Corresponding author at: Saudi Aramco, Research & Development Center, Dhahran 31311, Saudi Arabia.
E-mail address: saroj.panda@aramco.com (S.K. Panda).

https://doi.org/10.1016/j.fuel.2019.115881
Received 21 April 2019; Received in revised form 1 July 2019; Accepted 23 July 2019
Available online 28 August 2019
0016-2361/ © 2019 Elsevier Ltd. All rights reserved.
S.K. Panda, et al.
identified to be a key parameter significantly influencing the separation performance. It is apparent from this
study that size exclusion chromatography could provide some additional insights on demulsifier intermediate
chain length dispersity which could be correlated to actual separation performance.
1. Introduction
The demand for energy is mostly accelerated with the growth of the
world economy. In particular, the demand for crude oil, being the
dominant source of energy, is expected to persistently grow albeit at
different rates on a yearly basis considering the additional contribution
of other energy sources in various countries [1]. Therefore, it is desir-
able to enhance the crude oil supply to maintain the growth rate of the
world economy. The growing trend of oil demand can be met by the
discovery of new oil fields and/or the efficient utilization of available
reserves using modern technologies for production and processing.
When crude oil is produced, it flows in the form of an emulsion
(usually water dispersed in oil typically noted w/o emulsion). The
presence of water in the oil–water emulsion form causes a number of
problems during production and will enhance corrosion problems in the
subsequent refining processes. Consequently, water must be separated
and removed from the oil before further transportation [2]. The
emulsions are broadly classified into three categories viz. loose emul-
sions, medium emulsions, and tight emulsions depending on the time
required for the separation of oil and water phase [3,4]. The separation
process makes use of four different factors, i.e., thermal, mechanical,
chemical and electrical, and the separation takes place in a gas-oil se-
paration plant (GOSP) [5]. Undoubtedly, the strongest lever in all of
these factors is chemical separation with the use of specifically designed
surface-active molecules also known as demulsifiers or emulsion
breakers [5,6].
Demulsifiers are typically alkoxylated multifunctional oligomers or
macromolecules such as acid or base catalyzed phenol–formaldehyde
resins, epoxy resins, polyethyleneimines, polyamines or polyols. In
general, most demulsifier bases are relatively hydrophobic in nature
and available in organic solvents like alcohols or heavy aromatics and
mixtures of xylenes. An acceptable performance is obtained only
through a formulation of two to four types of demulsifier intermediates.
A formulation is generally selected and optimized on a case to case basis
for a specific field situation which may vary dramatically versus field
location and even throughout the production time of the wells. The
design of a new formulation is typically performed through a simulated
performance study i.e. bottle test before the field application. The bottle
test is a procedure in which a demulsifier formulation is added to a
crude oil emulsion to determine the effectiveness of separation of oil
and water phases [7]. In general, the challenge associated with de-
mulsification of crude oil lies in the fact that water drops are stabilized
by naturally occurring stabilizing species such as asphaltenes which are
often present at large concentration in oil [7–10]. This large excess of
asphaltenes in the system implies that monolayer to larger aggregates of
asphaltenes stabilizes water drops interfaces, prevents drops aggrega-
tion and coalescence. In addition, asphaltenes present at the oil–water
interface are large molecules and aggregates thus difficult to displace
[8,11]. Consequently, access to the oil–water interface is difficult for
the demulsifier molecules. From an extensive trial and error approach
and optimization, highly performing demulsifier molecules were
Table 1
Crude oil characterization: API gravity (°) and crude oil assay.
Crude oils from the fields API gravity (°) Saturates (wt%)
A 29 50
B 31 53.4
C 30 52.8
2
Fuel 257 (2019) 115881
designed and in many cases, only polymeric surface-active molecules
with complex architecture show the ability to disrupt asphaltenes layers
from the oil–water interface [12–16]. Overall destabilization should
occur from the subsequent abrupt decrease in interfacial tension be-
tween oil and water [17].
Whenever it comes to selecting a demulsifier base versus a given
field condition, attempts to develop improvement versus trial and error
bottle testing screening were reported in the literature [16]. Several
authors performed systematic studies on either model or real crude oil
regarding optimization of alkylated resins versus relative solubility
number (RSN) and molecular weight [18,19]. RSN relates to the hy-
drophilic/lipophilic balance of a compound and relates to its ability to
partition into water or oil phases [7]. It was demonstrated that a fairly
narrow optimum of performance versus both RSN and molecular
weights could be observed. As far as molecular weight is concerned, it
was demonstrated for alkylphenol formaldehyde resins that a minimum
of 4,000 g/mol was needed with an optimum in the range of
10,000–15,000 g/mol required to maximize separation performance
[19].
In this study, focus is put on a commercial grade of alkoxylated
substituted phenol–formaldehyde resin. Regarding this chemistry,
synthesis is performed through a 2 steps process. First, a condensation
polymerization of formaldehyde with substituted phenol is undertaken
[20,21]. Then, the resin is alkoxylated with typically ethylene or pro-
pylene oxide. For both steps, deviation from the standard model mo-
lecule may occur depending on how accurately the synthesis process is
being controlled [22]. As far as the resin condensation reaction is
concerned, the process is designed to favor the formation of linear
condensates with controlled molecular weight and limited dispersity.
Nevertheless, it has been reported in the literature that either cyclisa-
tion, [23,24] branching or even crosslinking may occur [25]. The
identification and determination of ratios of these various forms of
condensate are very difficult to detect and differentiate by any con-
ventional analytical techniques. Then, once the alkoxylation step is
completed, the final product can be a fairly complex mixture of dif-
ferent species. In general, conventional physical characterization tech-
niques used for quality control are not able to provide a comprehensive
identification and control over the mixture obtained. In the present
study, we aimed to develop an analytical approach using size exclusion
chromatography to refine the understanding of demulsifier base mole-
cular weight distribution and its correlation to overall water separation
performance. The method implemented can be used to control the
consistency of the demulsifier intermediate chain length distribution in
addition to potential applications in new chemistry developments.
2. Material and methods
2.1. Crude oil characterization
Samples of medium to light gravity crude oil from different Arabian
fields were tested in this study. The details on the crude oil composition
Aromatics (wt%) Resins (wt%) Asphaltenes (wt%)
32.6 12.7 3.5
34 9.8 2.0
34 9.9 1.9
S.K. Panda, et al. Fuel 257 (2019) 115881

Table 2
Elemental analysis of the crude oils.
Crude oils from the fields Carbon (wt%) Hydrogen (wt%) Nitrogen (wt%) Oxygen (wt%) Sulfur (wt%)

A 84 12.2 0.1 0.7 2.8

B 84.5 12.3 0.2 0.2 2.3
C 84.5 12.2 0.2 0.2 2.4

Table 3
Water cut content and its brine composition.
Water chemistry of corresponding crude oils Water cut Water cut Water cut TDS Water cut hardness NaCl (g/ CaCl2·6H2O (g/L) MgCl2·6H2O (g/L)
from the fields (%) pH (ppm) (ppm) L)

A 9 5.2 188,000 16,400 142 78 17

B 42 6.5 72,000 6,800 52 30 11
C 35 7.1 75,000 6,300 58 27 12

and the corresponding water chemistry are presented (Tables 1–3). It

Table 4
can be seen that crude oil sample from field A had a very low water
Characterization of alkoxylated alkylphenol-formaldehyde resin demulsifier
content as well as very high salinity and hardness brine. On the other
intermediates: viscosity was determined at 25 °C under 10 s-1 shear rate using a
hand, samples from fields B and C have slightly lower asphaltenes TA Instruments DHR 2 equipped with cone-plate geometry; RSN was de-
content, higher water cut with significantly lower salinity and hardness. termined using standard dioxane/toluene mixtures [4]; hydroxyl values were
It can be expected that emulsified crude from field A shall be more determined using ASTM E222-17 test method.
challenging to separate with low water cut; water drops are further
Demulsifier intermediate Viscosity (Pa.s) RSN Hydroxyl values (mg
apart thus more difficult to flocculate and coalesce. batches KOH/g)

Original 14.4 10.7 109

2.2. Demulsifier base & formulations
In the frame of this work, demulsifier intermediates are alkoxylated
alkylphenol-formaldehyde resins with strictly identical chemical com-
position. From the original reference batch, each of the batch repeats
was made with variations in process parameters and batch size. Each
batch was characterized using standard physical and chemical char-
acterization methods (see Table 4).
All batches with identical average composition show as expected
relatively consistent RSN values. Viscosities of products as is at 70%
active in the organic solvent are fairly scattered from 2.7 to 14.4 Pa.s
which would translate to some significant molecular weight distribu-
tion variation between samples. In addition, hydroxyl values also show
significant batch to batch variation with counterintuitive order versus
product viscosity. As alkoxylated resins are multifunctional molecules,
OH chain ends (e.g. degree of branching) may vary dramatically with
relatively close viscosity or molecular weight.
Further chromatographic characterizations were performed to re-
fine understanding of alkoxylated alkylphenol-formaldehyde resin de-
mulsifier intermediate microstructure. Then, in order to investigate
performance in realistic systems, oil–water separation tests were con-
ducted using formulations comprising 80% of the studied alkoxylated
alkylphenol-formaldehyde resin demulsifier intermediate and minority
synergist components. These were consistently identical for crude oil
samples from fields B & C and slightly adjusted to adapt for high con-
centration brine for crude oil from field A.
2.3. Bottle test procedure
Bottle tests were performed with the crude oil samples collected at
the upstream of the demulsifier injection points which are free from any
demulsifier chemicals. Demulsifier injection was carried out at a tem-
perature that usually reflects the real system conditions. Each product
was diluted with toluene (40 wt%). The crude oil sample was initially
equilibrated in a water bath to attain the required system temperature
for about 10 to 15 min prior to demulsifier injection. A known volume
Batch 1 5.4 12.9 65
Batch 2 6.5 11.5 71
Batch 3 2.7 11.5 82
of oil was poured into a graduated 100 mL centrifuge tube and a known
demulsifier dosage was added and subsequently shaken 200 times on a
holder rack. Then, the centrifuge tube was placed in a heated water
bath. Water separation was recorded over a period of specified ex-
perimental time at an interval of 5 or 10 min.
2.4. Size exclusion chromatography
Size Exclusion chromatography (SEC) was performed on an Agilent
1200 series high performance liquid chromatograph equipped with a
micro vacuum degasser, a binary pump, an auto-sampler, a column
thermostat. The detection system comprises a UV-diode array detector
set at 254 nm, a refractive index detector and a multi-angle laser light
scattering (MALLS – Mini Dawn TREOS) detector. Wyatt Astra software
was used for instrument control and data analysis. Tetrahydrofuran with
0.01 M tetrabutylammonium tetrafluoroborate was used as mobile
phase. The injection volume was 100 µL. The flow rate was maintained at
1 mL/min throughout the separation. Two GPC columns (Agilent
Polypore, 30 cm) were connected in series equipped with a pre-column
set at 35 °C. After evaporation of the majority of the synthesis solvent,
resin samples were dissolved in the mobile phase (0.35%, wt./vol.), al-
lowed to homogenize for at least 4 h and filtered using syringe filters
(0.45 µm Millipore) prior injection. The dn/dc ratio was set constant for
all samples at 0.11 mL/g which gives a quantitative recovery rate of 95%
for the original reference alkoxylated alkylphenol-formaldehyde resin.
3. Results and discussion
From the initial chromatogram run for the original sample, it can be
seen that molecular weight distribution is fairly broad and divides in

3
S.K. Panda, et al. Fuel 257 (2019) 115881

Alkoxylated alkylphenol-formaldehyde resin demulsifier intermediate chromatogram interpretation with MALLS determination of total polymeric species average Mn and Mw and RI deconvolution determining high and

High Mw fraction content

(%)

88
18
31
72
Low Mw fraction (g/
Fig. 1. Size exclusion chromatogram with refractive index detection of original

2,700
2,800
2,700
2,700
alkoxylated alkylphenol-formaldehyde resin demulsifier intermediate.

mol)
two peaks of polymeric species (see Fig. 1). Then at about 18 min elu-
tion time is observed a peak corresponding to slight variations of sta-
bilizing salt between samples and running mobile phase. At longer
elution times (around 20 min), a broad peak is observed corresponding

High Mw fraction (g/

to traces of remaining aromatic solvents employed in the synthesis. This
peak is also strongly visible in UV detection (not presented here).
In all batches investigated it appears that a systematic bimodal
polymeric distribution is observed in the identical range of molecular

17,200
12,300
11,800
18,200
mol)
weight (see Fig. 2). One broad population of high molecular weight
species in the range of 13–16 min elution time and a low Mw population Polydispersity (PD)
low molecular weight species average molecular weight as well as fraction of high molecular weight species.

2.9
1.2
1.4
2.9
Average Mn (g/

4,500
3,000
3,100
3,900
mol)
Average Mw (g/

13,000

11,300
3,700
4,500
mol)
Demulsifier intermediate

Fig. 2. Overlaid size exclusion chromatograms from original and three varia-
Original
Batch 1
Batch 2
Batch 3
batches
Table 5

tion batches of alkoxylated alkylphenol-formaldehyde resin demulsifier inter-

mediates with refractive index (top) and MALLS detection (bottom).

4
S.K. Panda, et al.
with a narrow distribution in the range of 16–18 min elution time are
observed. Both populations are polymeric and observable in the MALLS
detection signal. Full data analysis provides a classical number and
weight average molecular weights for the total of both polymeric species.
An averaging MALLS interpretation gives a very close number
average molecular weight for all samples (see Table 5). However, a
much broader distribution with a high dispersity of about 3 is observed
for original and batch 3. An analysis attempting to decorrelate poly-
meric species signals obtained from the refractive index detector was
performed. Refractive index detector was chosen over MALLS detector
because refractive index detector is concentration sensitive whereas
MALLS detector is molar mass sensitive. Moreover, considered as-
sumption is that that both high and low molecular species composition
is close enough that we can consider that both species have identical
refractive index increment e.g. dn/dc (in mL/g). Refractive index signal
obtained from the measuring polymer chain would then be directly
proportional to a weight concentration versus elution time. Refined
treatment, with deconvolution of the two species shows an identical
low molecular weight population of about 2,700 g/mol in all the sam-
ples. However, the average molecular weights of high molecular weight
species are more scattered with original and batch 3 as high as 17,000
to 18,000 g/mol. On the other hand, batches 1 and 2 are slightly lower
with about 12,000 g/mol. A dramatic difference in relative contents of
species can be observed with contents of high molecular weight species
ranging from 18 to about 90% depending on the sample.
3.1. Bottle test water separation performance
As already stated, for actual water separation and demulsification
performance tests, alkoxylated alkylphenol-formaldehyde resin de-
mulsifier intermediates are formulated with additional minority com-
ponents to perform realistic field application tests. Bottle test experi-
ments were conducted with the original formulation considered here as
Fig. 3. Plot of oil–water separation kinetics data for different batches of demulsifier formulations tested on crude oils from (a) field A, (b) field B, and (c) field C.
5
Fuel 257 (2019) 115881
a reference demulsifier formulation in order to measure the percentage
of oil–water separation kinetics over a period of time. Percentage of
resolved water was calculated using the formula:
% water resolved
= volume of water resolved / volume of water in wet emulsion
The plots of percentage water resolved versus time in minutes
performed in crudes oil from fields A, B & C show a systematic and
consistent high water separation yield in about 10 to 15 min only with
original resin sample (see Fig. 3). On the other hand, water separation
results using formulations based on alternative batches are either very
poor or highly dependent on the crude oil source.
Water resolution results appear to be highly correlated with al-
koxylated alkylphenol-formaldehyde resin demulsifier intermediate
molecular weight distribution and here specifically with high molecular
weight species content (see Fig. 4).
Indeed, it was seen from the size exclusion chromatography that both
high and low molecular weight species were of relatively identical mo-
lecular weight range and the key variation among samples was the re-
lative content of each species (see Table 3). Bottle test separation results
confirm that the separation of water from field A crude oil is more dif-
ficult than the other two crude oil samples investigated and very sensi-
tive to actual demulsifier intermediate high molecular weight fraction
content. Even intermediate from batch 3 with very close distribution
cannot match the original resin separation yield. It is also worth noting
that separation sensitivity with crude oil samples from fields B and C are
fairly different while crude oil and water cut analysis were very close in
many aspects. Crude oil from field C was more difficult to separate and
very sensitive to high molecular weight fraction in demulsifier inter-
mediate. It might be possible here that slightly higher pH in crude oil C
increases the charge density of carboxylic groups on asphaltenes and
makes separation more difficult than in crude oil from field B [26].
S.K. Panda, et al.
Fig. 4. Yield of oil–water separation after (a) 10 min and (b) 30 min for crude
oil from fields A, B & C versus high molecular weight content in the demulsifier
intermediate resins (dotted lines are only guidelines).
4. Conclusions
The efficiency of oil–water separation is influenced by many factors on
top of oil composition such as water cut, salt content in water and oper-
ating temperature. In this study, the focus was on a single demulsifier
intermediate resin molecular weight distribution and its impact on se-
paration performance. The developed analytical method based on size
exclusion chromatography permitted refinement of the understanding of
demulsifier intermediate performance. First, it was identified that al-
koxylated resins were present in two distinct species. One low molecular
weight population at about 2,700 g/mol and a high molecular weight
population at about 12,000–18,000 g/mol. Work performed here allowed
the refinement of the general statement from the literature [7,19] that
molecular weight has to be within 5,000 to 50,000 g/mol to obtain good
separation performance. Here, it was demonstrated with one base de-
mulsifier intermediate applied for separation of crude oil from three dif-
ferent fields that actual content of the high molecular weight species was
the critical factor to demulsifier performance. While the general industry
accepted method to evaluate demulsifier intermediates and optimize for-
mulations is the bottle test method, it remains laborious, time-consuming,
imprecise because of repeatability issue, and requires access to fresh crude
oil to perform realistic tests. It appears from this work that size exclusion
chromatography could provide some additional insights on demulsifier
intermediate molecular weight distributions which could be correlated to
actual separation performance. This method could be used for demulsifier
intermediate batch qualification prior to formulation without having ac-
cess to fresh crude oil. In addition, it could also be used as a guideline for
the design of new chemistries for difficult field conditions.
Acknowledgements
The authors would like to thank Saudi Aramco & Solvay for al-
lowing to publish the work. Mr. Thunayyan A. Al-Qunaysi is
Fuel 257 (2019) 115881
acknowledged for conducting some of the SEC measurements. Mr.
Sulaiman Jutaily and Mr. Mohammed Almansour are acknowledged for
their contributions to crude oil sampling and participation in the bottle
test experiments.
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