Journal Pre-proof

Effect of asphaltene structure on its aggregation behavior in toluene-normal alkane

mixtures

Abdolhossein Hemmati-Sarapardeh, Forough Ameli, Mohammad Ahmadi, Bahram

Dabir, Amir H. Mohammadi, Leila Esfahanizadeh

PII: S0022-2860(20)30930-3
DOI: https://doi.org/10.1016/j.molstruc.2020.128605
Reference: MOLSTR 128605

To appear in: Journal of Molecular Structure

Received Date: 25 March 2020

Revised Date: 20 May 2020
Accepted Date: 2 June 2020

Please cite this article as: A. Hemmati-Sarapardeh, F. Ameli, M. Ahmadi, B. Dabir, A.H. Mohammadi,
L. Esfahanizadeh, Effect of asphaltene structure on its aggregation behavior in toluene-normal alkane
mixtures, Journal of Molecular Structure (2020), doi: https://doi.org/10.1016/j.molstruc.2020.128605.

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Credit Author Statement

Abdolhossein Hemmati-Sarapardeh: PhD student

Forough Ameli: PhD student

Mohammad Ahmadi: Co-Supervisor

Bahram Dabir: Supervisor

Amir H. Mohammadi: Adviser

Leila Esfahanizadeh: PhD student

Effect of Asphaltene Structure on its Aggregation Behavior in Toluene-

Normal Alkane Mixtures

Abdolhossein Hemmati-Sarapardeh, a,* Forough Ameli, b Mohammad Ahmadi, c Bahram Dabir d

* Amir H. Mohammadi,f * Leila Esfahanizadeh d

a
Department of Petroleum Engineering, Shahid Bahonar University of Kerman, Kerman, Iran
b
School of Chemical Engineering, Iran University of Science and Technology, Tehran, Iran

c Department of Petroleum Engineering, Amirkabir University of Technology, Tehran, Iran

d
Department of Chemical Engineering, Amirkabir University of Technology, Tehran, Iran
f
Discipline of Chemical Engineering, School of Engineering, University of KwaZulu-Natal, Howard College

Campus, King George V Avenue, Durban 4041, South Africa

Abstract - Colloidal behavior of asphaltenes in normal alkane-toluene mixtures has been under

research over the past decades. However, the influence of asphaltene composition and its

structure on asphaltene aggregation in such mixtures has not been fully understood yet. In this

study, the colloidal behavior of asphaltene in normal alkanes-toluene mixture has been

investigated using image processing approach. Three various types of asphaltenes have been

extracted from Iranian oil reservoirs. Asphaltenes were characterized by elemental analysis, X-

Ray Diffraction (XRD), and Diffuse Reflectance Fourier Transform Infrared Spectroscopy

(DRIFTS). The effects of asphaltene concentration, type of normal alkane, ratio of normal alkane

to toluene, and structure of asphaltenes on onset of asphaltene flocculation (OAF) and aggregates

size were investigated. The onset of asphaltene flocculation decreased with increasing asphaltene

concentration. A mathematical model was developed to predict OAF for various normal alkanes

and asphaltenes. The proposed mathematical model has an exponential form with two constants

1
which should be tuned by experimental data. The results indicate that as asphaltene concentration

increases, larger aggregates are formed with an average (AS) size between 8 to 15 microns and

some aggregates greater than 100 micron may be formed. Moreover, the structure and

composition of asphaltenes is determinant of aggregates’ size. The lowest aggregate size refers

to asphaltene C with the lowest number of fused rings, polarity, and aromaticity, which is the

most stable asphaltene with the smallest aggregates size. Asphaltenes A and B have almost the

same size as polarity and aromaticity both contributed to the aggregates size. The aggregates

formed by n-C7 (AS≈ 7.5 to 8.5 microns) are larger than those of n-C10 (AS≈ 8.5 to 12 microns)

and n-C16 (AS≈ 9 to 14 microns). In addition, increasing the ratio of normal alkane to toluene

increased the size of asphaltene aggregates up to a maximum value and then gradually decreased.

Keywords - Asphaltene Aggregation; Asphaltene Structure; Image Processing; Toluene;

Normal alkane.

*Corresponding authors: A. Hemmati-Sarapardeh (aut.hemmati@gmail.com &

hemmati@uk.ac.ir) and B. Dabir (email address: drbdabir@aut.ac.ir) and A.H. Mohammadi

(amir_h_mohammadi@yahoo.com)

2
1. Introduction

The main constituents of a crude oil include aromatics, asphaltenes, saturates and resins

(SARA) [1, 2]. Asphaltene is soluble in benzene, toluene, or xylene (BTX) and insoluble in light

normal alkanes [3-5]. Asphaltene molecular and colloidal structure and the media of

precipitation lead to its deposition. The parameters affecting this issue include pressure,

temperature, solvent to oil ration and solvent type [6, 7]. To successfully predict the asphaltene

precipitation, studying the asphaltene aggregation mechanism and clusters’ structure are of

paramount importance [8]. Aromatic interactions caused by electrostatic attraction between

negative electrons and positive frame of aromatic rings of asphaltene lead to aggregation. On the

other hand, steric hindrance acts as an inhibitor of asphaltene aggregation [9, 10]. The clusters of

aggregates are formed by coagulating nanoaggregates, as they are of high molecular weight.

Attaching theses clusters and other nanoaggregates together, may lead to forming flocculates [8,

10, 11].

The colloidal states of asphaltenes in many solvents including normal alkanes have been

widely reviewed over the past decades; but there are still, uncertainties about the structures and

molar distributions of asphaltenes aggregates throughout the formed network [12]. Various

studies have been conducted to model asphaltene phase behavior and study asphaltene

precipitation during various operating conditions [8, 13-20]. In other studies, various

experiments have been conducted to quantify the amount of asphaltene precipitation in a

specified concentration of precipitant [21, 22]. Based on the experimental data, various models

have been developed to determine the crude oil stability [23-31].

Optical microscopy has been applied for studying asphaltenes precipitation in crude oil -

precipitant mixtures as a function of precipitant concentration [5, 32-34]. Refractive index was

3
another technique applied in crude oil-n-alkane mixtures to study asphaltene precipitation [35,

36]. The near infrared light transmittance technique was applied for determining the onset of

asphaltene precipitation from crude oil using a precipitant [37]. This technique was later

improved using UV light via an spectrophotometer [26, 38]. Some other techniques for

determining the onset of asphaltene precipitation are based on viscosity alterations [39]. Using

this technique, the viscosity of crude oil-precipitant mixture increases as asphaltene precipitates.

Other method is based on alteration in interfacial tension (IFT) of an oil/water mixture, which

suddenly increases as precipitation occurs which is due to the migration of precipitated

asphaltene to oil/water interface [40].

As stated earlier, there are many studies about variations in asphaltenes aggregates size;

however, to the best of the authors’ knowledge, none of them have considered the effect of

aggregates' structure on their size. Studying the effects of asphaltene structure and its

composition on the size of aggregates is very important[8]. Heteroatoms are included in many

functional groups namely, hydroxylic, thiophene, pyridinic, phenolic, and sulfoxide. All of these

structures could affect the asphaltenes size [42 ,41]. In a previous study, asphaltene structure

effect was evaluated on its aggregation behaviour in toluene. This was performed using dynamic

light scattering (DLS)[43]. In this study, we follow up our previous work and investigate the

effect of asphaltene structure in heptane-normal alkane systems.

In the present study, three different asphaltenes are extracted from various Iranian oil

reservoirs. Elemental analysis is used to find the composition of the three asphaltenes.

Characterization of asphaltenes is conducted using X-Ray Diffraction (XRD) and Fourier

transform infrared (FTIR) approaches. FTIR determines functional groups of asphaltenes and

XRD provides valuable information on asphaltene structure [43]. Afterward, some sample

4
toluene solutions with various asphaltenes concentrations are prepared and the precipitation

onset point (POP) of the toluene solutions are determined by adding different volumes of normal

alkanes to the solution. In addition, a mathematical model is proposed to predict the precipitation

onset point of model solution at different concentrations. Image processing software is applied to

determine the asphaltene particles’ size at different conditions. Moreover, the effects of

asphaltene concentration and the type of normal alkane on the aggregation size are investigated.

Aside from that, asphaltene structure effect on aggregation size is studied. Besides, the effect of

normal alkane to toluene ratio on aggregation size is determined. The results of this study would

lead to profound understanding on the effect of asphaltene composition and its structure on its

colloidal action.

2. Materials and Method

ASTM 2007-03 standard is a recognized approach for separation of asphaltene from

crude oil, which is applied in the present study. Three different asphaltenes were used which are

named A, B, and C. The following procedure was performed on each of these asphaltenes:

Sand, water, and other particles were first extracted from heavy oil using centrifugation

at 8000 rpm for 1 hour. A specified mass of crude oil was provided and n-heptane with the ratio

of 1 to 40 (g/ml) was added to the container. It was sealed, sonicated for 30 min and thoroughly

mixed with speed of 700 rpm. The mixture was then kept at ambient temperature for 24 hours to

reach equilibrium. The precipitated asphaltene was filtered and washed for several times using n-

heptane with the ratio of 1/4 (g/ml) and centrifuged for 30 min at 5000 rpm. Then, it was filtered

using the filter paper of size 2.5 μm (Whatman no. 42, England) and washed again using n-

5
heptane to obtain shiny black asphaltenes. The precipitated asphaltene was then dried for 24 h at

temperature of 60 °C and placed at desiccator [44].

2.1. Asphaltenes characterization

The characterization techniques for three of the asphaltenes that were reported in our

previously published work [43], are briefly represented as follows:

The CHN content of asphaltene was determined using Elemental analyzer (2400 series II,

Perkin Elmer Inc., AB, Canada). The sulfur quantity was specified using combustion sulfur

analyzer (Mitsubishi TS-100). Oxygen atom quantity was determined by deduction the weight

percent of CHNS from 100. These lead to determination of the main constituents of asphaltenes.

The negligible contents of metals in asphaltene aggregates were disregarded. Diffuse Reflectance

Fourier Transform Infrared Spectroscopy (DRIFTS) on a Nicolet iS50 spectrophotometer

(Thermofischer, USA) was conducted to determine the asphaltene functional groups [43].

As the three asphaltenes had various compositions and structures, DRIFTS tests were

performed to determine the functional groups that are present in asphaltene, as already

mentioned. However, this test does not give any information on asphaltene structures.

Asphaltenes structures were determined using XRD test. The apparatus specifications are

represented in our previous study[43].

2.2 Oil model solutions preparation

6
 The stock asphaltene solution was prepared by solving a defined amount of asphaltene

into toluene to reach the concentration of 3000 ppm. The prepared solution was then sonicated

and mixed for totally 1 hour at 150 rpm. Various asphaltene solutions were then prepared by

dilution of the stock solution using toluene. Concentrations of under test solutions were 100, 200,

500, 1000, 2000, and 3000 ppm. This leads to six concentrations for each asphaltene to be tested.

2.3 Image processing software

Various optical approaches have been conducted to study the precipitation of asphaltene

from crude oil [5, 32-34]. Average size of aggregates was determined by processing the images

of a digital camera (COOLPIX 5500) attached to a microscope. The high quality pictures were

exported to image processing software ‘ANALYSIS’. Various parameters including average

diameter of aggregates were reported for the selected image. A simple schematic of the

experimental set-up is shown in Figure 1. A multi-step filtering tool was applied in the software

to modify the image and make it detectable for the ANALYSIS software. This process delivered

a collection of clear and sharp contrast pictures for analyses. The sequence of changes made by

filtering process is depicted in Figure S1.

3. Results and Discussion

The characterization of the three asphaltenes was completely described in our previous

study [43]. Here, we briefly explain the differences of the three asphaltenes based on their

compositions, structures, and functional groups. The results are presented in Table S1. The two

techniques indicate different results with the same trends. The amount of heteroatoms sample A
7
is the most and sample C has the minimum value[43]. However, carbon content is the least for

sample A and the most for sample C. The measured composition of the three asphaltenes based

on elemental analysis is in better agreement to the literature. The ratio of H/C is an indicative for

aromaticity of asphaltene and is ranked as: B > A > C.

Characterization of an asphaltene would not thoroughly be determined by its

composition. To determine the size and structure of asphaltenes, XRD analysis was utilized. The

XRD pattern of asphaltenes is depicted in Figure S2. One peak of XRD pattern at 2θ about 20º is

attributed to γ band as the consequence of spacing between aliphatic layers. Moreover, another

peak at 2θ about 25º, appointed as graphene band, is the indicator for spacing between aromatic

layers in asphaltenes [44]. The area under the peaks of 25° , 20° andindicate that aromaticity of

asphaltene B is significant in comparison to asphaltene A. The least value is for asphaltene C

with the minimum portion of aromatic part. The results are also approved by H/C ratio for the

three asphaltenes. The higher values for H/C ratio lead to less aromaticity. The last peak which is

clear at 2θ about 43° represents the aromatic sheets of asphaltene [45].

Figure 2 depicts the structure of one asphaltene nanocluster. The parameters specified in

this figure include, space between saturated sections of the molecules (dr), layer distance

between two aromatic sheets (dm), average height of aromatic cluster sheets perpendicular to

plane of sheets (Lc), average diameter of the aromatic sheets (La). This asphaltene is composed of

seven aromatic rings in each sheet and four aromatic sheets. Some dimensionless parameters

which are determined using XRD include carbons number per aromatic structural unit (CAU),

number of aromatic rings for each of the sheet (Ra), and number of sheets in a cluster (Me) [46,

47]. The above stated parameters are tabulated in Table 1. The value of dr varies from 4.42 to

4.61 Å that have little difference. Also, the spaces between the two sheets of asphaltenes (dm) are

8
the same for the three asphaltenes and vary from 3.49 to 3.50 Å. This parameter is smaller for the

pure graphite structure, in comparison to asphaltenes (dm=3.4 Å). This reveals steric hindrance

which is due to existence of circumferential substituents for asphaltene aromatic sheets in the

clusters [44]. Moreover, the saturated molecules distance is more than aromatic sheets. The

values of Lc for asphaltenes A, B, and C are 29.83, 27.14, and 20.82 Å respectively, which are

within the reported values from other sources [44, 46-51]. In addition, the values of La for

asphaltenes A, B, and C were reported 17.21, 17.14, and 9.36 Å which do not follow the size

trends for the three asphaltenes; however, both of them report the smaller size of asphaltene C in

comparison to asphaltenes A and B. Ra is also an important parameter. Average values of this

parameter for the three asphaltenes A to C are 6.45, 6.43, and 3.51, respectively. The mean

number of rings reported in literature is approximately 7 [52]. The number of aromatic sheets in

clusters of three asphaltenes is 9.45, 8.73, and 6.95, respectively. Moreover, for A, B, and C

asphaltenes, the values of CAU are 28.37, 28.27, and 16.30, respectively. Another important

parameter obtained using XRD was aromaticity index (fa) which was reported as 0.45, 0.41, and

0.33 for asphaltens B, A, and C, respectively. As it is clear, the aromaticity of asphaltene B is

more in comparison to the other asphaltenes [43].

The functional groups of asphaltenes are of paramount importance but could not be

determined using XRD analysis. To study this issue, FTIR analysis was performed for the three

asphaltenes. Generally, normalization of all of the spectra was done for better comparison of the

results[53, 54]. The asphaltenes normalized FTIR is reported in Figure S3. The peaks are almost

the same for the three asphaltenes; however, asphaltene C represents two more peaks which are

for C-O and C-O-C stretching, respectively [55, 56]. The peaks are interpreted in Table S2 [55-

60]. Aliphatic compounds of asphaltenes are represented by aliphatic index. On the other hand,

9
the aromatic index states all aromatic components of asphaltene. Also, the long chain index

represents straight chain alkanes including at least 4 carbon atoms. Substitution index 1 states

benzene structure with one H attaching to C atoms in benzene ring. Substitution index 2 reveals

benzene structure with three H attaching to C atoms of benzene ring. The aforementioned indices

of the three asphaltenes are reported in Table S3. It is obvious that aliphatic indices reveal the

following order: asphaltenes C > B > A, on the other hand, for aromatic index, the order would

be asphaltene B > A > C. The value of long chain index for asphaltenes A, B, and C are 0.051,

0.047, and 0.040, respectively. Substitutions 1 and 2 state that asphaltene A is slightly more

condense in comparison to asphaltenes B and C [43].

Moreover, H/C ratios for stated asphaltenes are 1.01, 1.06, and 1.11, respectively. More

values for H/C show less aromaticity. This is also confirmed using the data in Table 1. The

amount of aromaticity index, fa, obtained by XRD analysis for asphaltenes B, A, and C is 0.45,

0.41, and 0.33, respectively. This trend is also repeated using FTIR analysis. The FTIR aromatic

indices are, respectively, reported as 1.58, 1.48, and 1.30. Moreover, the aliphatic indices of

asphaltenes A, B, C are reported 0.25, 0.35, and 0.32, respectively, which again suggests the

highest aromaticity of asphaltene B. The polarity of asphaltene is analyzed differently. Two

various techniques were applied for determining the composition of crude oil. The results

indicated the highest amount of heteroatoms in asphaltenes A followed by B, and C. Moreover, it

is obvious from the results of FTIR that asphaltene A possesses two more functional groups[43].

Different asphaltene solutions were prepared by adding toluene to asphaltenes to make

solutions with concentrations of 100, 200, 300, 500, 1000, 2000, and 3000 ppm. Three normal

alkanes namely, n-C7, n-C10, and n-C16 were added to the prepared solutions to specify the ratio

of n-alkanes to toluene in which asphaltene precipitates form and appear under microscope. The

10
average size of the visible precipitates under microscope is 0.5 microns. Experimental data and

modeling of onset of asphaltene flocculation based on the added volume of n-C7 to toluene

solution at different concentrations of asphaltene is presented in Figure 3. As it is obvious in this

figure, for asphaltene C this ratio is significantly more in comparison to asphaltenes B and A

which indicates that more n-C7 is needed to be added to the prepared solution to attain the onset

of asphaltene flocculation. The trend of variations in n-C7/toluene ratio is the same for all the

three asphaltenes. For low concentrations of asphaltene solution, asphaltenes B and A data are

separated from each other and converge as the asphaltene concentration increases. Moreover, the

experimental data were also modeled using an exponential function which is also depicted in

Figure 3. The results indicate that modeling results are in good agreement with experimental

data. The proposed model has two constants and for each asphaltene the constants can be

obtained by matching the experimental data to the model. This model could be tuned for any

type of asphaltene which can be applied easily in software packages.

OAF=aeb(x) (1)

In this model, x shows the concentration (ppm) and a and b are constants. The results of

modeling for n-C7 normal alkane and the three asphaltenes are reported in Table 2.

Asphaltene A was then selected and the onset of the flocculation of this asphaltene was

obtained using three different solvents. Figure 4 indicates the ratios at which asphaltene

flocculation begins in various concentrations. The selected solvents in addition to n-C7 were n-

C10, and n-C16. The general trends for variations of asphaltene onset are the same as Figure 3

Moreover, asphaltene flocculation is delayed using n-C10 and n-C16. This is because of long

chains of n-C16 in comparison to n-C10 and n-C7 which leads to higher solubility of asphaltene in

n-C16 solvent and causes asphaltenes to precipitate in higher solvent to toluene ratios.

11
 Increasing the asphaltene concentration in toluene, leads to the lower ratios of solvent to

toluene for the asphaltene flocculation onset. Moreover, the exponential variation trends for the

data are also depicted in Figure 4, which are in good agreement with experimental data. This

functionality was formulated as an exponential equation which was described by Eq. 1. OAF is

the onset of asphaltene formation, A and B are constants which are reported in Table 2 that are

obtained using experimental data. The last column of this table is R2 for all the models. As it is

obvious, the proposed model can correlate the data with high accuracy. The R2 values for all

systems are higher than 0.95 which show an excellent performance of the developed model. This

would be a proper empirical based-model for further investigations on modeling the onset of

asphaltene flocculation.

After finding the onset of asphaltene flocculation for different systems, the effects of

asphaltene concentration, type of normal alkane, type of asphaltenes and the ratio of normal

alkane to toluene solution on the mean size of asphaltene aggregation were investigated. The

ratio of normal alkane to toluene of 2 was used as this ratio is higher than onset of asphaltene

flocculation in all the investigated systems. It should be noted that the size of asphaltene clusters

were measured 3 hrs at which no significant change in the sizer were observed. This time was

close to equilibrium time with no change in the size of asphaltene clusters. Studying kinetics of

aggregation is out of the scope of this study which was investigated completely in literature.

Figure 5 depicts the schematic representation of mico-aggregates of asphaltene B at 2000 ppm,

Rv of 2 and n-C7. As is recommended by this figure, asphaltene clusters with different sizes are

observed. Figure 6 illustrates asphaltene B size distribution of for three various concentrations of

asphaltenes in toluene solution (1000, 2000, and 3000 ppm) with a constant value of Rv =2. This

figure reveals that increasing asphaltene concentrations shifts the curves to the right, meaning

12
formation of asphaltene aggregates with larger mean diameter. As stated earlier, asphaltene has a

low tendency for aggregation in toluene which is mainly because of aromatic interactions

between benzene ring in toluene and core of asphaltenes [8]. Adding normal heptane to the

toluene solution lowers this interaction and causes the precipitation of asphaltene and producing

larger aggregates [61]. For the concentration of 1000 ppm, 16.44% of all asphaltene aggregates

have the mean diameter of 5.2 micron and the largest aggregates have the size of 69.94 micron

with distribution of 0.96%. For the case of n-C7 with concentration of 2000 ppm, 16.36% of

aggregates are formed with average size of 12.13 micron. For the case of n-C7 with concentration

of 3000 ppm, the largest asphaltene aggregates have the mean diameter of 106.2 micron and

most of the aggregates (16.2%) are distributed with mean diameter of 9.2 micron. In addition, by

increasing the concentration of asphaltene in toluene solution, the effect of adding n-C7 increases

and larger asphaltene particles are formed because more asphaltenes are in the system which are

in the form of monomer, dimer and nanoclusters and they are gradually attached to each other to

form micro-cluster.

Aggregates mean diameter for asphaltene B is indicated in Figure 7 for three different

concentrations of n-C7, n-C10, n-C16 at constant value of Rv equal to 2. For the three normal

alkanes, average size of aggregates of asphaltene B increases with increasing asphaltene

concentration, which is due to coalesce of asphaltene clusters [61, 62]. Increase in the strengths

of aromatic interactions between two asphaltenes lead to its association. Moreover, increasing

the length of normal alkane namely, n-C16 leads to decreasing the average size of precipitated

asphaltene in comparison to n-C7 and n-C10. The same results were obtained for asphaltene A. As

it is obvious in Figure S4, increasing the concentration of the solution leads to larger aggregates

as the trends in the figure confirm it. Increasing the length of solvent leads to lower interaction

13
with asphaltene solution and hence decreasing the average diameter of aggregates. Mean

diameter of asphaltene C was also determined using image analysis, in various concentrations of

asphaltene and different normal alkanes including n-C7, n-C10, and n-C16. Rv of the solution was

also kept constant at 2. Similar results were obtained as for asphaltenes A and B. The results of

asphaltene C are indicated in Figure S5.

Figure 8 shows the variations of particle mean diameter at Rv of 2 for different

asphaltenes and various concentrations. Increasing the asphaltene concentration leads to an

increase in average size of aggregates. This trend can be seen for all the three asphaltenes.

Another point is that variations in asphaltenes A and B sizes are approximately the same. On the

other hand, asphaltene C has the minimum aggregates sizes. The structure and various

components of asphaltene lead to variations in size of aggregates. It worth mentioning that

asphaltene aggregates are not rigid bodies, but also there are hydrogen bonding and van der

Waals forces between molecules. The ranking of affective parameters on aggregate sizes is not

still fully understood and there are still debates about it. Molecular dynamics (MD) simulation is

a practical tool for studying various parameters on aggregates behaviour [8, 41, 63]. Aray et al.

[63] revealed that increasing in number of fused rings leads to increasing the aromaticity and

various heteroatoms including N,S, and O augments the solubility parameter. Moreover, Rogel

[64] stated that using energy minimization method in accompanied by Consistent Valence Force

Field confirms that heteroatoms, intermolecular changes, and hydrogen bonds, are not

responsible for stabilization of asphaltene molecules. Takanohashi [65] studied the structure of

three asphaltenes aggregates at high temperatures and denoted that aliphatic side chains and

functional groups of heteroatoms are responsible for trimmers’ stability. The solubility of

asphaltene in various solvents increases as the number of heteroatoms and aromatic rings

14
augments. Moreover increase in aliphatic group lengths leads to their solubility decrease [41]. A

study was conducted by Hosseini et al. [66] through which the rate of aggregation was increased

by increasing the number of heteroatoms in asphaltene. Also, Mahdavi et al. [67] investigated the

effect of interfacial tension on asphaltene precipitation and revealed that it is directly

proportional to H/C ratio. As this is obvious, there is no unified agreement on various affecting

parameters on asphaltene aggregation.

To find the possible reason for the effect of asphaltene composition and structure on the

onset of asphaltene flocculation and their size, these parameters for the three asphaltenes were

reviewed. The highest ratio of H/C in asphaltene C is an indicative of its most stability. In

addition, the lowest values in aromaticity index, aromatic index, and the number of heteroatoms,

lead to the higher stability of the latter asphaltene. The aromaticity of asphaltene B is more in

comparison to asphaltene A. The number of benzene rings is the same for asphaltenes A and B

and more than C. The polarity and aromaticity of asphaltene C designated it as the most stable

asphaltene with lower size. As stated earlier, a combination of various parameters would control

the overall behaviour of asphaltenes. The most number of heteroatoms and functional groups is

attributed to asphaltene A, although the aromaticity of asphaltene B is the highest. The

aggregates size in asphaltenes A and B is almost the same which the higher polarity of

asphaltene A is attributed to the size similar to the higher aromaticity of asphaltene B.

Variations in average size of aggregates vs. volume ratio of normal alkane to toluene

solution is depicted in Figure 9 using image processing software. The selected ratios are 0, 0.5, 1,

2, and 4. For ratio of 0, i.e., only toluene, no aggregate was observed. In a previous study, it was

found that the sizes of asphaltene aggregates in toluene are in the range of few nanometers which

are not detectable by microscope. The largest aggregates were diagnosed for n-C7 for all ratios of

15
normal alkane to toluene solutions. For the ratio of 0.5, the average sizes are 12.6, 11.2, and 8.9

for n-C7, n-C10, and n-C16, respectively. The maximum values for average size of aggregates in

asphaltene A using n-C7, n-C10, and n-C16 are reported 14.7, 12.5, and 10.4 microns. The average

size increases up to the ratio of unity and then decreases smoothly. The reason behind this

behavior is as follows, at initial steps of this test, as normal alkane volume increases, the polarity

and aromaticity mechanism of asphaltene aggregation lead to an increase in the average size of

aggregates using various solutions. However, in constant concentration of asphaltene - toluene

solution, more increase in normal alkanes would lead to decrease in the amount of asphaltene in

total solution (toluene + normal alkane) followed by decrease in average size of asphaltene

aggregates. The aggregates’ mean diameters of n-C16 are the least in comparison to other

asphaltenes which is due to the fact that increasing the length of n-alkane leads to less interaction

between precipitant and the core of asphaltene which results in larger aggregates. When pure

toluene is the solvent, the aromatic ring of toluene interacts effectively with the asphaltene

aromatic rings, which inhibits asphaltene aggregation through aromatic π-π interactions.

However, in the case of normal alkanes + toluene mixtures, interactions of asphaltenes occur

with the size chain, and the aggregation facilitates by decreasing the retarded forces of side

chains [41]. With increasing the length of normal alkane, the retarded forces of side chains

increases; therefore, the asphaltene aggregation decreases.

4. Conclusions

In the present study, image processing software was applied to determine the onset of

asphaltene flocculation and average size of aggregated asphaltenes and to study the effects of

16
composition and structure of asphaltenes on their aggregation in normal alkane-toluene mixtures.

Various asphaltenes were selected and characterized by elemental analysis, XRD, and FTIR.

Main points of this study are summarized as follows:

(1) The onset of asphaltene flocculation for the three asphaltenes was obtained. A

mathematical exponential model was developed to correlate the onset of asphaltene

flocculation as a function of concentration. The proposed model has only two tuning

parameters.

(2) Increasing the values of asphaltene concentration would lead to increase in aggregates’

size and some aggregates with sizes greater than 100 micron are formed.

(3) The size of aggregates is a function of asphaltene composition and structure. The lowest

aromaticity, number of fused rings in each sheet, and polarity are attributed to asphaltene

C which results in the lowest aggregate sizes in various concentrations of n-alkanes.

(4) The mean size of asphaltene A is almost the same as that of asphaltene B. Asphaltene A

has lower aromaticity and more functional groups and higher polarity compared to

asphaltene B. This indicates that both heteroatoms and aromaticity play a key role in

average size of asphaltene.

(5) The aggregates yielded by n-C7 (average size ≈ 7.5 to 8.5 microns) are larger than that of

n-C16 (average size ≈ 8.5 to 12 microns) and n-C10 (average size ≈ 9 to 14 microns).

(6) Increasing the ratio of normal alkane to toluene increases the size of asphaltene particles

up to a maximum value (10.5 micron for n-C7, 12.5 for micron n-C10, and 14.7 micron

for n-C16) and then gradually decreases.

17
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25
Table 1: Structural analysis for asphaltenes A, B, and C based on XRD results [43].

A B C Unit
dr 4.43 4.42 4.61 Å
dm 3.50 3.49 3.49 Å
Lc 27.14 29.83 20.82 Å
La 17.21 17.14 9.36 Å
Me 8.73 9.54 6.95 -
Ra 6.45 6.43 3.51 -
Cau 28.37 28.27 16.30 -
fa 0.41 0.45 0.33 -

26
Table 2: Correlations coefficients for predicting onset of asphaltene flocculation (AOF) for

various normal alkanes as a function of solvent concentration.

Asphaltene type Normal alkane a b R2

B n-C7 1.4029 -9×10-4 0.9506
-4
C n-C7 2.0015 -2×10 0.9907
-4
A n-C7 1.1487 -9×10 0.9883
-4
A n-C10 1.2762 -7×10 0.9822
-4
A n-C16 1.1487 -9×10 0.9883

27
Figure captions

Figure 1. Schematic of the experimental set-up

Figure 2. A schematic representation of a cross section of asphaltenes nanoclusters [43].

Figure 3: Experimental data and modeling of onset of asphaltene flocculation (AOF) based on

volume of n-C7 to toluene solution at different concentrations.

Figure 4. Experimental data and modeling of onset of asphaltene flocculation (AOF) based on

volume of normal alkane to toluene solution at different concentrations of asphaltene A.

Figure 5 Schematic illustration of asphaltene aggregates

Figure 6. Asphaltene size distribution of asphaltene B at three different concentrations at Rv of 2

for n-C7 to toluene solution

Figure 7. Particles mean diameter of asphaltene B at Rv of 2 and different normal alkanes and

concentrations.

Figure 8. Particles mean diameter of different asphaltenes at Rv of 2 for n-C7 to toluene and

different concentrations.

Figure 9. Particles mean diameter of asphaltene A at different Rv and normal alkanes at constant

concentration of 3000 ppm.

28
Figure 1

1
Figure 2

2
 2.5
asphaltene A
asphaltene B
Ratio of nC7 to Toluene Solution,

asphaltene C
2 Expon. (asphaltene A)
Expon. (asphaltene B)
Expon. (asphaltene C)
1.5

0.5

0
0 500 1000 1500 2000 2500 3000
Asphaltene Concentration in Toluene (ppm)

Figure 3

3
 1.6
nC7
1.4 nC10
Ratio of nC7 to Toluene Solution,

nC16
Expon. (nC7)
1.2
Expon. (nC10)
Expon. (nC16)
1

0.8

0.6

0.4

0.2

0
0 500 1000 1500 2000 2500 3000
Asphaltene A Concentration in Toluene (ppm)

Figure 4

4
Figure 5

5
Pecentage number of particles, % 18.00
16.00
14.00 1000 ppm-nC7
12.00
10.00
8.00
6.00
4.00
2.00
0.00

Mean diameter, µm

18.00
Pecentage number of particles, %

16.00
14.00 2000 ppm-nC7

12.00
10.00
8.00
6.00
4.00
2.00
0.00

Mean diameter, µm

14.00
Pecentage number of particles, %

12.00
3000 ppm-nC7
10.00

8.00

6.00

4.00

2.00

0.00

Mean diameter, µm

Figure 6

6
 14 nC7
nC10
12
Average aggregates size, µm

nC16
10

0
1000 ppm 2000 ppm 3000 ppm

Figure 7

7
 16 asphaltene A

14 asphaltene B
Average aggregates size, µm

asphaltene C
12

10

0
1000 ppm 2000 ppm 3000 ppm

Figure 8

8
 16

Average aggregates size, µm

12

nC7
4
nC10
nC16

0
0 0.5 1 1.5 2 2.5 3 3.5 4
Volume ratio of normal alkane to toluene solution

Figure 9

9
Research Highlights

• Asphaltene colloidal behavior is studied using image processing technique.

• Various techniques are used to characterize asphaltenes structures and compositions.

• A mathematical model is developed to predict onset of asphaltene flocculation.

The authors state that there is no conflict of interest