Subscriber access provided by UNIV OF LOUISIANA
Fossil Fuels
Synthesis, Characterization, and Mechanism of Copolymer Viscosity Reducer for Heavy Oil Xiaobo Lv, Weiyu Fan, Qitian Wang, and Hui Luo Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.9b00217 • Publication Date (Web): 04 Apr 2019 Downloaded from http://pubs.acs.org on April 5, 2019
Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.
is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.
Page 1 of 23 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
1
Synthesis, Characterization, and Mechanism of Copolymer
2
Viscosity Reducer for Heavy Oil
3
Xiaobo Lv,† Weiyu Fan,*,† Qitian Wang,‡ Hui Luo†
4
†
5
China
6
‡
7
Abstract: A functional copolymer viscosity reducer based on molecule dynamics (MD)
8
simulations was synthesized using monomers of mixed ester, 4-vinylpyridine, and styrene. The
9
possible structure and number of hydrogen bonds with in the complex structure of heavy oil were
10
simulated and analyzed after the copolymer was added. Results showed that the number of
11
hydrogen bonds in asphaltene in the simulation structure decreased from 36 to 28 per unit volume
12
with the addition of the copolymer. The original plane overlap structure of asphaltene was
13
damaged as soon as interactions occurred between the asphaltene and copolymer molecule. The
14
system potential energy was higher with the addition of the copolymer, while the non-bond energy
15
difference of the two systems was not obvious. The stereo-hindrance effect of the copolymer
16
viscosity reducer molecules either broken or improved the interlocking structures of the asphaltene,
17
helping to decrease the viscosity of the heavy oil.
18
Key words: Heavy Oil , Copolymer Viscosity Reducer , Solution Polymerization , Molecular
19
Simulation
20
1. Introduction
21
The low molecular weighted hydrocarbon component of crude oil (especially heavy oil) accounts
22
for 20% to 60% or less of the total oil content-far below that of light crude oil. Generally, there are
State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Qingdao.266580, Shandong,
China Petrochemical Lubricant Co., Ltd. Jinan Branch, Jinan 250101, P. R. China
ACS Paragon Plus Environment
Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
1
aggregations of interlocked network structures in heavy oil. Inside these structures, the
2
hydrocarbon component is surrounded by asphaltenes, resins and kinds of paraffin clumped
3
together in the form of gel1 which is responsible for the density and viscosity of the oil and the
4
resulting decline of flow behavior.2,3 The high viscosity and pour point of heavy oils have caused a
5
series of operational and engineering challenges in the pipeline transportation of crude oil,
6
particularly of heavy oil, for developmen and exploitation.1 Therefore, research into the viscosity
7
and drag reduction of crude and heavy oils has become a difficult, yet attractive topic of
8
research.4,5
9
Across the world, pour point depressants are typically used for viscosity reducer in crude oil. In
10
fact, viscosity reduction usually consists of both physical and chemical technologies.6 Oil-soluble
11
polymer viscosity reduction technology, based on pour depressant technology, is relatively new
12
and is yet to be used in most oil-producing countries. Research progress into this technology has
13
been relatively slow, only recently starting in China. Currently, the viscosity reduction mechanism
14
has no unified conclusion. It is generally considered that the viscosity reduction polymer
15
molecules in the colloid structure of asphaltenes have the ability to form hydrogen bonds, and
16
have strong permeability and dispersion effects.7,8 The original plane overlap structure is partly
17
broken into aggregates by the polymer that form a new random packing structure. These new
18
aggregate structures are loose in heavy oil, the stacking order is relatively low, and the elongation
19
space is not large enough, thereby reducing the viscosity of heavy oils.9-11 Because of the
20
differences characteristics of crude and heavy oils from different regions, oil-soluble functional
21
copolymer viscosity reducers are focused on breaking or weakening the stability of the crude and
22
heavy oil interlocking network structure, so as to improve flow behavior.12-14 Thus far,
ACS Paragon Plus Environment
Page 2 of 23
Page 3 of 23 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
1
experimental comparisons have mainly been carried out on only four types of oil-soluble
2
functional polymer viscosity reduction materials: condensation compounds, homopolymers of
3
unsaturated monomers, copolymers of unsaturated-monomers, and polymeric surface active
4
agents.15,16 Therefore, further research on oil-soluble functional polymer viscosity reduction
5
materials for viscosity reduction is necessary.
6
In this study, a molecular dynamics simulation is used to simulate the possible structure and
7
number of hydrogen bonds existing within the complex structure of heavy oil. Based on the results
8
of the molecular simulation, the molecular structure of a viscosity reducer was designed. A
9
functional copolymer viscosity reducer based on mixed ester was synthesized using monomers of
10
stearyl methacrylate, lauryl methlacrylate, methyl methacrylate, n-butyl acrylate, vinyl acetate,
11
4-vinylpyridine, and styrene. Heavy oil was added to a copolymer, and then its structure and
12
possible hydrogen bonds were simulated and analyzed. Interactions between the copolymer
13
viscosity reducer and heavy oil glial asphaltene were confirmed from the perspective of molecular
14
dynamics which provided the basis for the viscosity reduction mechanism.
15
2. Background of Molecular Simulation
16
2.1. Simulation of Hydrogen Bonds in Asphaltene. Asphaltene is the main constituent that
17
affects the viscosity of heavy oil, however, low temperature promoting the crystallization of the
18
paraffins mainly affects the pour point. In general, the higher the content of asphaltenes, resins,
19
and paraffins in heavy oil, the higher the increase in viscosity. In fact, both differences and
20
relationships exist between the viscosity and the pour point in terms of certain physical properties
21
that affect the viscosity of heavy oil. Thus, asphaltene should be considered the main factors
22
affecting viscosity reduction, but the effects of resin and paraffin and the self-aggregation
ACS Paragon Plus Environment
Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
1
behavior of the highly viscous contents of crude oil should not be ignored.17
2
Asphaltene consists of alkyl branches made up of C, H, and O and the functional groups of
3
heterocyclic polycyclic and aromatic hydrocarbons or naphthene. The molecules of asphaltene
4
interact with each other to form hydrogen bonds as an interlocking network of complex
5
structures.18 The heterocyclic and polycyclic aromatic hydrocarbons overlap on the molecular
6
surfaces of asphaltene and are fixed by the hydrogen bonds of the polar segment, piled into
7
particles, and then accumulate into asphalt micelles of different sizes. The asphaltene molecules
8
overlap on the surface of the resin molecules and are fixed by the hydrogen bonds in the
9
heterocyclic and polycyclic aromatic hydrocarbons, which form the cover layer of the resin
10
particles. The particles can also interconnect via hydrogen bonds and form micelles with a high
11
molecular weight19, contributing to the high viscosity of heavy oil. Therefore, the main factors that
12
affect heavy oil viscosity are the microstructure and the molecular inter-force properties of
13
asphaltene and these would be key factors of viscosity and development of a drag reducer at the
14
molecular level.20-22
15
2.2. Molecular Design of Functional Copolymer. According to previous studies and hydrogen
16
bond theories, 5,13,16,18 an ester-based compound has a high combining capacity to form hydrogen
17
bonds, especially a compound containing an N atom like a pyridine ring. At the same time, when
18
the copolymer was synthesized using 4-vinyl pyridine and ester-based compounds, both the
19
benzene ring resonance effect and the reactivity ratio affected the polymerization degree and the
20
structure of the copolymer.1,23 These effects resulted in either a breakdown or improvement of the
21
polymerization progress to the proper interlocking network structure.24 Consequently, a more
22
efficient functional copolymer for viscosity reduction materials could be synthesized.25,26
ACS Paragon Plus Environment
Page 4 of 23
Page 5 of 23 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
1
3. Method and Simulation Details
2
3.1. Simulation Details
3
3.1.1 Simulation of Hydrogen Bonds in Asphaltene. The temperature of the simulation
4
system was 303K, which was above the pour point of Shengli (China) heavy oil, which
5
considerably decreased the effect of paraffins in the simulation system. In terms of the possible
6
hydrogen bond types among asphaltenes, the studied molecular simulation model27-30 was
7
established with proportions of 10:4:10:3:9:10:4:4:4:4:4:4 according to the ability of the alkyl
8
fluorenol, alkyl benzfluorenol, alkyl benzfluorenone, abietic acid, alkyl anthracenecarboxylic acid,
9
alkyl dibenzothiophenecarboxylic acid, 2-alkyl quinoline, benzquinoline, benzcarbazole, alkyl
10
pyridine, benzthiophene, and alkyl thiophene, to form complex molecules by hydrogen bonds,
11
some of the groups were displayed in Figure 1.
12 13 14
Figure 1. Structures of hydrogen bonds in the simulation system of asphaltene
Structures of representative asphltene molecules could be found in Figure S1. As a construction
ACS Paragon Plus Environment
Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 6 of 23
1
tool for the amorphous cells, the Materials Studio was adopted to build the molecular model. The
2
hydrogen bond molecular system of asphaltene was simulated using the NVT system in the
3
Compass force field, and the system’s molecular simulation was studied. The system was made up
4
of C, H, O, N, and S to form 19 different atom types. The number of molecules was 70, the
5
number of atoms was 2439, and the number of bonds was 2575.
6
Next, 5000 steps of energy minimization were implemented with a minimizing tool (Smart
7
Minimizer) at the convergence level (Medium). The molecular dynamics simulation was carried
8
out at 303K by adopting the NPT system of the Dynamics tool in Discover Tools, and 10000 steps
9
were implemented; the step length was 1.0 fs, and the information was stored every 50 steps. Then,
10
hydrogen bonds were built according to the criterion of maximum hydrogen-acceptor distance:
11
2.5Å, minimum donor-hydrogen-acceptor angle: 90º.
12
3.1.2. Molecular Design of the Copolymer. The theoretical simulation model of the viscosity
13
reducer could reduce the viscosity of heavy oil was mainly based on its composition of ester group,
14
aromatic ring, pyridine ring, and alkyl chain.24,27 Therefore, the copolymer that with viscosity
15
reduction
16
lauryl methlacrylate, methyl methacrylate, n-butyl acrylate, vinyl acetate, 4-vinylpyridine, and
17
styrene. The structure scheme was schematically illustrated in Figure S2. Styrene was added to
18
adjust the polymerization degree and the interlocking structure of the polymer. Materials Studio
19
simulated the molecular dynamics modelling of synthesis processes within functional copolymers
20
of the viscosity reduction materials derived from mixed ester, styrene, and 4-vinyl pyridine
21
monomers.
22
function
could
be
synthesized
using
monomers
of
stearyl methacrylate,
The simulation factors were designed to be the same as the simulation of the hydrogen bonds in
ACS Paragon Plus Environment
Page 7 of 23 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
1
asphaltene.31 The system was made up of C, H, O, N, and S to form 21 different atom types when
2
the viscosity reducer was added. The number of molecules was 71, the number of atoms was 3534,
3
and the number of bonds was 3687.
4
The construction tool for amorphous cells was adopted to build the simulation models, and 5000
5
steps of energy minimization were implemented on the system. Then, a dynamics simulation was
6
carried out using the Dynamics tool of Discover Tools at 348K, deemed the most suitable
7
temperature for this solution polymerization reaction.32–34 The thermodynamic date of the
8
synthesis was obtained from the simulation process.
9
3.2. Synthesis of Copolymer Viscosity Reducer
10
3.2.1 Experimental Reagents. The following substances were used in this research project:
11
stearyl methacrylate (Tokyo Chemical Industry Co. Ltd.), lauryl methacrylate (ACROS), n-butyl
12
acrylate (Beijing Yili Fine Chemical Co. Ltd.), methylacrylate (Sinopharm Shanghai Co. Ltd.),
13
vinyl acetate (Tianjin Damao Chemical Co. Ltd.), styrene (Sinopharm Chemical Co. Ltd.),
14
4-vinylpyridine (ACROS), AIBN (Shanghai Shisi Hewei Chemical Co. Ltd.), methylbenzene
15
(Laiyang Kangde Chemical Co. Ltd.), dehydrated alcohol (Tianjin Fuyu Fine Chemical Co. Ltd.),
16
and high-purity nitrogen (Ji’nan Deyang Special Gas Co. Ltd.).
17
3.2.2 Synthesis and Characterizations. The main reactor consisted of a 250-mL five-necked
18
flask equipped with a reflux condenser, a mechanical stirrer, and a heating system. The monomer
19
ratio of styrene, 4-vinylpyridine, stearyl methacrylate, lauryl methacrylate, n-butyl acrylate,
20
methylacrylate, and vinyl acetate was 3:1:3:3:3:3. All of the monomer reagents were added into
21
the five-necked flask with toluene as the dissolvent. The reactor was heated to 60°C, and then, half
22
the amount of the initiator AIBN was added. The temperature was increased to 75°C and
ACS Paragon Plus Environment
Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
1
maintained for 18 h with nitrogen protection. At the 9th h, the left initiator was added. After the
2
polymerization had finished, the solution was cooled at room temperature and transferred to a
3
beaker. The polymer was washed with dehydrated alcohol, separated, and then dried in the oven.
4
The polymer had a yellow viscous liquid appearance.
5
The copolymer synthesized based on ester, benzene and pyridine ring functional groups was
6
studied by Vertex-70 Infrared Spectrometer (Bruker Company, Germany), Dawn Heleos Laser
7
Light Scattering Spectrometer (Wyatt Company, USA), 515 Gel Permeation Chromatograph
8
(Waters Company, USA), and DSC 822e Simultaneous Thermal Analyzer (Mettler Company,
9
Switzerland). More importantly, the polymer was dissolved in kerosene acting as the viscosity
10
reducer before it was added to 20 g of Shengli (China) heavy oil. To obtain the results in
11
accordance with accurate rheological measurements, the crude oil was left standing for half an
12
hour. Afterwards, the kinematic viscosity was measured with the RheoStress RS75 rotary
13
rheometer (HAAKE Company, Germany). The measurements were carried out at 30°C for 180 s,
14
and the test rotation speed was within 0-400 rpm.
15
4 Results and Discussion
16
4.1 Simulation of Hydrogen Bonds in Asphaltene. Figure 2 shows the molecular simulation
17
of hydrogen bonds in the asphaltene, with and without the viscosity reducer molecules added.
18
Figure 3 shows the local structures of hydrogen bonds in the asphaltene system (O…H, N…H, and
19
S…H). In Figure 2, the dotted line represents hydrogen bonds, with 36 hydrogen bonds formed in
20
the simulation structure of asphaltene per volume unit. However, the number of hydrogen bonds in
21
asphaltene in the simulation structure decreased from 36 to 28 per unit volume with the viscosity
22
reducer added as shown in Figure 2b. This was attributed to the copolymer viscosity reducer based
ACS Paragon Plus Environment
Page 8 of 23
Page 9 of 23 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
1
on ester, benzene and pyridine ring functional groups having better oil solubility. On the other
2
hand, the electronegativity of the copolymer was higher than that of the hydrogen bond atoms in
3
asphaltene of heavy oil. Thus, the combination of hydrogen bonds with the copolymer molecule
4
could be forecasted first, and they either broke or improved the interlocking network structure.35,36
5
This proved that number and the types of hydrogen bonds varied upon the addition of the viscosity
6
reducer.
7 8
Figure 2. Molecular simulation structure. a. hydrogen bond in asphaltene. b. hydrogen bonds in asphaltene with
9
viscosity reducer copolymer added
10 11
Figure 3. The local structures of hydrogen bonds: a. O…H, b. S…H, and c. N…H
12
Differences in temperature and simulation times of hydrogen bonds in asphaltene could be used
13
to evaluate the system energy absorbed from the environment. As displayed in Figure 4,
ACS Paragon Plus Environment
Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
1
significant discrepancies in heating rates were observed where the system with the added viscosity
2
reducer exhibited a relatively low heating rate compared with the system with no added reducer
3
before 3000 fs, although the simulation system temperature became stable after 3000 fs. This
4
indicated that the original plane overlap structure of asphaltene was damaged as soon as
5
interactions occurred between the asphaltene and the copolymer molecule after the viscosity
6
reducer molecule was added to the heavy oil system.
7 8
Figure 4. The relationship between temperature and simulation time of molecular simulation of hydrogen bond in
9
asphaltene. a. The molecular dynamics simulation system. b. The system with functional copolymer viscosity
10
reducer
11
The potential energy and non-bond energy of the system as a function of time are given in
12
Figure 5. As can be seen in Figure 5a, the potential energy and the non-bond energy of the
13
simulation system became stable from 3000 fs onwards. The potential energy was about 11500
14
kcal/mol, and the non-bond energy was about −800 kcal/mol. While in Figure 5b, it can be seen
ACS Paragon Plus Environment
Page 10 of 23
Page 11 of 23 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
1
that the potential energy was about 12300 kcal/mol, and the non-bond energy was about −800
2
kcal/mol. The molecular dynamics simulation results suggest that the potential energy of the two
3
systems (molecular dynamics simulation system and system with functional copolymer viscosity
4
reducer) significantly differed with simulation time at a temperature of 303K. The system
5
potential energy of the system with the addition of the functional copolymer was higher than that
6
of the system with no copolymer, however, the non-bond energy remained invariant. This
7
demonstrated that the interlocking structure of asphaltene changed with the existence of the
8
copolymer viscosity reducer molecules.37 The distance expanded between the molecules of
9
asphaltene in aggregations, indicating the molecular potential energy had increased. However, the
10
non-bond energy (static electricity and van der Waals force) difference between the two systems
11
was not obvious due to the hydrogen bond energy being relatively lower than bond energy, thus
12
the macroscopic interaction between the aggregations had no obvious change. 38,39
13 14
Figure 5. Potential energy and non-bond energy of systems as a function of time for hydrogen bond in asphaltene.
ACS Paragon Plus Environment
Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
1
a. The molecular dynamics simulation system. b. The system with functional copolymer viscosity reducer.
2
4.2 Characterization of the Synthesized Copolymer. The chemical structure of the prepared
3
copolymer was studied through an FTIR spectral analysis. The spectrum of the copolymer is
4
shown in Figure 6. The copolymer spectra clearly show the peaks corresponding to both the
5
aromatic heterocycle and the bending =CH vibrations of the benzene ring of the polymerized
6
styrene at 1410–1586 cm−1 and 702 cm−1, respectively. The absorption peak at 3650~3500 cm-1
7
indicated a carboxyl from the dissociation reaction of acrylic ester in the polymerization process.
8
A chain of unsaturated double bonds was not obviously detected in any spectrum. The ester
9
groups absorption peak was at 1744 cm−1 and 1100 cm−1, corresponding to carbonyl and C–O,
10
respectively. The characteristic strong absorption peak of –CH3, –CH2–, and CH stretching
11
vibration of pyridine ring were at 2850~2950 cm−1. Furthermore, pyridine ring’s stretching
12
vibration and out-of-plane bending of aromatic rings were evidenced at 1500~1600 cm−1, and
13
700~900 cm−1, respectively. –C–H stretching vibration absorption peak of aromatic rings at
14
3100~3000 cm-1 could be also clearly evidenced. These suggesting that the copolymer based on
15
ester, benzene and pyridine ring functional groups had been obtained.
16 17
Figure 6. The infrared spectrum of the synthesized copolymer
ACS Paragon Plus Environment
Page 12 of 23
Page 13 of 23 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
1
Dynamic light scattering (DLS) is a technique in physics that can be used to determine the size
2
distribution of small particles in suspension or polymers in solution. The polymer was dissolved in
3
tetrahydrofuran and was tested with a laser light scattering spectrometer. The dynamic light
4
scattering of the polymer is illustrated in Figure 7 where the three scatter areas represent different
5
grain diameters, as the polymer was synthesized using esters with different chain lengths. The
6
numerical integration reveals the average grain diameter of 23.6 nm.
7 8
Figure 7. Dynamic light scattering of the synthesized copolymer
9
A common means of expressing the chain length of a polymer is the degree of polymerization,
10
which quantifies the number of monomers incorporated into the chain.40 As with other molecules,
11
molecular size of a polymer may be also expressed in terms of molecular weight. Since synthetic
12
polymerization techniques typically yield a statistical distribution of the chain lengths, the
13
molecular weight is expressed in terms of weighted averages, and the number-average molecular
14
weight (Mn) is most commonly used.41 In our study, the polymer was dissolved in tetrahydrofuran
15
and was tested using gel permeation chromatography. Figure 8 shows the scatter of the molecular
16
weight of the copolymer. Since a copolymer is a mixture compound which derived from more
17
than one species of monomer, the scatter curve showed a continuing distribution. The
ACS Paragon Plus Environment
Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
1
number-average molecular weight was 15079,42 the mass-average molecular weight was 29665,
2
and the diffusion coefficient was 1.9686, proving that the scatters of the molecular weight were
3
relatively concentrated.
4 5
Figure 8. Scatters of molecular weight of the synthesized copolymer
6
The glass-transition temperature Tg of a material characterizes the range of temperatures over
7
which this glass transition occurs. It is always lower than the melting temperature, Tm, of the
8
crystalline state of the material. Rubber elastomers are used above their Tg, that is, in the rubbery
9
state, where they are soft and flexible.41 Figure 9 shows the differential scanning calorimeter (DSC)
10
curve of the synthesized copolymer. The polymer was tested at temperatures ranging from –20°C
11
to 150°C in a nitrogen atmosphere. The glass transition temperature of the polymer was –18 ℃
12
shown in the inset. Furthermore, no new phase emerged between –15℃ and 140℃, illustrating
13
that the polymer had a suitable range of temperature for application above 0℃.
ACS Paragon Plus Environment
Page 14 of 23
Page 15 of 23 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
1 2
Figure 9. DSC curve of the synthesized copolymer
3
The viscosity reduction effect of the functional copolymer on heavy crude oil is shown in
4
Figure 10. It can be seen that the kinematic viscosity of the heavy oil sample with kerosene was
5
737.37 mPa·s, the heavy oil with kerosene and the polymer (260 ug/g) sample was 227.27 mPa·s,
6
and the heavy oil with the kerosene and the polymer (463 ug/g) sample was 154.04 mPa·s. This
7
demonstrated that the ester-based benzene and pyridine ring functional group viscosity reducer
8
had a better effect on the Shengli (China) heavy oil, and the viscosity reducing effect improved
9
with an increase in the amount of polymer added. The rate of viscosity reduction reached 79% at
10
30 ℃
when the amount of the copolymer was 463 ug/g. This was because the comb-type
11
copolymer viscosity reducer adsorbed the small sheet-like micelles to accumulate on the surface of
12
the molecules, which reduced the number of small sheet-like micelles and extended the distance
13
between the micelle groups.23,43 On the other hand, the stereo-hindrance effect of the copolymer
14
viscosity reducer molecules either broke or improved the interlocking structures of the asphaltene.
15
Besides, the eutectic and the adsorption effects of the paraffin molecules with the long-chain
16
alkyls of the polymer contributed to the improved interlocking structure.16 Subsequently, the
ACS Paragon Plus Environment
Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
1
possibility of interactions between micelle aggregations decreased, reducing the viscosity of heavy
2
oil.
3 4
Figure 10. Visbreaking curve of the heavy oil with different proportion of viscosity reducer at 30℃. a. heavy oil
5
with kerosene. b. heavy oil with kerosene and polymer (260 ug/g). c. heavy oil with kerosene and polymer (463
6
ug/g)
7
The crude oil sample was also observed under a cold field scanning electron microscope (SEM,
8
JEOL JSM-7600F). Figure 11 shows the surface SEM images of the heavy oils with and without
9
the viscosity reducer added and illustrates that the state of aggregation changed significantly.44,45
10
The micelles showed in Figure 11A are probably the high viscosity condensed polar molecule
11
crystallizations which are the key facter that causing aggregation of asphaltene groups. However,
12
the micelles disappeared with the addition of viscosity reducer illustrated in Figure 11B. This
13
corresponded to the fact that the asphaltene micelles were adsorbed on the surface of the polymer
14
molecules upon the addition of the viscosity reducer which reduced the number of small sheet-like
15
micelles and extended the distance between the asphaltene groups, helping to decrease the
16
viscosity of the heavy oil. Combined with the result of the cold field scanning electron microscopy,
17
we believe that the heteroatoms of the designed copolymer viscosity reducer interacted with the H
ACS Paragon Plus Environment
Page 16 of 23
Page 17 of 23 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
1
atoms of the hydroxy ions among asphaltenes, which is in accordance with the fact that the
2
original colloidal particles were atomized.7,8
3 4
Figure 11 A. A surface SEM image of the heavy oil. B. A surface SEM image of the heavy oil with the viscosity
5
reducer added
6
5 Conclusions
7
From the simulation of the structure and number of hydrogen bonds in heavy oil, we found that
8
the number of hydrogen bonds in asphaltene in the simulation structure decreased from 36 to 28
9
per unit volume at 303K when the viscosity reducer was added. This indicated that the polar
10
segment of the viscosity reducer molecules could insert themselves into the overlap structure of
11
asphaltenes and prevent the formation of hydrogen bonds. Therefore, the distance between the
12
molecules of asphaltene in aggregations expanded, and the molecular potential energy increased.
13
Since hydrogen bond energy is relatively lower than bond energy, the macroscopic interaction
14
between the aggregations had no obvious change, so the non-bond energy of the two-simulation
15
system remained invariant. The heating rate of the system with the viscosity reducer was relatively
16
lower than the system without the viscosity reducer, indicating that the original plane overlap
17
structure of asphaltene was damaged as soon as interactions occurred between the asphaltene and
18
copolymer molecule. Therefore, the viscosity of the heavy oil was decreased with the copolymer
ACS Paragon Plus Environment
Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
1
viscosity reducer.
2
According to the result of the MD simulation, we synthesized the copolymer viscosity reducer
3
and studied it through an FTIR spectral analysis, dynamic light scattering analysis, gel permeation
4
chromatography analysis and thermal analysis. The infrared spectrum of the copolymer at
5
1410–1586 cm−1, 1744 cm−1, 3450 cm−1 and a strong absorption peak around 3000 cm−1, suggest
6
that the copolymer based on ester, benzene and pyridine ring functional groups had been ottained.
7
The copolymer showed good performance for its proper average grain diameter (23.6 nm),
8
average molecular weight (15079), and mass-average molecular weight (29665). Besides, the
9
glass transition temperature of the polymer was −18℃ and no new phase emerged between –15°C
10
and 140°C so the polymer had a suitable temperature range for the application.
11
To validate the result of the simulation, the polymer viscosity reducer was added to Shengli
12
(China) heavy oil and observed under SEM. The kinematic viscosity of the heavy oil decreased
13
from 737.37 mPa·s to 154.04 mPa·s at 30℃ when the amount of copolymer viscosity reducer was
14
463ug/g. The viscosity reduction rate of heavy oil as high as 79%. The copolymer exhibited a
15
good viscosity reduction effect on the heavy oil, highlighting the potential for industrial
16
applications. The surface SEM images of the heavy oils, with and without the added viscosity
17
reducer, showed that the state of aggregation changed significantly, indicating that interactions
18
between the copolymer viscosity reducer and heavy oil glial asphaltene are in accordance with
19
confirmed facts from the perspective of molecular dynamics, the basis for the viscosity reduction
20
mechanism.
21
Author Information
22
Corresponding Author:
ACS Paragon Plus Environment
Page 18 of 23
Page 19 of 23 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
1
*Weiyu Fan
2
*Email:
[email protected] 3
Author Contributions
4
The manuscript was written through contributions of all authors. All authors have given approval
5
to the final version of the manuscript.
6
Notes
7
The authors declare no competing financial interest.
8
References
9
(1) Sébastien S, Nenningsland A L , Herschbach E , et al. Extraction of Basic Components from
10
Petroleum Crude Oil. Energy Fuels 2010, 24, 1043-1050.
11
(2) Xiao C, Prepare and evaluation of viscosity reducer for crude oils, Master dissertation of
12
southwest petroleum university 1999. (in Chinese)
13
(3) Zhang F Y, Prepare and evaluation of oil-soluble viscosity reducer for crude oils. Master
14
dissertation of southwest petroleum university 2006. (in Chinese)
15
(4) Luo T H, Pipeline transportation and rheological behavior of paraffin crude oil, Beijing
16
sinopec press 1991. (in Chinese)
17
(5) Chen Q F, Wang D X and Liu R B, Progress of oil-soluble viscosity reducer for crude oil. Oil
18
Drill & Pro Tech 2004, 26. (in Chinese)
19
(6) Fang L , Zhang X , Ma J , et al. Investigation into a Pour Point Depressant for Shengli Crude
20
Oil. Ind. Eng. Chem. Res. 2012, 51, 11605-11612.
21
(7) Xu H and Lu F J, Viscosity reducer MSA for high viscosity crude oil, New Chem Mater 1999,
22
02, 38-39
ACS Paragon Plus Environment
Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
1
(8) Fan Z X, Wang J X and Sun M B, Preparation of sulfonated styrene/ hydrolyzed maleic
2
anhydride copolymer SSHMA as viscosity reducer for drilling fluid, Oilfield Chem 2005, 22,
3
195-198
4
(9) Cristiane X. da Silva, Dellyo R.S. Alvares et al, New Additives for the Pour Point Reduction
5
of Petroleum Middle Distillates. Energy Fuels 2004, 18, 599-604
6
(10) E.P. Glozman and R.S. Akhmetova, Properties of asphaltenes and asphalts from various
7
sources. Chem Tech Fuels Oil 1975, 11, 107-109
8
(11) Pan Z R. Polymer Chemistry. Beijing: Chemical Industry Press 2007. (in Chinese)
9
(12) Laura V. Castro and Flavio Vazquez, Copolymers as Flow Improvers for Mexican Crude Oils.
10
Energy Fuels 2008, 22, 4006-4011.
11
(13) Srushti Deshmukh and D.P. Bharambe, Synthesis of polymeric pour point depressants for
12
Nada Crude oil (Gujarat, India) and its impact on oil rheology. Fuel Process. Technol 2008, 89,
13
227-233.
14
(14) Zhu Y, Li J T and Ma J H. Preparation of bipolymeric pour point depressants for waxycrude
15
oils. Oilfield Chem 2002. 19, 319-321. (in Chinese)
16
(15) Mao J , Liu J , Peng Y , et al. Quadripolymers as Viscosity Reducers for Heavy Oil. Energy
17
Fuels 2018, 32, 119-124.
18
(16) Yang Y , Guo J , Cheng Z , et al. New Composite Viscosity Reducer with Both Asphaltene
19
Dispersion and Emulsifying Capability for Heavy and Ultraheavy Crude Oils. Energy Fuels 2017,
20
31, 1159-1173.
21
(17) Choi S , Choi S Q , Kim J D , et al. Partially Oxidized Asphaltene as a Bitumen Viscosity
22
Reducer. Energy Fuels 2017, 31, 9240-9246.
ACS Paragon Plus Environment
Page 20 of 23
Page 21 of 23 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
1
(18) Yang X , Hsu S L . Application of molecular simulation techniques to simulate vibrational
2
spectroscopic features associated with hydrogen bonds in crystalline polymers. Macromolecules
3
2002, 26, 1465-1467.
4
(19) Kou J , Jin B , Zongqing B , et al. Effects of Aromatic Solvents and Temperature on
5
Rearrangement of Hydrogen Bonds in Brown Coals. Energy Fuels 2013, 27, 6419-6429.
6
(20) Han T, Wang X Y and Yu P. React IRTM study of the synthesis of octadecyl
7
methacrylate-based oil soluble polymer. J. Shandong Univ (Eng. Sci) 2011, 41, 144-148. (in
8
Chinese)
9
(21) Shadi W. Hasan, Mamdouh T. Ghannam et al, Heavy crude oil vicosity reduction and
10
rheology for pipeline transportation. Fuel 2010, 89, 1095-1100
11
(22) Rafael Martinez-Palou, Maria de Lourdes Mosqueira et al, Transportation of heavy and
12
extra-heavy crude oil by pipeline: A review. J Petrol Sci Eng 2011, 75, 274-282.
13
(23) Boek E S , Yakovlev D S , Headen T F . Quantitative Molecular Representation of
14
Asphaltenes and Molecular Dynamics Simulation of Their Aggregation. Energy Fuels 2009, 23,
15
1209-1219.
16
(24) Chávez-Miyauchi, Tomás Eduardo, Zamudio-Rivera L S , Barba-López, Victor. Aromatic
17
Polyisobutylene Succinimides as Viscosity Reducers with Asphaltene Dispersion Capability for
18
Heavy and Extra-Heavy Crude Oils. Energy Fuels 2013, 27, 1994-2001.
19
(25) Wang Z J. The chemistry and physics of petroleum asphaltens partⅡ chemical composition
20
and structure of petroleum asphaltens. Petrol Asphalt 1996, 10. (in Chinese)
21
(26) Yu P, Li C Y and Zhang C Q et al , Drag reduction and shear resistance properties of
22
ionomer and hydrogen bond systems based on lauryl methacrylate. Petrol Sci 2011, 8, 357-364.
ACS Paragon Plus Environment
Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
1
(27) Iwase M , Sugiyama S , Liang Y , et al. Development of Digital Oil for Heavy Crude Oil:
2
Molecular Model and Molecular Dynamics Simulations. Energy Fuels 2017, 32, 2781-2792.
3
(28) Vanommeslaeghe, K.; Hatcher, E.; Acharya, C.; Kundu, S.; Zhong, S.; Shim, J.; Darian, E.;
4
Guvench, O.; Lopes, P.; Vorobyov, I.; MacKerell, A. D., Jr CHARMM General Force Field: A
5
Force Field for Drug-Like Molecules Compatible with the CHARMM All-Atom Additive
6
Biological Force Fields. J. Comput. Chem. 2010, 31, 671-690.
7
(29) Vanommeslaeghe, K.; Raman, E. P.; MacKerell, A. D., Jr Automation of the CHARMM
8
General Force Field (CGenFF) 2: Assignment of Bonded Parameters and Partial Atomic Charges.
9
J. Chem. Inf. Model. 2012, 52, 3155-3168.
10
(30) Yu, W.; He, X.; Vanommeslaeghe, K.; MacKerell, A. D., Jr Extension of the CHARMM
11
General Force Field to Sulfonyl-Containing Compounds and Its Utility in Biomolecular
12
Simulation. J.Comput. Chem. 2012, 33, 2451-2468.
13
(31) Zong D , Hu H , Duan Y , et al. Viscosity of Water under Electric Field: Anisotropy Induced
14
by Redistribution of Hydrogen Bonds. J. Phys. Chem. B, 2016, 120, 4818-4827.
15
(32) Xing W G, Zhang C Q and Yu P et al, Polymerization Mechanism of α-Linear Olefin.
16
Chinese J Chem Phys 2010, 23, 39-44.
17
(33) Li B, Sheng X and Xing W G et al, Molecular Dynamic Simulation on the Absorbing Process
18
of Isolating and Coating of α-olefin Drag Reducing Polymer. Chinese J Chem Phys 2010, 23,
19
630-636.
20
(34) Li B, Xing W G and Dong G L et al, Preparation of microencapsulated α-olefin drag reducing
21
polymer used in oil pipeline transportation. Petrol Sci 2011, 8, 99-107.
22
(35) Larsen, J. W.; Baskar, A. J., Hydrogen bonds from a subbituminous coal to sorbed solvents.
ACS Paragon Plus Environment
Page 22 of 23
Page 23 of 23 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
1
An infrared study. Energy Fuels 1987, 1, 230-232.
2
(36) Zheng M , Li X , Liu J , et al. Initial Chemical Reaction Simulation of Coal Pyrolysis via
3
ReaxFF Molecular Dynamics. Energy Fuels 2013, 27, 2942-2951.
4
(37) Malkin A Y , Zuev K , Arinina M P , et al. Modifying the viscosity of crude heavy oil by
5
using surfactants and polymer additives. Energy Fuels 2018, 32, 11991-11999.
6
(38) Gao F , Xu Z , Liu G , et al. Molecular Dynamics Simulation: The Behavior of Asphaltene in
7
Crude Oil and at the Oil/Water Interface. Energy Fuels 2014, 28, 7368-7376.
8
(39) Minerva LM, Jobson M , Smith R . Simulation–Optimization-Based Design of Crude Oil
9
Distillation Systems with Preflash Units. Ind. Eng. Chem. Res. 2018, 57, 9821-9830.
10
(40) Vollmert B . Polymer Chemistry. Springer 1973.
11
(41) Ward I M , Klein P G . Polymer Physics// Encyclopedia of Magnetic Resonance. John Wiley
12
& Sons, Ltd 2007.
13
(42) Liu J W. Prepare and evaluation of oil-soluble viscosity reducer for crude oils. Master
14
dissertation of southwest petroleum university 2018. (in Chinese)
15
(43) Estrella R. Simulation of Interactions in Asphaltene Aggregates. Energy Fuels 2000, 14,
16
566-574.
17
(44) Takanohashi T, Iino M, Nakamura K. Evaluation of Association of Solvent-Soluble
18
Molecules of Bituminous Coal by Computer Simulation. Energy Fuels 1994, 8, 291-7.
19
(45) Headen T F , Boek E S , Jackson G , et al. Simulation of Asphaltene Aggregation through
20
Molecular Dynamics: Insights and Limitations. Energy Fuels 2017, 31, 1108-1125.
ACS Paragon Plus Environment