China Petroleum Processing and Petrochemical Technology

Simulation and Optimization 2013, Vol. 15, No. 2, pp 74-81 June 30, 2013

Effects of Fatty Acids on Low-Sulfur Diesel Lubricity:

Experimental Investigation, DFT Calculation and
MD Simulation
Luo Hui; Fan Weiyu; Li Yang; Zhao Pinhui; Nan Guozhi
(State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Qingdao 266555)

Abstract: The continuous reduction in sulfur content of fuels would lead to diesel fuel with poor lubricity which could re-
sult in engine pump failure. In the present work, fatty acids were adopted as lubricity additives to low-sulfur diesel fuel. It
was attempted to correlate the molecular structures of fatty acids, such as carbon chain length, degree of saturation and hy-
droxylation, to their lubricity enhancement, which was evaluated by the High-Frequency Reciprocating Rig (HFRR) meth-
od. The efficiency order was supported by the density functional theory (DFT) calculations and the molecular dynamics (MD)
simulations. The lubricity enhancing properties of fatty acids are mainly determined by the cohesive energy of adsorbed
films formed on iron surface. The greater the cohesive energy, the more efficiently the fatty acid would enhance the lubricity
of low-sulfur diesel fuel.
Key words: lubricity; fatty acid; DFT; MD simulation; adsorption

1Introduction which true metal to metal contact occurs[7]. For a given

polar group, it is shown that the lateral cohesive interac-
The environmental requirements demand the governments tions between the hydrocarbon chains in the monolayer
of numerous countries to impose strict regulations on the play a major role in reducing friction and that the sum of
sulfur content of commercial petroleum fuels. However, these interactions approximates the enthalpy of fusion[8].
the natural lubricating components of the fuels would be
removed simultaneously during the desulfurization pro-
cess, which would result in poor lubricity of the desulfur-
ized fuel. The engine and fuel injection system would be
damaged when using liquid fuel with poor lubricity[1-2].
This damage could be avoided by the addition of lubric-
ity additives to restore the fuel lubricity. Various types of
lubricity additives have been proposed, such as long chain
fatty acids, fatty esters, fatty acid dimers, aliphatic amines
and alkoxyamides, etc.[3-4] Among these compounds, long
chain fatty acids have been found to be quite effective.
Boundary lubrication formed by the polar additives plays
a key role in the lubrication of fuels [5-6]. As shown in
Figure 1Schematic diagram of the polar additives adsorbed
Figure 1, the polar head of additives are adsorbed on the
on the metal surface to form a film
metal surface, either by chemisorption or physical adsorp-
tion, and the long chain tails are aligned directionally to
form a film by the van der Waals interaction and dipole Recieved date: 2013-01-21; Accepted date: 2013-03-28.
interaction between molecules. This film is considered to Corresponding Author: Professor Fan Weiyu, E-mail: fanwyu@
be most important for reducing the number of points at upc.edu.cn.

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Luo Hui, et al. Effects of Fatty Acids on Low-Sulfur Diesel Lubricity: Experimental Investigation, DFT Calculation and MD Simulation

The interactions between the additives and the metal duration of 90 min. The lubricity of the test sample was
surface, especially the interactions between the additives estimated by measuring the average wear scar diameter
themselves, can hardly be measured experimentally. How- (WSD) of the spherical specimen with a photomicro-
ever, the density functional theory (DFT) calculations scope. A smaller WSD value means better lubrication.
and molecular dynamics (MD) simulations would be the Table 1Properties of hydrotreated diesel fuel
powerful methods to investigate the adsorption behavior
Items Data Items Data
at microscopic molecular level and provide useful infor-
3 2
Density (20 ), g/cm 0.7714 Viscosity (40 ), mm /s 1.84
mation[9-12]. To assess an effective lubricity enhancing ad-
ditive, the effect of the molecular structure of additives on Sulfur content, mg/g 9.21 Nitrogen content, mg/g 2.58

their performance is the key issue. DFT calculations have Distillation, Hydrocarbon type, m%
been employed by many researchers to study the effect IBP 196 Alkanes 60.4
of the polar group of additives on their tribological per-
50% 219 Cycloalkanes 28.7
formance[13-15]. However, interactions between the chain
90% 262 Aromatics 10.9
tails of additives and their effects on the performance of
lubricity enhancement have rarely been studied. EP 294 HFRR WSD Value, m 648

The aim of this work is to correlate the molecular struc-

tures of some fatty acids used as lubricity additives with
their lubricity properties. The lubricity enhancing proper-
ties of the fatty acids in low-sulfur diesel fuel were evalu-
ated by a high frequency reciprocating rig (HFRR) appa-
ratus. The HFRR results will be supported by the density
functional theory (DFT) calculations and the molecular
dynamics (MD) simulations.
2E xperimental and Computational
Methods
2.1Lubricity measurements
A hydrotreated diesel was used as the test fuel in this
study, and its typical properties are listed in Table 1. The
fatty acids, such as octanoic acid (C8:0), decanoic acid
(C10:0), lauric acid (C12:0), myristic acid (C14:0), pal-
mitic acid (C16:0), stearic acid (C18:0), oleic acid (C18:1),
linoleic acid (C18:2), and ricinoleic acid (C18:1 OH),
were used as lubricity additives. All the fatty acids were
commercially available chemicals and their purity were
nearly 99 m% without further purification.
The additives were added to the test fuel in a concentra-
tion range of between 50500 g/g. All lubricity mea-
surements were performed by using the high-frequency
reciprocating rig (HFRR) apparatus according to the ISO-
12156 method. Specifically, 20 mL of test sample was
placed in the test reservoir at 60 , and the test was car-
ried out at a frequency of 50 Hz under a load of 2 N for a
2.2Quantum chemistry calculations
DFT calculations were performed by means of the DMol3
program[16-17] in the Materials Studio 5.5 package devel-
oped by Accelrys Ltd. The molecules of the fatty acids
were first simulated in Materials Visualizer. Then, the
geometry optimizations were performed and the struc-
tural properties were obtained by means of the General-
ized Gradient Approximation (GGA) with the Becke Lee
Yang Parr (BLYP) correlation functions[18-19]. The double-
numeric quality base set with polarization functions
(DNP) was applied in this work. The convergence criteria
for these optimizations consisted of threshold values of
1.010-5 Ha, 0.002 Ha/ and 0.005 for energy, force
and displacement convergence, respectively, and the self-
consistent field (SCF) density convergence threshold
value was set at 1.010-6 Ha.
The global reactivity of the molecules was analyzed
through evaluating the energy of the highest occupied
molecular orbital (EHOMO), the energy of the lowest unoc-
cupied molecular orbital (ELUMO), the absolute electroneg-
ativity (), the hardness (), and the electrophilicity index
().
Absolute electronegativity () and hardness () of the ad-
ditives were calculated as described by Pearson[20]:
E + ELUMO
= HOMO (1)
2
EHOMO + ELUMO
= (2)
2

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China Petroleum Processing and Petrochemical Technology 2013,15(2):74-81

As introduced by Parr, et al. [21], the electrophilicity index

was used to measure the electrophilic capacity of the mol-
ecules, which was defined as follows:
= (3)
2

2.3MD simulations
The adsorption behavior of the fatty acids onto Fe (110)
plane was investigated by means of molecular dynam-
ics (MD) simulations. The Forcite package contained in
Accelrys Materials Studio 5.5 was adopted and the con-
densed-phase optimized molecular potentials for atomis-
tic simulation studies (COMPASS) [22] forcefield was used
for the MD simulations. The Fe (110) plane composed
of eight Fe layers was first built and relaxed to minimize
its energy by using the Smart Minimizer method. Next,
the surface area was increased to 3.4753 nm3.4753 nm
and its periodicity was changed by constructing a super
cell. Then, a vacuum slab with 6.0 nm of thickness was
built on the Fe (110) plane, which was large enough to
avoid the interaction between the adsorbate (fatty acids)
and the periodic image of the bottom layer of atoms in the
plane. Finally, 49 molecules of fatty acid were introduced
into the simulation box, and the initial structure model is Figure 2Structure model of oleic acid molecules adsorbed
shown in Figure 2 (a), in which only stearic acid adsorbed on the Fe (110) plane: (a) the initial structure, (b) the
on Fe surface was presented as the representative. equilibrium structure after MD simulation
Prior to the dynamics run, all systems were optimized
with an approximation of the average density correction.
using the Smart Minimizer algorithm, and the conver-
The simulation time and step length were set at 100 ps
gence criterion adopted for the value of maximum force
and 1 fs, respectively, and a frame was exported on each
was 103 kcal/(mol) for the Steepest Descent method,
10 kcal/(mol) for the Conjugate Gradient method, and 1000 fs for statistical analysis.
10-5 kcal/(mol) for the Newton-Raphson Gradient meth- The equilibrium of the simulation systems was judged by
od. The minimized systems were subsequently relaxed by the fluctuation of energy and temperature. Relative de-
simulated annealing through preheating gradually from viations of energy and temperature were less than 0.1 %
300 K to 500 K during 20 ps using the velocity scale tem- and 10 %, respectively, and after about 20 ps it could be
perature control method in the constant particle volume concluded that the simulation system had reached equi-
temperature (NVT) ensemble. Equilibration and produc- librium after 20 ps. The equilibrium model is shown in
tion simulations were conducted in the constant NVT Figure 2 (b).
ensemble, and the temperature was set at 298 K which The binding energy of fatty acids adsorbed on Fe (110)
was controlled by means of the Andersen method[23]. The plane were calculated using Equation (5):
summation methods for short-range interactions and non- Ebinding=Etotal-(Esurface+Efilm) (5)
bonds van der Waals and Coulomb interactions were the where Etotal is the total energy of the surface and additives,
atom based, with a cutoff of 1.55 nm (0.10 nm for Spline Esurface is the energy of the surface without the additives,
width and 0.10 nm for Buffer width), and the intermolec- and Efilm is the energy of the adsorbed film of additives
ular interactions beyond the cut distance were corrected without the surface.

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Luo Hui, et al. Effects of Fatty Acids on Low-Sulfur Diesel Lubricity: Experimental Investigation, DFT Calculation and MD Simulation

The cohesive energy of adsorbed film is defined as follows [24]:
Ebinding=Eisolated-Eperiodic (6)
where Eisolated is the energy of additive molecule in the iso-
lated state, and Eperiodic is the energy of additive molecule
in the adsorbed film.
3Results and Discussion
3.1Lubrication properties
It is well known that the long chain fatty acids are sur-
face active materials, which are used widely to enhance
the lubricity of synthetic or mineral fuels. The fatty acids
can be adsorbed on the rubbing surfaces and form a hy-
drodynamic film, resulting in a low shear stress layer at
a majority of metal-to-metal contact points. Their long
carbon chains could increase the thickness of the film and
enhance the intermolecular forces in the film.
Figure 3 presents HFRR lubricity versus carbon chain
length of saturated fatty acids. It can be seen that the lu-
bricity of the diesel fuel blend improves regularly with an
increasing concentration of fatty acids in diesel fuel and
there is a specific influence of the carbon chain length of
these fatty acids on the fuel lubricity. The saturated fatty
acid with longer carbon chain shows a higher efficiency
to improve the lubricity of the fuel.
The results of HFRR analysis for 18-carbon-chain fatty
acids with different chain structures are shown in Figure 4,
and this series of fatty acids exhibited a clear trend associ-
ating the carbon bond unsaturation degree with fuel lubric-
ity enhancement. It can be confirmed that the fuel lubricity
enhancement increased with an increase in the degree of
carbon bond unsaturation. Especially, the hydroxylated
fatty acid, ricinoleic acid, which was used in this study
displayed more effective lubricity enhancement than the
non-hydroxylated one, oleic acid, and was ultimately bet-
ter than all the nonhydroxylated fatty acids studied.

3.2Q uantum-chemical parameters of the

Figure 3HFRR lubricity evaluation for saturated fatty acids
of increasing chain length in low-sulfur diesel fuel
Octanoic acid; Decanoic acid; Lauric acid;
Myristic acid; Palmitic acid; Stearic acid
Figure 4HFRR lubricity evaluation for 18-carbon-chain
fatty acids in low-sulfur diesel fuel
Stearic acid; Oleic acid; Linoleic acid; Ricinoleic acid
fatty acids
Geometric and electronic structures of the fatty acids
were calculated by means of DFT, with the optimized
structures shown in Figure 5, in which only stearic acid
and linoleic acid are presented as the representatives. The
quantum chemical parameters are presented in Table 2.
The highest occupied molecular orbital (HOMO) and the
lowest unoccupied molecular orbital (LUMO) are very
important quantum chemical indicators. EHOMO is directly
related to the electron-donating ability of the molecule,
and ELUMO is associated with the ability of the molecule to
accept electrons. The higher the value of EHOMO is, more
probably the molecule would donate electrons to appro-
priate acceptor molecules with low energy. Conversely,
the lower the value of ELUMO is, more possibly the mol-
ecule would accept electrons [10].
It can be seen from Table 2 that the total energy (ETotal)
of fatty acids decreases with an increasing carbon chain
length, and the value of ETotal decreases approximately
by 2.0105 kJ/mol for each additional ethyl chain. The
chain length has no significant effect on other parameters
of saturated fatty acids, such as EHOMO, E, , and .
So the carbon chain length has no effect on the ability of

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China Petroleum Processing and Petrochemical Technology 2013,15(2):74-81

Figure 5Optimized geometries of the fatty acids obtained by DFT calculations: (a) stearic acid; (b) linoleic acid

fatty acid to accept electrons or donate electrons. Double
bonds introduced in the carbon chain of the fatty acid
could lead to significant increase in EHOMO, or decrease in
E, , and . And these parameters would change ob-
viously with an increase in the number of double bonds.
This means that the ability of fatty acid to donate elec-
trons would be improved by an addition of double bonds.
If the carbon chain of the fatty acid contains double bond
and hydroxyl group at the same time, such as ricinoleic
acid, ETotal decreases approximately by 2.0105 kJ/mol,
but the changes in EHOMO, E, , and are less obvious
compared with the effect of double bonds alone.
Judging from HFRR values of these fatty acids and the
results of DFT calculations, it can be found out that an in-
crease of ETotal or a decrease of E, , and can lead to
a more lubricity enhancing efficiency.
3.3Results of MD simulations
In the current study, the fatty acids have been simulated
as adsorbate on Fe (110) substrate to investigate the pref-
erential adsorption phenomenon. Figure 6 shows the rela-
tive concentration profile of fatty acids in the adsorbed
films on Fe (110) substrate. These concentration profiles
suggest that the films have a higher density close to Fe
(110) substrate indicating that the fatty acids can stick on
the iron surface because of adsorption. With the increase
of carbon chain length, the thickness of the adsorbed film
increases obviously. However, the double bonds or hy-
droxyl group contained in carbon chain has no significant
effect on the concentration profile of fatty acids.

Table 2Quantum chemical parameters derived for the fatty acids calculated with DFT method
Additive ETotal, 106kJ/mol EHOMO, kJ/mol ELUMO, kJ/mol E, kJ/mol

Octanoic acid -1.22 -610.66 -93.00 517.66 351.83 258.83 239.12

Decanoic acid -1.43 -610.47 -93.20 517.27 351.84 258.63 239.31

Lauric acid -1.63 -610.15 -92.12 518.03 351.13 259.01 238.01

Myristic acid -1.84 -610.33 -90.58 519.75 350.60 260.05 236.30

Palmitic acid -2.05 -610.65 -90.55 520.10 350.46 259.87 236.34

Stearic acid -2.25 -609.57 -90.20 519.37 349.89 259.69 235.71

Oleic acid -2.25 -528.52 -92.55 435.97 310.54 217.98 221.19

Linoleic acid -2.25 -521.82 -92.52 429.30 307.17 214.65 219.78

Ricinoleic acid -2.45 -538.24 -95.18 443.06 316.71 221.53 226.39

Note: E=ELUMO-EHOMO

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Luo Hui, et al. Effects of Fatty Acids on Low-Sulfur Diesel Lubricity: Experimental Investigation, DFT Calculation and MD Simulation

Besides the adsorption interactions between additives and Table 3Results calculated by means of MD simulation for
Fe surface, the interactions of additive molecules them- adsorption of fatty acids on Fe (110) plane
selves in the adsorbed film could not be ignored as it has Ebinding, Ecohesive, kJ/mol
Additive
been demonstrated in Figure 1. The binding energy of kJ/mol van der Waals Electrostatic Total
fatty acids adsorbed on Fe (110) plane and the cohesive Octanoic acid 173.59 43.25 28.37 71.62
energy of the adsorbed film are shown in Table 3. Decanoic acid 172.10 56.31 27.40 83.71
It can be seen from Table 3 that the fatty acids adsorbed
Lauric acid 173.42 66.86 27.16 94.02
on Fe (110) plane have the same or nearly the same bind-
Myristic acid 172.38 82.75 25.71 108.46
ing energy, which demonstrates that for the fatty acids,
Palmitic acid 172.42 93.69 24.70 118.39
the interaction between additives and Fe surface is not
the most important factor affecting the lubricity enhanc- Stearic acid 173.02 107.31 22.97 130.28

ing properties. With the increase in carbon chain length Oleic acid 173.58 106.96 26.32 133.28

of saturated fatty acids, the cohesive energy of the film Linoleic acid 173.98 105.15 31.19 136.34
increases; and the double bonds or hydroxyl group intro- Ricinoleic acid 173.51 105.05 51.81 156.86
duced in the carbon chain can enhance the cohesive en-
ergy. Ricinoleic acid could form an adsorbed film with a
maximum cohesive energy during the simulation process.

Figure 7Relationship between the cohesive energy and

Octanoic acid; Decanoic acid; Lauric acid;
Myristic acid; Palmitic acid; Stearic acid
Stearic acid; Oleic acid;
Linoleic acid; Ricinoleic acid
Figure 6Concentration profile of fatty acids in the adsorbed
films on Fe (110) surface: (a) saturated fatty acids with
different carbon chain length; (b) 18-carbon-chain fatty acids
HFRR lubricity evaluation of the fatty acids at a
concentration of 500 g/g in diesel fuel
Figure 7 presents HFRR lubricity of the fatty acids at a
concentration of 500 mg/g versus the cohesive energy of
the adsorbed films, and it can be seen that the increase in
cohesive energy leads to a regular increase of the lubri-
cation effectiveness. Highest value of cohesive energy
indicates that ricinoleic acid is the most efficient lubricity
enhancer among the fatty acids tested thereby.
The cohesive energy of the adsorbed film consists of two
parts: the van der Waals part and the electrostatic part.
With the increase of carbon chain length, the van der
Waals part of the cohesive energy increases, but the elec-
trostatic part decreases slightly. The double bonds or hy-
droxyl group contained in carbon chain have no obvious
effect on the van der Waals interaction, but can enhance
the electrostatic interaction, especially with respect to hy-
droxyl group.

79
China Petroleum Processing and Petrochemical Technology
4Conclusions
HFRR measurements of fatty acids in low-sulfur diesel
fuel suggest that an increase in the carbon chain length
leads to a higher lubrication efficiency. For the C18 fatty
acids series, lubricity enhancement increased with an in-
creasing unsaturation degree of fatty acids, and ricinoleic
acid was better than all the nonhydroxylated fatty acids.
The lubricity enhancement efficiencies were explained in
terms of molecular parameters obtained from DFT cal-
culations and the adsorption behavior described through
MD simulation. The total energy of molecules could be
lowered by an increase of the carbon chain length or an
addition of hydroxyl group. Other electronic properties
could change with the introduction of double bonds in
the carbon chain of fatty acids. The cohesive energy of
adsorbed films formed on the iron surface could be im-
proved by an increase of the carbon chain length, which
is mainly attributed to the increase of the van der Waals
interaction. An increase in the unsaturation degree of fatty
acid or an addition of hydroxyl group could also lead to
higher cohesive energy, which is mainly attributed to the
increase of electrostatic interaction. The lubricity enhanc-
ing properties of fatty acids are mainly determined by the
cohesive energy, and an increase of cohesive energy leads
to an increase in fuel lubricity.
Acknowledgment: This work was supported by the Funda-
mental Research Funds for the Central Universities of China
(11CX06036A).
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Experiments on Separation of C5 Fraction Completed at Jilin
Petrochemical Company
The Jilin Petrochemical Company (JPC) has accom-
plished the supplementary tests of C5 fraction separation
package technology. It is said that the comprehensive
indicators of this technology has reached the internation-
ally advanced level, which has symbolized the successful
completion of C5 fraction separation project at JPC.
The commercial test of C5 fraction separation package
technology is a key project envisaged by the PetroChina
headquarters for the construction of the C4 and C5 frac-
tions processing bases. The commercial test was first
started in 2009, and JPC has developed a novel process
flow scheme coupled with associated polymerization
inhibitor system and solvent regeneration technology,
Unit for Hydroaromatization of C4 Hydrocarbons at Hengrun
Petrochemical Company Attained Design Target
The 200 kt/a C4 hydroaromatization unit at the Hengrun
Petrochemical Co. in Puyang city, Henan province has
been operating for 10 months since its commissioning in
2012. The aromatization product from this unit has an oc-
tane rating in the range of RON 9496 and a distillation
range of 36204 , and is basically aromatics-free. Dur-
ing the aromatization reaction the light ends yield reaches
1.92%, and the LPG yield is equal to 65.74%, showing
that the operating level of the commercial aromatization
unit has fully meet the design target.
It is learned that this C4 hydroaromatization package tech-
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systems of industrial interest [J]. Progress in Organic Coat-
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which can allow for production of qualified diolefin prod-
ucts separated from C5 fraction. The yield of isoprene is
equal to 92.31%, with its purity reaching 99.89%; the
piperylene purity exceeds 79%; and the yield of dicyclo-
pentadiene reaches 89% with its purity exceeding 95%.
It is learned that previously the C5 hydrocarbons resource
was processed along the technical route of hydrotreating
and steam cracking. After construction of the C5 fraction
processing base, the isoprene obtained via C5 hydrocar-
bons separation will be used to manufacture isoprene
rubber and piperylene will be used to produce petroleum
resins, which would promote the structure readjustment
of JPC and scientific allocation of industry chain.
nology developed by the Petrochemical Research Institute
of PetroChina can convert refinery C4 hydrocarbons, which
are used as the feedstock in the presence of nano-scale
zeolite catalyst in a fixed bed reactor, into mixed aromatics
or gasoline component with high add-value to realize deep
processing and effective utilization of C4 hydrocarbons.
Compared with the similar domestic or overseas tech-
niques, this technology features mild reaction regime, high
conversion rate, stable operating condition, and environ-
mentally friendly advantages, with its technical proficiency
being on a par with internationally advanced level.
81