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Optimization of Processing Parameters and Macrokinetics for

Hydrodesulfurization of Coal Tar

Article  in  Energy Sources Part A Recovery Utilization and Environmental Effects · December 2015
DOI: 10.1080/15567036.2011.649336

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Optimization of Processing Parameters and

Macrokinetics for Hydrodesulfurization of Coal Tar

D. Li, W. H. Li, Q. C. Liu, Z. Fan, H. Li, W. Ma & S. H. Yan

To cite this article: D. Li, W. H. Li, Q. C. Liu, Z. Fan, H. Li, W. Ma & S. H. Yan (2015) Optimization
of Processing Parameters and Macrokinetics for Hydrodesulfurization of Coal Tar, Energy
Sources, Part A: Recovery, Utilization, and Environmental Effects, 37:23, 2591-2600, DOI:
10.1080/15567036.2011.649336

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 Energy Sources, Part A: Recovery, Utilization, and Environmental Effects, 37:2591–2600, 2015
Copyright © Taylor & Francis Group, LLC
ISSN: 1556-7036 print/1556-7230 online
DOI: 10.1080/15567036.2011.649336

Optimization of Processing Parameters and Macrokinetics for

Hydrodesulfurization of Coal Tar
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D. Li,1 W. H. Li,1 Q. C. Liu,1 Z. Fan,1 H. Li,1 W. Ma,1 and S. H. Yan1

1
School of Chemical Engineering, Northwest University, Xi’an, China

In this work, a systematic study has been conducted to optimize the process conditions and to evaluate
kinetic parameters for hydrodesulfurization of coal tar. Experiments were performed in a trickle-bed
hydrogenation unit at the temperatures, hydrogen pressures, and liquid hourly space velocities of
643–683 K, 9.6–13.6 MPa, and 0.3–0.5 h–1, respectively. Hydrogen to oil volume ratio was maintained
constant at 1,200 LN/L in all cases. Optimization for hydrodesulfurization process conditions was
investigated using the Box-Behnken experimental design by response surface methodology. A mathe-
matical model that can be used for predicting sulfur content in products after hydrotreating was
statistically developed and proven with analysis of variance. Kinetic studies for hydrodesulfurization
reactions were studied using a power law model. The power law model showed that hydrodesulfuriza-
tion of coal tar followed second-order kinetics and the activation energy was 42.15 kJ/mol, which is
lower than other petroleum fractions.

Keywords: coal tar, hydrodesulfurization, macrokinetics, mathematical modeling, optimization

1. INTRODUCTION

Shaanxi province is a major coal-producing region in China, 170 billion tons of which have been
developed already. The main way to make use of the abundant coal is low temperature pyrolysis
process, which can produce char and coal tar by internally heated vertical retort furnaces. Now
there are more than 300 corporations using this process in Shaanxi province and the output of coal
tar has reached thousands of tons every day (Jiang, 2009). The coal tar is mainly used as raw fuel
directly, and is causing serious environmental problems (Sun et al., 2011).
The gradual shortage in the supply of crude oil creates an interest in finding alternative sources
of energy. These huge reserves of coal and large output of coal tar are attracting attention in
converting these materials into cleaner feedstock for producing transportation fuel. Hydrogenation
has been investigated in recent years as a potential method for upgrading coal tar (Tian, 2007; Li,
2009). Coal tar contains large amounts of contaminants, especially char, oxygen, nitrogen, and
sulfur. Sulfur compounds in coal tar mainly include dibenzothiophene, thiophene, benzothiophene,
phenylthioalcohol, thionaphthol, etc. The presence of sulfur compounds in the coal tar causes
problems in meeting the stringent emission specifications. The presence of sulfur compounds also

Address corresponding to Dr. D. Li, School of Chemical Engineering, Northwest University, Xi’an, 710069 China.
E-mail:lidong@nwu.edu.cn
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/ueso.

2591
 2592 D. LI ET AL.

adversely affect the stability of fuel during storage and deactivates the catalyst used in the
hydrocracking. Therefore, the sulfur compounds present in the coal tar need to be removed before
further processing. Hydrodesulfurization (HDS) is perhaps the only commercial process for redu-
cing the levels of sulfur content in these stocks.
The literature on HDS has grown substantially, especially in recent years with the need for
processing heavier and synthetic feedstocks. However, most studies are concerned with the reaction
mechanisms and kinetics of petroleum fractions. Although these studies have provided a funda-
mental understanding of HDS, the results may not be indicative of actual phenomena during the
hydrotreatment of coal tar. In the present work, a statistical design has been performed to optimize
the process conditions for HDS of low temperature pyrolysis process coal tar. A kinetic study was
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also performed for HDS reactions using the power law model.

2. EXPERIMENTAL

2.1. Materials
The coal tar sample was obtained from pyrolyzed Shenmu (Shaanxi province, China) coal at 600°
C. The properties of the feed material are given in Table 1. It can be concluded that coal tar is
inferior oil with greater density, heavier fraction, higher nitrogen content, higher colloid content,
and relative lower sulfur content. Similar compositions are found in liquids derived from coal
gasification (Dieter, 2006).

2.2. Catalysts
The hydroguard catalysts and the hydrotreating catalysts used in these studies were commercially
available nickel molybdenum supported on γ-alumina. All catalysts were available in the form of

TABLE 1
Properties of Coal Tar

Property Value

Density (20°C), g/mL 1.0442

Carbon, wt% 83.42
Hydrogen, wt% 8.31
Nitrogen, wt% 1.14
Sulfur, wt% 0.38
Viscosity(50°C), mm2/s 14.29
Carbon residue, wt% 7.81
Ash, wt% 0.173
Distillation range, °C
IBP 214
30% 315
50% 351
70% 414
90% 462
EBP 510
Composition, wt%
Saturated hydrocarbon 44.38
Aromatic hydrocarbon 18.49
Colloid 27.51
Asphaltum 9.62
 HYDRODESULFURIZATION OF COAL TAR 2593
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FIGURE 1 Schematic of experimental equipment. 1. Hydrogen storage tank; 2. Metering pump; 3. Compressor; 4.
Reactor-1; 5. Reactor-2; 6. High-pressure gas-liquid separator; 7. Low-pressure gas-liquid separator; 8. Pressure
regulator; 9. Ball valve; 10. Check valve; 11. Furnace; 12. Needle valve; 13. Back pressure regulator; 14. Wet-test
meter.

extrudates of 1.5-mm diameter. The catalysts’ composition and physicochemical properties were
measured as described elsewhere (Li et al., 2009).

2.3. Trickle-bed Reactor System

For about 40 years, chemical engineers have been using trickle-bed reactors in the laboratory in
order to evaluate catalyst efficiency, study chemical kinetics, and predict the behavior of industrial-
scale reactors. The experiment was conducted in a fixed-bed hydrogenation unit as can be seen in
Figure 1. The reaction unit is 1,500 mm long and its inside diameter is 26 mm. The reactor consists
of two 316 stainless steel tubes, which were packed with catalysts and operated in trickle-bed mode
with concurrent flow of gas and liquid. The tube was encased in six 1-kW electric heaters, each
with independent temperature control and monitoring via thermocouples.

2.4. Catalysts Activation

The volume of catalysts was maintained at 200 mL. The catalysts were pre-dried in nitrogen at 120°C
and 0.1 MPa for 8 h prior to sulfidation. Then, nitrogen was replaced by hydrogen, and the reactors
were pressurized to 8.0 MPa. The catalysts were sulphided with a 2 wt% CS2 in straight-run diesel
oil. Sulfidation experiments were performed at the liquid hourly space velocities (LHSV) and
hydrogen to oil volume ratio of 1.5 h–1 and 1,200 LN/L, respectively. The temperature of the reactor
was ramped hourly from 120°C in steps of 10 to 250°C, at which temperature it was kept for 2 h.
H2S breakthrough was monitored in the off gas by means of gas detector tubes (ND-1040, Jiangda
Company, Nanjing, China). A 2,000 vppm H2S concentration in the off gas was seen as sufficient in
order to proceed in increasing the temperature further to 360°C, at which temperature it was kept for
another 8 h. Thereafter, the reactor temperature was decreased to 240°C. When sulfidation was
completed, the reactor pressure was raised and hydrogen was introduced at the desired feed rate.

2.5. Hydrotreatment Procedure and Analytical Method

The details of the experimental procedures are given elsewhere (Li et al., 2009). Catalysts activity
was monitored by drawing product samples from the reactor after steady-state conditions were
 2594 D. LI ET AL.

reached, typically after a period of 24 h. The following 8 h period was used to collect a
representative sample for product analysis. The feed and liquid products were analyzed for sulfur
contents by a chemiluminescence method (using a TSN-2000SN analyzer) following the GB/T
11140-2008 method.

3. RESULTS AND DISCUSSION

Before collecting experimental data, the catalysts surface was stabilized at the temperature,
pressure, LHSV, and hydrogen to oil volume ratio of 663 K, 12 MPa, 0.4h–1, and 1,200 LN/L,
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respectively, and the experiment lasted for 10 days. The activity decreased after 3 days of time on
stream and then remained constant for the next 7 days.
A central composite inscribed method was used to design the experiments. The purpose of using
this method is to optimize the process conditions with the minimum number of experiments.
Statistical analysis of experimental data, process optimization, and kinetic studies for HDS reac-
tions are described below.

3.1. Statistical Analysis of Experimental Data

Statistical design of experiments refers to the process of planning the experiment so that appro-
priate data that can be analyzed by statistical methods will be collected, resulting in valid and
objective conclusions. A factorial experiment is a useful tool for dealing with several factors, in
which factors are varied together instead of one at a time. In order to investigate influence of
process parameters, their interactions on the response and their optimum combination for a central
composite design was applied. The experimental data were analyzed statistically using the software
DESIGN-EXPERT 7 (Stat-Ease, Inc., Minneapolis, MN, USA) for optimizing the process
conditions.
Three important response factors, such as temperature, hydrogen pressure, and LHSV, were
chosen in this work, which have significant effects on HDS reactions. Previous studies (Turgut
et al., 1984) indicated that high hydrogen pressure and low LHSV favored the hydrotreating of
coal-derived liquids and combined with higher reaction temperature, kinetically favored
heteroatom removal as well. Based on these studies, the temperature, hydrogen pressure, and
LHSV were varied in the range of 643–683 K, 9.6–13.6 MPa, and 0.3–0.5 h–1, respectively. The
hydrogen to oil volume ratio of all experiments is kept at a fixed level of 1,200 LN/L.
According to the experimental design, 17 experimental results are given in Table 2. Run number
13 was repeated five times.
With multiple regression analysis of the obtained data, mathematical description of the HDS
process was expressed with a regression equation obtained from real values.
Sp ¼ 50:60  20:38  Temperature  47:25  HydrogenPressure  17:13  LHSV
þ 1:25  Temperature  Hydrogen Pressure  1:50  Temperature  LHSV
þ 4:75  Hydrogen Pressure  LHSV þ 0:70  ðTemperatureÞ2
þ 45:45  ðHydrogen PressureÞ2 þ 11:7  ðLHSVÞ2
An analysis of variance (ANOVA) table for HDS response surface reduced quadratic model is
given in Table 3.
The test statistics, F and R2, were used to justify the model with the experimental results. F and
R are defined as F = MSR/MSE and R2 = 1 – SSE/SST, where MSR is mean square of regression
2

obtained by dividing the sum of squares of regression by the degrees of freedom. MSE is mean
 HYDRODESULFURIZATION OF COAL TAR 2595

TABLE 2
Experimental Results for HDS at Different Operating Conditions for Optimizing Process Conditions

Run No. Reaction Temperature, K Hydrogen Pressure, MPa LHSV, h–1 Sulfur Content of Products, mg/kg

1 643 9.6 0.4 164

2 683 9.6 0.4 115
3 643 13.6 0.4 76
4 683 13.6 0.4 32
5 643 11.6 0.3 58
6 683 11.6 0.3 26
7 643 11.6 0.5 103
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8 683 11.6 0.5 65

9 663 9.6 0.3 151
10 663 13.6 0.3 38
11 663 9.6 0.5 168
12 663 13.6 0.5 74
13 663 11.6 0.4 50
14 663 11.6 0.4 54
15 663 11.6 0.4 48
16 663 11.6 0.4 51
17 663 11.6 0.4 48

TABLE 3
ANOVA Analysis for Response Surface Reduced Quadratic Model for HDS

Sources Sum of Square Degree of Freedom Mean Square F-Value Prob > F

Model 33,233.02 9 3,692.56 66.03 <0.0001

Temperature 3,321.13 1 3,321.13 59.39 0.0001
Hydrogen pressure 17,860.50 1 17,860.50 319.39 <0.0001
LHSV 2,346.13 1 2,346.13 41.95 0.0003
Temperature × Hydrogen pressure 6.25 1 6.25 0.11 0.7479
Temperature × LHSV 9.00 1 9.00 0.16 0.7003
Hydrogen pressure × LHSV 90.25 1 90.25 1.61 0.2445
Temperature2 2.06 1 2.06 0.037 0.8531
Hydrogen pressure2 8,697.69 1 8697.69 155.53 <0.0001
LHSV2 576.38 1 576.38 10.31 0.0148
Lack of fit 348.25 3 116.08 10.75 0.0220
Pure error 43.20 4 10.80
Residual 391.45 7 55.92
Total 3,3624.47 16

squares of errors from the analysis of variance. SSE is sum of squares of errors, and SST is sum of
squares of the total. R2 is the multiple regression coefficient. A value close to 1 for R2 signifies a
perfect fit to the experimental data. The calculated value of R2 using the SSE and SST values is
0.9884. The theoretical F value at 95% confidence interval is 5.19. R2 = 0.9884 and F = 66.03
larger than F0.05 (= 5.19), indicate that regression equation fits well with the experimental data.
Also, in this model the “Pred R-Squared” of 0.8323 was in reasonable agreement with the “Adj
R-Squared” of 0.9734. In general, a term that has a probability value less than 0.01 would be
considered a significant effect. It can be seen from Table 3 that the probability of F (prob > F) is
less than 0.05, indicating that temperature, hydrogen pressure, LHSV, (hydrogen pressure)2, and
LHSV2 have very significant effects on HDS.
 2596 D. LI ET AL.

To accomplish this, the surface response plots were made, which are given in Figure 2.These
figures represent the surface response plots for the combined effects of temperature–hydrogen
pressure, temperature–LHSV, and hydrogen pressure–LHSV on HDS, respectively.
Process optimization for HDS was also studied using ANOVA. Analysis of experimental data and
regression equation gave one maximum HDS point. It is observed that the minimum sulfur content of
products can be obtained at the temperature, hydrogen pressure, and LHSV of 681.25 K, 13.1 MPa,
and 0.32 h–1, respectively. The expected sulfur content of the product is 12.2622 mg·kg–1. According
to the optimum conditions of response surface methodology, the results of three repeated experiments
demonstrate that the sulfur content of products is 12–16 mg·kg–1, which is very close to the
prediction value.
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3.2. Kinetics for HDS Reactions

The observable kinetic behavior of a compound, even in a reacting mixture, can be predicted given
the mechanism of the reaction and a knowledge of the other intrinsic species. Since a wide range of
different sulfur compounds are present in coal tar and the nature of these compounds in oils is not
simple, the HDS mechanisms become complex. Li et al. (1993) found that the higher the boiling
point of the oil is, the more difficult it is to perform HDS reactions. In this case, the reaction order
for HDS of coal tar may be complex. The nth order kinetics with respect to total sulfur concentra-
tion is usually applied, in which n value depends on several factors, such as type and concentration
of sulfur compounds, catalyst properties, type of feed, operating conditions, experimental device,
among others.
In general, the Langmuir-Hinshelwood model is used to identify the rate equation in the study of
hydrotreating reactions (Whiteherst et al., 1998). Because too many parameters need to be
determined in this model and the complicacy of coal tar in this article, a power-law model is
used to determine the kinetic parameters. Assuming that the reaction order of HDS is n, and
considering the effect of hydrogen pressure on HDS reaction, the rate equation of HDS can be
written as:
dS=dt ¼ kapp S n PH2
a
; (1)
–1
where kapp is the apparent reaction rate constant; S is the content of sulfur in oil, mg·kg ; t is the
residence time; PH2 is the hydrogen pressure, MPa; n is the reaction order; and a is the hydrogen
pressure index.
Equation (1) can be written as:
SP1n  Sf1n ¼ ð n  1Þ kapp P aH2 t; (2)
where Sp is the content of sulfur in products, mg·kg–1; and Sf is the content of sulfur in feed,
mg·kg–1.
Take into account that the fluid in the fixed-bed unit may depart plug flow, and index b was
introduced to revise LHSV:
SP1n  Sf1n ¼ ðn  1Þkapp P aH2 ðLHSV Þb ; (3)
where b is LHSV index, h–1.
Assuming the reaction rate constant of HDS expressed using an Arrhenius equation:
Sp1n  Sf1n ¼ ½ðn  1Þk0 P aH2 ðLHSV Þb exp ðE=RT Þ; (4)
where k0 is the pre-exponential factor of Arrhenius equation; E is the apparent activation
energy of reaction, kJ/mol; T is reaction temperature, K; and R is universal factor, 8.314 J/
(mol·K).
 HYDRODESULFURIZATION OF COAL TAR 2597
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FIGURE 2 Surface response plot for HDS of coal tar.

 2598 D. LI ET AL.

Equation (4) can be rearranged as:

Sp ¼ ½ðn  1Þk0 PH2

a
ðLHSV Þb expðE=RT Þ þ Sf1n ð1=1nÞ : (5)

Equation (5) is the established kinetics model.

The experimental data (see Table 2) were calculated with the software SPSS 16.0 (SPSS, Inc.,
Chicago, IL, USA) and were fitted by the Levenberg–Marquardt method. The parameters of the
kinetic equation were found as:

E ¼ 42; 150; n ¼ 2:022; a ¼ 3:905; b ¼ 0:666; k0 ¼ 472; 500:

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The kinetic expression equation can be written as:

Sp ¼ ½43077PH3:905
2
ðLHSV Þ0:666 expð42150=RT Þ þ Nf1:022 0:978 : (6)

Experimental information about reaction orders and activation energies of HDS of real feedstocks
are scarce in the literature. The comparison of reaction order and activation energies for HDS
reaction of coal tar with other literature is given in Table 4. Apparent reaction orders were found in
the range of 1–2, and most of the values of the reaction orders increased as the molecular weight of
feed also increased. Some data did not follow this trend, which was attributed to differences in
experimental conditions. However, this general increasing tendency of n with respect to molecular
weight of feed was not observed for activation energies. The activation energy of the HDS reaction
for coal tar, which ranged from 37.62 to 71.06 kJ/mol, was lower than other petroleum fractions,
which may be due to the relative lower sulfur content in coal tar. The activation energy of the HDS
reaction obtained by Callejas and Martínez (1999) is higher than other literature, which is 287.16
kJ/mol. The possible reason can be that the distillation range of the feed that Callejas and Martínez
(1999) used is higher, and reaction temperature has a greater effect on HDS reaction.
In order to examine the reliability of the model, another five experiments have been done. The
relative errors from the combination kinetic model are all smaller than 2%, which illustrates that the
model can be used to predict the sulfur content of products accurately.

TABLE 4
Comparison of Reaction Order and Activation Energies for HDS Reaction of Different Feedstocksa

Sulfur, wt Distillation Range, Order of HDS Activation Energy,

Feed % °C Reaction kJ·mol–1

Present work Coal tar 0.38 214–510 2.02 42.15

Anderson et al. (1968) Coal tar 0.94 200–360 1 71.06
Qader et al. (1968) Coal tar 0.83 200–325 Pseudo first 37.62
Alvareza and Ancheyta Crude oil 5.47 NA 1.17 104.04
(2008)
Ancheyta et al. (1999) AGO 1.31 213–368 1.57 84.96
Bej et al. (2000) AGO 1.47 NA 1.65 104.65
Yui and Ng (1995) HGO 4.33 242–566 1.5 94
Callejas and Martínez AR 3.45 IBP–540 = 63 vol% 2.0 287.16
(1999)
Chen et al. (1990) AR 3.72 281–538 2.0 121.39
Wang et al. (2007) AR 2.83 NA 1.5 114.00
Diaz-real et al. (1993) Bitumen 4.1 210–655 Pseudo first 176
a
NA: not available; AGO: atmospheric gas oil; AR: atmospheric residue; HGO: heavy gas oil.
 HYDRODESULFURIZATION OF COAL TAR 2599

4. CONCLUSIONS

In this article, optimization for coal tar HDS process conditions were investigated using the
Box–Behnken experimental design. HDS reactions are described by a quadratic model. The
obtained mathematical model was an empirical quadratic model with R2 values of 0.9884,
showing excellent variability of the model and the ability to predict sulfur content in the
products. ANOVA analysis of experimental data indicated that the optimum operating
conditions were found to be: reaction temperature of 681.25 K, hydrogen pressure of 13.1
MPa, hydrogen to oil volume ratio of 1,200 LN/L, and LHSV of 0.32 h–1, under which the
sulfur content of products was 12–16 mg/kg.
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Based on the power law model, the kinetics model for HDS of coal tar has been built. The
parameters of the kinetic equation were found to be: E = 42,150; n = 2.022; a = 3.905; b = –0.666;
and k0 = 472,500. The HDS reaction of coal tar follows second-order kinetics, and the activation
energy is lower than other petroleum fractions. The results indicate that the model could predict the
sulfur mass fraction of hydrogenation products accurately. These findings provide some valuable
information for further researches in the coal tar hydro-upgrading process.

FUNDING

The authors gratefully acknowledge the financial support by the “13115” Key Technologies R&D
Programme of Shaanxi province (2008ZDKG-50, 2010ZDKG-42), Natural Science Fund of
Shaanxi province (2010JM2002), Key Innovation Research Plan of Xi’an (CXY1021),
Educational Commission of Shaanxi Province (2010JK874, 2010JC23), Science Foundation of
Northwest University (09NW06), National Natural Science Foundation of China (21206136),
Overall Science and Technology Innovation Project of Shaanxi province (2014KTCL01-09), and
Independent Innovation Project of Northwest University (09YZZ50).

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