F U E L P R O CE SS I NG T EC H NOL O G Y 8 9 (2 0 0 8 ) 6 4 36 5 0

w w w. e l s e v i e r. c o m / l o c a t e / f u p r o c

Simulated delayed coking characteristics of petroleum

residues and fractions by thermogravimetry
Aijun Guo, Xuejun Zhang, Zongxian Wang
State Key Laboratory of Heavy Oil Processing, College of Chemistry and Chemical Engineering, China University of Petroleum (East China),
Dongying 257061, China

AR TIC LE I N FO

ABS TR ACT

Article history:

Simulated delayed coking characteristics of five petroleum residues from various sources in

Received 1 August 2007

China and four fractions from one of the residues were investigated by thermogravimetry

Received in revised form

(TG), and interactions among the fractions were thus revealed. Results showed that

2 December 2007

properties of these petroleum residues and fractions varied over a broad range. The

Accepted 10 December 2007

coke yields from residues were closely related to their carbon residues and those from

Keywords:

saturates N aromatics N resins N asphaltenes, while actual overall cracking intensity

Residue

appeared in reverse order when measured by the heat effect derived from differential

Thermogravimetry

thermal analysis (DTA). The apparent cracking reactions of the fractions and their parent

Delayed coking

residue could be described in first order kinetics in two coking temperature zones with

Fraction

activation energies being 75120 kJ mol1 and 130210 kJ mol1. Saturates promoted coke

Kinetics

formation from other fractions, while aromatics inhibited coke formation from both resins

Coke formation

and asphaltenes; the coke yield from a residue was smaller than that by physical

Asphaltene

summation based on residue's compositional fractions. It is thus possible to inhibit coke

the fractions varied much. Apparent thermal-cracking activity was in the order

formation and enhance liquid distillate production by delayed coking of certain mixed
petroleum residues.
2007 Elsevier B.V. All rights reserved.

1.

Introduction

High conversion of petroleum residue is a focus for petroleum

scientists and engineers. Since the 1970s, petroleum price has
risen from time to time and the world market petroleum has
got increasingly heavier and more inferior. However, the
market share of refined light oil products is rising and that of
refined heavy ones (such as residual fuel oils) is declining. This
prompts the discrepancies of the market [1]. Therefore the
task aiming at increasing light oil supply by converting residue
severely is becoming very urgent, and refineries have to solve
this problem. Delayed coking technology is a major means to
upgrading inferior residue in major petroleum refining
countries, because this technology requires low equipment

investment and simple process scheme, and is fit for processing petroleum residues of high CCR (Conradson carbon
residue), high sulfur content and high metal content to obtain
highest yields of distillate liquid [2]. Delayed coking is a central
part in most US refineries through which petroleum residues
are processed as a first step and their vacuum gas oil products
are further cracked to gasoline and diesel fuel distillates by
hydrocracking or fluid catalytic cracking. Because of the
overwhelming demand for gasoline and diesel fuel in China
coupled with a high vacuum residue content at 4050 wt.% for
China's major crude oils, its delayed coking capacity has
tripled for the recent ten years and has reached a surprising
level of over 55 Mt/a till 2006, and still more delayed coking
units are under way or in the plan. If coke formation from

Corresponding author. Tel.: +86 546 8396049; fax: +86 546 8391971.
E-mail address: ajguo@mail.hdpu.edu.cn (A. Guo).
0378-3820/$ see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2007.12.006

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Table 1 Selected properties of residues from various sources

Property
Molecular weight (by VPO)
Density (20 C)/g cm3
Viscosity (100 C)/mm2s1
CCR/wt.%
Ash/wt.%
Elemental analysis
C/wt.%
H/wt.%
NH/NC
N/wt.%
S/wt.%
SARA composition/wt.%
Saturates
Aromatics
Resins
n-C7 asphaltenes
Metal content/g g 1
Ni
V
Fe
Ca

Jinzhou

Liaohe

Gudao

Shengli

Daqing

1120
0.9917
1660
17.3
0.080

990
1.0013

19.0
0.056

810
0.9756
1430
15.6
0.030

810
0.9614
690
13.9
0.036

820
0.9357
118
9.1
0.010

87.1
11.4
1.56
0.91
0.34

86.1
11.1
1.53
1.22
0.36

85.1
11.3
1.58
1.07
3.12

85.0
11.6
1.63
0.78
1.31

87.0
12.7
1.74
0.43
0.20

17.2
29.6
51.3
1.9

18.8
26.4
52.7
2.1

22.3
32.1
42.1
3.5

18.8
33.7
45.7
1.8

38.4
34.0
27.5
0.1

118.3
2.0
38.4
65.9

122.6
2.9
37.5
95.6

48.0
2.2
13.8
33.8

86.7
4.3
41.8
25.4

9.5
0.2
8.6
16.3

coking could be slightly inhibited and thus the liquid yield is

increased just by 1 wt.%, it would mean a huge economic
benefit for the challenging refinery industry [3].
Delayed coking is a high temperature process and thermogravimetric tools have been frequently employed to investigate high temperature characteristics of materials such as coal
and coal tar pitch [46], refuse derived fuels [79], petroleum
residue or coke [1012], oil shale [13,14], animal product [15],
and their blends possibly with biomass [1618], which shows
the feasibility of thermogravimetry in the study of in situ
coking and pyrolysis of macromolecular material. Goncalves
et al. [10] found that it was possible to anticipate volatile and
coke yields during thermal cracking of petroleum residues by
thermogravimetry. Guillh et al. [4] found on the other hand
that high coke yields from coal tar pitches are associated with
molecular structure of reactants, i.e. a highly condensed
volatile fraction in which alternant peri-condensed polycyclic
aromatic hydrocarbons predominate over non-alternant systems. Some authors [79,17] found that complex material's
pyrolysis product distribution is the physical summation of
the reactant's individual component contribution. However,
others [11,16,18] suggested that interactions are exhibited by
the fact that the product slates from the co-coking reactions

are not linear combinations of the products from the feedstocks reacted individually.
Compositions of delayed coking feedstock have changed a
lot from what they were in the past when delayed coking
process was initially put into practice, therefore the existing
coking process has to be updated in time accordingly. Critical
bases for the timely optimization are the coking characteristics of residues and related fractions, and the interactions
between different fractions [11,19]. However, related coking
reports on petroleum residues are sparse, especially on typical
residues from various sources in China. This research aims to
investigate the coking characteristics of representative petroleum residues of different Chinese origins and related fractions by thermogravimetric analysis.

2.

Experimental

2.1.

Samples

Samples (Table 1) were the Jinzhou vacuum residue and its four
fractions, and four vacuum residues from other sources different than Jinzhou refinery. The four fractions were saturates,

Table 2 Selected properties of the fractions from Jinzhou residue

Property
Molecular weight (by VPO)
Elemental analysis
C/wt.%
H/wt.%
NH/NC
N/wt.%
S/wt.%
Aromaticity
Average molecular formula

Saturates

Aromatics

Resins

Asphaltenes

510

900

1380

10,860

86.1
13.6
1.89

0.08
C37H69

87.4
11.7
1.59
0.57
0.42
0.24
C66H104N0.2S0.1

86.9
10.3
1.41
1.56
0.43
0.34
C100H141N0.8S0.2

87.0
8.4
1.15
2.81
0.33
0.49
C786H904N11.0S1.1

F U E L P R O CE SS I NG T EC H NOL O G Y 8 9 (2 0 0 8 ) 6 4 36 5 0

Fig. 1 TG analysis curves of Jinzhou residue () and its

reproducibility experiment with a different sample size
(). Operating conditions: heating rate at 5.0 C min 1, flow
rate of nitrogen carrier gas at 50 mL min 1. G0, Gt, and Gf
denote initial sample weight, residual sample weight at any
temperature in the heating process, and residual sample
weight at the final reaction temperature (i.e. 680 C),
respectively. T0, Tt, and Tf denote starting temperature (i.e.
200 C), any temperature in the heating process, and the final
reaction temperature, respectively. Thus coke yield and
cracking conversion of the initial sample can be estimated via
the first two formulae in Section 2.3, respectively.

aromatics, resins, n-C7 asphaltenes (i.e. SARA fractions) and were

obtained by a referenced method [20]. A selection of properties of
the fractions from Jinzhou residue is presented in Table 2.

2.2.

Thermogravimetric analysis

645

Fig. 3 Relation between the coke yields from TG curves due

to thermal cracking of Jinzhou residue and its fractions:
asaturates, baromatics, cresins, dasphaltenes,
eresidue.

was 680C, the residual sample weight was constant and the
reaction was terminated. The whole test was operated at ambient
pressure. All TG analyses were duplicated or replicated to test
their reproducibility, which was found to be very good.

2.3.

Calculation

cokek Gf =G0  100k

a G0  Gt =G0  Gf
where coke% is the coke yield in wt.% (Figs. 2 and 3), and is the
cracking conversion of the initial sample (Fig. 4).
By using Sharp's differential method [21], thermogravimetric
kinetic parameters can be derived. Thermal cracking of samples
can be expressed as
heat

Sample Y Volatiles Coke;

Samples were analyzed by using a WCT-2 thermogravimetric

analyzer. When a run was performed, 510 mg of sample was
placed in an alumina crucible. High purity nitrogen gas, with a
flow rate of 50 mL min1, was used as a carrier gas and protecting
atmosphere against oxidation. Reaction temperature was attained
by an electric furnace with a heating rate () of 5.0 C min1. TG (see
Fig. 1 for typical collections for a residue), DTG, and DTA curves
were collected simultaneously by the instrument-specific RSZ
software, enabling one to obtain corresponding data at any point
in the experimental temperature range. Data were collected at
temperatures of 200C and up, and when reaction temperature

where is the heating rate during thermogravimetric analysis, n is

the reaction order, Ea is the activation energy, and A is the preexponential factor. At different reaction temperature zones during
thermal cracking, or coking, first order reaction laws (i.e. n = 1)
were applied respectively. By linear regression, slopes and

Fig. 2 Relation between the coke yields from TG curves and

CCR (Conradson carbon residue) of residues from different
sources.

Fig. 4 Cracking conversions of the fractions from Jinzhou

residue: Same legend as in Fig. 3.

and Sharp's method is given as follows,


ln


da
Ea
=1  an ln A 
RT
dT

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intercepts in the kinetic plots could be determined to calculate Ea

and A, respectively. Furthermore, by the intersection point of both
regressed lines, the critic temperature (Tc) [13] between both
temperature zones was obtained.

3.

Results and discussion

3.1.

Characterization of residues and fractions

Evaluation of feedstock properties is fundamental for understanding feedstock coking and thermal-cracking behaviors. It
is shown in Table 1 that the Jinzhou residue is characteristic of
high viscosity, high carbon residue, high metal content, high
nitrogen content, high resin content, low H/C atomic ratio,
low sulfur content, and low saturate content. Overall the five
vacuum residues presented in Table 1 can be grouped into
three categories based on density, carbon residue and metal
content. Jinzhou and Liaohe residues are high in these specification items, implying high coke yields at coking conditions.
In contrast, Gudao and Shengli residues are in the medium
coke yield category and Daqing residue in the low coke yield
category. High coke yield at elevated temperatures is mainly
the result of condensation reaction of highly carbonaceous
material; part of the metals as in the form of sulfides, will
dehydrogenate less carbonaceous hydrocarbons to facilitate
coking of the reactants [5], thus may render coke yield even
higher.
Fractions from Jinzhou residue are further characterized
and the properties are provided in Table 2. It is shown that the
H/C atomic ratios of the four fractions (i.e. saturates, aromatics, resins, and asphaltenes, or SARA) are 1.89, 1.59, 1.41,
and 1.15, respectively, leading to rising aromaticities (fA),
which are 0.08, 0.24, 0.34, and 0.49, respectively. The very low
aromaticity of saturates may be a result of incomplete fractionation by alumina column chromatography; mono-ring
aromatics carrying long alkyls may behave actually as
saturate hydrocarbons, for example. The molecular weights
of the SARA fractions are 510, 900, 1380, and 10860, respectively. Thus the asphaltene fraction of the residue is of the
most highly carbonaceous molecular polyaromatics among
SARA, and will be prone to produce the highest coke yield at
elevated temperatures.

3.2.

Coking of residues and fractions

Petroleum residue tends to produce coke when they are

processed at elevated temperatures for prolonged duration.
Residue's coking tendency is usually evaluated in terms of
carbon residue such as CCR. Since thermogravimetric analyzer
is an instrument of easy access, it may be convenient to estimate the coking tendency of a residue by TG test. Thus the
establishment of a relation between both coking tendencies
indicated by CCR and the coke yield from TG test may be
useful. TG curves for Jinzhou residue using different sample
sizes (i.e. 5.2 mg and 5.6 mg) are shown in Fig. 1 and the coke
yield of this residue is estimated to be 21.7 0.4 wt.%. The coke
yields of the five residues from different sources via thermogravimetry are presented in Fig. 2. There appears that coke
formation of a residue is closely related to its carbon residue.

Hence coking tendency can also be evaluated by the thermogravimetric coke yield. It is also shown that coke formation
from Jinzhou residue is much greater than that from Daqing,
Shengli, and Gudao ones, which are of lower carbon residues;
it is just lower than that from Liaohe residue, which is of
highest carbon residue.
Compositions of a petroleum residue are very complex.
They may vary in molecular structure and thermal reaction
characteristics to a certain degree, however, compositions of
each fraction are quite similar [1,2]. Therefore fractions are
usually used to investigate residue's detailed structure and
reaction characteristics [22,23]. The relation between coke
formation of Jinzhou residue and its fractions during thermal
coking is shown in Fig. 3. It is shown that coke formation
of the fractions is determined by both aromaticity and
molecular size. It follows the order saturates b aromatics b
resins b asphaltenes. Coke formation from the residue is
between that from aromatics and resins. It is noteworthy
that coke formation from saturates amounts only to about
5 wt.%, while coke formation from asphaltenes is more than
50 wt.%. These findings indicate that an important way to
increase cracking yield and to decrease coke formation is to
decrease coke formation from the asphaltic fractions in the
coking feedstock.
Further investigation reveals that although coke formation
from Jinzhou residue is 21.7 0.4 wt.% (Fig. 1), physical
summation of coke formation of the four fractions is as high
as 23.2 0.3 wt.%, which is greater than the former value. Thus
co-coking of the four fractions inhibits coke formation from
them. Therefore, interactions of the fractions during thermal
coking will be studied in depth later in this research. Coke
formation from experimental co-coking of petroleum residue
with FCC decant oil [11] or sugarcane bagasse [18] was reported
to be higher than physical summation of the coke formation
from individual coking, and reverse phenomenon, which was
very similar to the finding here, was also documented [11].

3.3.

Thermal reaction activities of fractions

3.3.1.

Apparent activities of fractions during thermal cracking

Apparent activities of fractions during thermal cracking can be

indicated by characteristic conversion temperatures (Ts) where
the same cracking conversion () is reached. s of the fractions
from Jinzhou residue with reaction temperature are presented
in Fig. 4. There is a range for each curve where slopes are very
large. The corresponding temperature range therefore shows
the intensive cracking that happened. Based on the data in
Fig. 4, comparisons can be made on certain Ts (e.g. T0.2, T0.5
and T0.9) at selected s (correspondingly 0.2, 0.5, and 0.9). Thus
Table 3 is derived. Evidently T of saturates is the lowest

Table 3 Characteristic conversion temperature (T) of

Jinzhou residue fractions
Fractions
Saturates
Aromatics
Resins
n-C7 asphaltenes

T0.2/C

T0.5/C

T0.9/C

327
394
408
414

367
434
441
445

412
459
478
492

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Table 4 Apparent characteristic kinetic values of Jinzhou residue fractions during thermal cracking
Fraction
Saturates
Aromatics
Resins
Asphaltenes
a

Maximum cracking rate,

rM 103/C 1

Temperature at maximum
cracking rate, TM/C

Conversion at maximum
cracking rate, M

Temperature range of
intensive cracking a/C

9.8
14.9
14.9
28.1

400
450
450
440

0.792
0.743
0.650
0.440

263437
330478
339496
299561

Corresponding to apparent cracking rate (r) greater than 0.001 C1.

among those of the four fractions, hence the apparent

thermal-cracking activity of saturates is the highest among
them. The order of the apparent activity is thus saturates N aromatics N resins N asphaltenes. It is also interesting that
the activity difference between saturates and aromatics is
much greater than that between aromatics and resins or
between resins and asphaltenes.

3.3.2. Apparent kinetic characteristics of fractions during

thermal cracking
By applying numerical differentiation method to the curves in
Fig. 4, relation between apparent cracking rate r (r = d / dT) and
reaction temperature T can be derived. Thus apparent kinetic
characteristics of each fraction can be obtained, such as maximum cracking rate rM, reaction temperature TM at rM, cumulative
cracking conversion M at rM, and temperature range of intensive
cracking. These parameters are summarized in Table 4.
rM may indicate the apparent cracking intensity of a
fraction. It is shown that rM tends to increase with increasing
aromaticity and molecular size of a fraction. The rMs of
aromatics and resins are quite similar, and that of asphaltenes
is much greater than the other fractions. TM seems to follow a
similar tendency except that asphaltenes' TM is a little lower
than that of aromatics or resins. As far as M is concerned,
however, it decreases with increasing aromaticity and molecular size of a fraction, that is saturates N aromatics N resins N
asphaltenes. Hence with rising aromaticity and molecular
size of a fraction, it would release lesser cracked volatile
products. As for the temperature range of intensive cracking,
temperature of intensive cracking tends to increase with
rising aromaticity or molecular size of a fraction.

3.3.3. Intrinsic cracking intensity of fractions during thermal

cracking
In the immediately above two sub-sections thermal-cracking
activity was dealt with in view of apparent thermal-cracking
results. Both physical volatilization and thermal cracking,
which are endothermic processes, are the causes of those
apparent results. It is well known that the absolute value of
enthalpy of a chemical reaction may be greatly higher than
that of a physical change, such as enthalpy of volatilization.
On the other hand, when a fraction or residue thermally
cracks at ambient pressure, the volatile product will escape
from the bulk reactants, probably leaving the reaction bulk as
a solid or semi-solid phase, which will cause unfavorable mass
transfer. This will lead to minimized condensation reactions
and hence minimized exothermic enthalpies. Therefore the
absolute value of the apparent heat consumed by both
thermal cracking and volatilization in the thermal-cracking

period will help to illustrate at least qualitatively the relative

thermal-cracking intensity of a fraction. DTA records the endothermic peak area (Aen) of a fraction during thermal cracking,
and the Aens are summarized in Table 5. Here Aen is an
indirect measure of the absolute value of the heat consumed
during thermal cracking. It is shown that under thermalcracking conditions, heat consumed by saturates is least
(Aen = 0.42 A.U.). It is only about a third of that by aromatics, an
eighth by resins, and a fourteenth by asphaltenes, indicating
the thermal-cracking intensity of the fractions is in the order
saturates b aromatics b resins b asphaltenes.
This sequence of heat consumed by fractions is dictated by
the physiochemical properties of the species in and from
them. Saturate species include alkanes of straight chains,
branched chains, and cyclic rings. These molecules evaporate
easily, which is evidenced by the fact that the T0.2 of this
fraction is as low as 327 C as shown in Table 3 (while evident
thermal-cracking temperatures of petroleum molecules are
usually reported to be greater than 350 C [24]). However
species in the other three fractions have benzene-ring structures. These species have lower volatility with rising condensation of benzene-ring systems. Actually the property of
physical evaporation is the main restriction for thermogravimetric analysis on residue's thermal cracking and especially
on its cracking kinetics [25]. As for the three aromatic
fractions, both molecular weight and aromatic sheet numbers
increase from aromatics through resins to asphaltenes [1].
Therefore in order to vaporize the molecules at limited temperatures, the chemical bonds to be broken up must increase
in numbers, and the total heat consumed increases, resulting
in increasing thermal-cracking intensity. Furthermore, the
high reactivity of asphaltenes also confirms Wiehe's result by
kinetic rate constant analysis [26].

3.4.
Apparent cracking kinetics of Jinzhou residue and its
fractions during simulated delayed coking process
Under industrial delayed coking process fractions of Jinzhou
residue do evaporate physically in the same way as what was
just discussed. Thus it is important in utility to study in open
system under inert carrier gas the apparent cracking kinetics
Table 5 Endothermic peak area (Aen) of Jinzhou residue
fractions during thermal cracking
Fraction
Aen/A.U.
a

Saturates

Aromatics

Resins

Asphaltenes

0.42

1.28

3.26

5.78

Arbitrary unit.

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Table 6 Kinetic parameters of Jinzhou residue and its fractions during thermal cracking
Critic
temperature,
Tc/C

Reaction
temperature zone

Temperature
range, T/C

Activation energy,
Ea/kJ mol 1

Pre-exponential factor,
ln(A) / lns 1

Saturates

390

Aromatics

400

Resins

410

Asphaltenes

390

Residue

420

1
2
1
2
1
2
1
2
1
2

b390
390420
b400
400460
b410
410450
b390
390420
b420
420460

77.0 1.5
132.4 2.2
75.3 2.6
184.2 5.4
92.9 5.4
184.6 4.2
117.3 5.4
211.4 5.7
84.2 3.9
187.8 2.4

12.17 0.30
22.16 1.29
9.94 0.52
29.35 0.93
12.95 1.02
29.06 0.71
17.94 0.99
34.31 4.40
11.59 0.72
29.69 0.40

Item

of residue and its fractions [11,19,25]. After the completion of

the kinetic plots (i.e. plot of 1 / T against ln[(d / dT) / (1 )])
of the fractions from Jinzhou residue, which give correlation
coefficients of greater than 0.97, the derived kinetic parameters are then given in Table 6. For comparison, related
parameters for the parent residue are also shown.
From the data presented, thermal cracking of the fractions
during the simulated coking process follows first order
reaction kinetics when the reaction temperature ranges are
divided into two zones at the critic temperature (Tc) [11,13] and
the data are processed by Sharp's differential method [21]. The
Tcs for the fractions are within a narrow range of 390410 C,
which is in the general range of 300450 C [11,13]. Under lower
and higher temperatures (i.e. zones 1 and 2 in Table 6, respectively), activation energies are 75120 kJ mol 1 and 130
210 kJ mol 1, respectively. The evident difference in activation
energies at different temperature zones indicates different
reaction mechanisms at different temperature zones for any
certain fractions [11]. At lower temperatures the process is
dominated by scission of weak bonds (i.e. single bonds of
carbon with sulfur or nitrogen atom) and volatilization, and
scission of stronger bonds needs more energy and will thus
predominate at higher temperatures. This may be dictated by
the relative complex composition of a fraction. Molecules in a
fraction are different in molecular weight and thus having
different cracking abilities. In either zones, the activation
energies tend to increase in the order saturates b aromatics b
resins b asphaltenes. This means that in such an order of
fractions, more bonds need to be broken up before the
fractions get volatilized.

It can also be observed that the parent residue also follows a

two-zone first order kinetics (Table 6). The activation energies
are similar to those for aromatics and resins in either zone.

3.5.
Interactions of fractions during simulated delayed
coking process
It was discovered previously in this research that the coke
yield from Jinzhou residue is less than the physical summation of the coke yields from its four fractions by weight
composition during simulated delayed coking process. Thus
fractions may inhibit coke formation when all the fractions are
co-coked in certain proportions. In order to further investigate
the underlying chemistry of coke inhibition by blending, mixture of fractions can be made to perform simulated delayed
coking process by TG analysis. Coke formation from five mixtures (dual system) is tabulated in Table 7.
It is clear that these dual systems can be categorized into
two groups as far as coke inhibition or coke promotion effect is
concerned. The first group includes the first three systems,
which shows that saturates may promote coke formation
when mixed with the other fractions. This promotion on coke
formation was documented when petroleum residue was cocoked with biomass [18]. The second group includes the rest
two systems, which shows that aromatics inhibit coke
formation when mixed with resins or asphaltenes. Similar
inhibition on coke formation was also mentioned in the
literature [11].
The coke promotion effect of saturates is greatest on aromatics, moderate on resins, and least on asphaltenes, and the

Table 7 Coke formation of mono and dual systems of Jinzhou residue fractions
Mono-system, coke yield/wt.%
Reactant
Saturates
Aromatics
Resins
Asphaltenes

a
b
c

Dual system, coke yield/wt.%

Experimental value

Reactants a

Experimental value

Physical summation b

Increment c

5.7 0.6
15.4 0.5
32.4 0.5
53.7 0.6

Saturates + aromatics
Saturates + resins
Saturates + asphaltenes
Aromatics + resins
Aromatics + asphaltenes

22.6 0.5
27.2 0.4
35.6 0.6
21.0 0.3
30.8 0.4

10.5 0.4
19.1 0.4
29.7 0.4
24.1 0.4
34.8 0.4

12.1 0.6
8.1 0.6
5.9 0.7
3.1 0.5
4.0 0.6

Both fractions in each mixture are in mass ratio of 50:50.

Summation of experimental coke formation from mono-systems. Summation factor for either fraction is 0.5.
Difference by subtracting physical summation from experimental value.

F U E L P R O CE SS I NG T EC H NOL O G Y 8 9 (2 0 0 8 ) 6 4 36 5 0

corresponding coke increment for dual systems of saturates

with aromatics, resins, or asphaltenes are 12.1 wt.%, 8.1 wt.%,
and 5.9 wt.%, respectively. Factors related to the interaction
between fractions are multiple. Compared with mono-systems, fractions in dual systems may disperse and dilute each
other, resulting in coke inhibition [11]. On the other hand in
dual systems of reaction, hydrogen transfer occurs between
saturates and the other fractions. Saturate molecules crack
thermally to produce fragmental alkenes and free radicals,
which are hydrogen lean and are reactive species. These
fragments hence abstract hydrogens from other fractions and
thus produce immediate coke precursors, resulting in coke
promotion [27]. Therefore based on the experimental results, it
can be concluded that in mixtures of saturates and any other
fractions, thermal cracking and the ensuing hydrogen abstraction are the main factors leading to coke promotion effect.
As for the second group, coke inhibition effect of aromatics
is lesser on resins than on asphaltenes, and correspondingly
coke decrement of the dual systems of aromatics with resins
or asphaltenes are 3.1 wt.% and 4.0 wt.%, respectively. Because
of the evident aromaticity of aromatics, aromatics physically
disperse, or solve, resins and asphaltenes better than saturates do. Hence as for the coke inhibition ability due to
physical dispersing effect, aromatics are more effective than
saturates. On the other hand, residue's aromatic molecules
are actually hydro-aromatics. Under thermal treatment these
molecules will donate hydrogens to coke precursors and cap
asphaltic free radicals from combination reaction that would
otherwise lead to coke formation. Because both the physical
dispersing effect and the chemical hydrogen donation of
aromatics inhibit coke formation, coke yields from mixtures of
aromatics with resins or asphaltenes decrease spontaneously.
Jinzhou residue, together with other residues, is actually a
natural mixture of the four fractions by chemical composition
(Table 1). Because of both physical dispersing and hydrogen
transfer among all the fraction molecules, coke formation
from residue during coking is inhibited compared to coking its
fractions separately. Thus the coke reduction is as high as
1.5 wt.%. Therefore it can be deduced that co-coking of various
petroleum residues may inhibit coke formation and enhance
the yield of liquid distillate product in contrast to separate
coking of the individual residues.

4.

Conclusions

Petroleum residues from different sources may be different in

both properties and chemical compositions, leading to different coking characteristics. The same is also true for the
different fractions from a single residue.
The coke yields from residues by TG test correlate well with
their CCR, and thus the TG coke yield can be another measure
of coking tendency. The coke yield from Jinzhou residue is
higher than that from Daqing, Shengli, and Gudao oilfields
residues, and is just lower than that from Liaohe oilfield
residue.
The coke yields from the fractions of Jinzhou residue increase
in the order saturates b aromatics b resins b asphaltenes. The
coke yield from the residue is between those from resins and
aromatics.

649

During thermal cracking of the fractions from Jinzhou

residue, the order of the apparent cracking activity is saturates N aromatics N resins N asphaltenes. However, intrinsic
cracking intensity of the fractions is in exactly reverse order
as revealed by the endothermic effect detected by DTA.
Apparent kinetic study showed that during thermal cracking/coking of Jinzhou residue and its fractions, cracking
reaction follows first order reaction in two different temperature zones. Since the activation energies are quite different in
the two zones, cracking follows different reaction mechanisms in different temperature zones.
Saturates may promote coke formation from the other
fractions, while aromatics may inhibit coke formation from
resins and asphaltenes. The coke promotion effect of saturates is greatest on aromatics, moderate on resins, and least
on asphaltenes. Because of both physical dispersing and
hydrogen transfer among all the fraction molecules, coke
formation from residue during coking is inhibited compared to
coking its fractions individually. An implication of this
experimental phenomenon is the possibility of inhibiting
coke formation and enhancing liquid distillate production by
delayed coking of certain mixed petroleum residues.

Acknowledgements
Financial support of PetroChina for the research is greatly
appreciated. The authors are also grateful to Miss Minhong
Zang for assistance in performing part of the experimental
work.

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