A Delayed Coking Model Built Using The Structure-Oriented

A Delayed Coking Model Built Using the Structure-Oriented
Lumping Method
Lida Tian, Benxian Shen,* and Jichang Liu
State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237,
Peoples Republic of China
ABSTRACT: A total of 7004 types of molecular lumps and 92 types of reaction rules were proposed to characterize the feedstock
and describe the reaction behaviors of delayed coking. The reaction rate constants were estimated as equations of structure vectors.
A reaction kinetic model has been built to predict the products distribution of delayed coking. The good prediction accuracy of the
model has been proven by the comparison of calculation results and experimental results of delayed coking.
1. INTRODUCTION
In 1992, Quann and Jaffe proposed the concept of structure-
oriented lumping (SOL).
1,2
This concept made the kinetic
lumping method extend to the molecular level and made it
possible to describe the reaction behaviors of complex reaction
systems. In recent decades, the SOL method has been applied
in some fields. In addition, some SOL models have been built
continually.
3,4
In 2005, Jaffe extended this concept to residue
describing.
5
However, building kinetic models of delayed
coking still had two problems: the feedstock residue is
difficult to characterize, and the reaction rate constants are
difficult to calculate. This paper solved the two problems
and built a kinetic model of delayed coking using the SOL
method.
2. CHARACTERIZATION OF THE FEEDSTOCK
2.1. Structure Vectors To Characterize Feedstock. In
SOL, 22 structure vectors were proposed to characterize the
feedstock.
1,2
To characterize the residue, Jaffe proposed two
more structure vectors to represent nickel and vanadium.
5
For
the specific delayed coking process, this work changed some
structure vectors slightly. The RS, RN, and NO vectors were
neglected and a vector called cc was considered to represent
the strength and carbon numbers between cores and cores. The
22 new structure vectors and their stoichiometric matrices are
shown in Table 1.
2.2. Molecular Lumps and Their Contents Calculation.
According to the SOL method, this paper proposed 92 types of
single-core seed molecules and 46 types of multicore seed
molecules to characterize the residue. After adding different
numbers of CH
2
to seed molecules, a total of 7004 types of
molecular lumps were generated to characterize the molecular
composition of residues. Figures 1 and 2 show single-core seed
molecules and metal compound multicore seed molecules,
respectively.
To calculate the contents of the proposed molecular
lumps, a cut of feedstock, such as that described in Figure 3,
is needed.
After doing this, a simulated annealing algorithm (SA) could
be used to search the suitable contents.
3. SIMULATE THE MOLECULAR REACTION
BEHAVIORS
3.1. Reaction Rules. Reaction rules were used to describe
the molecular behaviors. They were the standard to judge
that how the material molecular matrix turned to a product
molecular matrix. Each reaction rule included reactant
selection rule and product generation rule.
6
Reactant
selection rule selected the molecules (structure vector
groups), whether this type of reaction will occur. Product
generation rule generated the product molecules (structure
vector groups) from reactant molecules of this type of
reaction.
Delayed coking is a thermal cracking process that obeys
the free-radical mechanism.
7
The reactions of delayed
coking are complex. But overall, all the reactions could be
divided into cracking and condensation. According to the
reaction types in delayed coking, 92 types of reaction rules
were established to describe the reaction behaviors of
heavy oil delayed coking. Some typical reaction rules are as
follows:
(1) Side Chain Breaking of Single-Core Molecules (All)
Reactant selection rule:
> > >
> + < <
[(A6 0) (N6 0) (N5 0)]
(R me KO) (A6 10) (N6 10)
Product 1:
=
= >
R R me KO,
br (br 1) (br 0); the rest: 0
1
1
Product 2:
= + = R me KO, br 0; the rest: invariant
2 2
Received: October 14, 2011
Revised: November 21, 2011
Published: December 16, 2011
Article
pubs.acs.org/EF
2011 American Chemical Society 1715 dx.doi.org/10.1021/ef201570s | Energy Fuels 2012, 26, 17151724
e.g.,
Reactant:
A6 A4 A2 N6 N5 N4 N3 N2 N1 R br me IH AA NS AN NN RO KO Ni V cc
1 0 0 0 0 1 0 0 0 6 1 1 0 0 0 0 0 0 0 0 0 0
Product 1:
0 0 0 0 0 0 0 0 0 5 0 0 0 0 0 0 0 0 0 0 0 0
Product 2:
1 0 0 0 0 1 0 0 0 1 0 1 0 0 0 0 0 0 0 0 0 0
Table 1. Structure Vectors and Stoichiometric Matrices
a
C 6 4 2 6 5 4 3 2 1 1 0 0 0 0 1 1 1 0 0 0 0 0
H 6 2 0 12 10 6 4 2 0 2 0 0 2 2 2 1 1 0 2 2 0 0
S 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0
N 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 1 0 0 0 0 0
O 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 1 0 0 0
Ni 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0 0
V 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0
a
The meanings of the 22 structure vectors are as defined in Chart 1.
Chart 1. Structures and Definitions Used in Table 1
Energy & Fuels Article
dx.doi.org/10.1021/ef201570s | Energy Fuels 2012, 26, 17151724 1716
(2) Multicore Molecules Cracking (First Joint)
Reactant selection rule:
= = fix rem fix rem [ ( (cc, 100)/10) 3] [ ( (cc, 100)/10) 2]
Product 1:
= + = + = = rem rem rem X rem X R (R, 100) (cc, 10), me (me, 10) 1, cc 0; the rest: ( , 10)
1 1 1
Product 2:
= = + = = fix fix fix X fix X R (R/100), IH (IH/10) 1, cc (cc/100); the rest: ( /10)
2 2 2 2
e.g.,
Here, the symbol means or; the symbol means and;
the subscript 1 means product 1; the subscript 2 means
product 2; without subscript means reactant; invariant
means equal to reactant; rem means remainder and f ix
means eliminate the decimal to recent integer.
According to the method proposed by the authors previous
paper,
4
simultaneous differential equations could be generated. In
addition, the product molecular matrix could be calculated from
the reactant molecular matrix, using the fourth- and fifth-order
RungeKutta methods.
3.2. Estimate of Reaction Rate Constants. To solve the
above differential equations, the reaction rate constant of each
reaction should be known. However, the number of equations would
be huge. Some reaction rate constants could be obtained from the
literature,
8,9
but far from the standard to solve such differential
equations. It is also inappropriate to obtain these rate constants by
experiment. Based on transition-state theory, rate constants could be
calculated by formula. Molecular simulating software was used to
search the transition state and calculate some kinetic parameters.
However, for delayed coking, this method was limited by two factors:
(1) There are so many reactions in delayed coking, it is very
time-consuming to calculate the rate constant one by one
with this method; and
(2) Only simple molecules with a small number of atoms
were available for the transition-state search. For the
reactions involving complex molecules, it is difficult to
Figure 2. Metal compounds multicore seed molecules.
Reactant:
101 100 0 10 0 243 0 0 0 10301 0 101 0 0 0 0 0 0 0 0 0 2231
Product 1:
1 0 0 0 0 3 0 0 0 2 0 2 0 0 0 0 0 0 0 0 0 0
Product 2:
10 10 0 1 0 24 0 0 0 103 0 10 1 0 0 0 0 0 0 0 0 22
Figure 1. Single-core seed molecules.
search its transition state with molecular simulated
software such as Materials Studio.
Since it is hard to calculate every reaction rate constant exactly,
it is necessary to estimate the value of rate constants. The
concept that molecular kinetic properties and structure vectors
could be associated with molecular structure provides the basis
for estimating a large number of reaction rate constants.
The first approximation to estimate the rate constants was
that all reactions in a class had the same reaction rate constant,
because they underwent the same reaction pathway. However, this
approximation was insufficient, because, within each reaction class,
the molecular structure of reactant and product could influence
the rate constants. So the second approximation was that a
perturbation to the reaction rate constants arose, considering the
influence of different molecular structures on the reaction rate
constants. The structureactivity relationship in kinetics was not
a new concept. Such studies were done by Hammet, Taft, and
Swain.
10,11
Structure vectors were used to describe the molecular
structure in the SOL method. Therefore, this perturbation could be
associated with structure vectors.
In transition-state theory, eq 1 could be used to calculate the
reaction rate constant:
4
=

k T
k T
h
T S E
RT
( ) exp
B
(1)
Here, k
B
is the Boltzmann constant, h the Planck constant, T the
temperature, R the ideal gas constant, S the entropy changes
before and after reaction, and E the reaction energy barrier.
Therefore, if S and E were known, the reaction rate constant
under certain temperatures could be calculated.
For simple reactions, S and E could be calculated using
Materials Studio software directly. For complex reactions, S
and E could be estimated by functions with structure vectors.
A common function type was
= + + + + y a x a x a x c
b b
n n
b
1 1 2 2
n 1 2
(2)
After calculating S and E of simple reactions as a regression
aggregate with Materials Studio software and using lsqcurvefit
function and the Matlab optimization toolbox, equations to calculate
S and E could be obtained. These equations are shown in
Tables 2 and 3.
Figure 4 shows the residual error distributions of these
equations for extrapolated prediction.
It could be found that the residual errors were slightly far
from the zero point. To revise them, the reaction rate constants
should be treated as follows:
= + k k(1 ) (3)
Here, k represents the reaction rate constant after revision, k is
the reaction rate constant before revision, and denotes the rate
revision index. The influence of each reaction class on product
distribution of delayed coking is considered to be the same.
Therefore, each reaction class has the same value. Sixteen groups
of results from delayed coking experiments of different feedstock
under different operating conditions were taken as objectives.
Moreover, these values could also be calculated using the SA
method. One thing we want to explain is that these functions
are only valid for the temperature range of 460500 C.
Table 4 includes these values.
4. SIMULATE THE DELAYED COKING PROCESS
4.1. Simplification and Assumption. The delayed coking
process includes several components, such as coking, fractionation,
gas recovery, coking processing, and venting system. The predic-
tion of the SOL model is directed only at the reaction system.
Therefore, the delayed coking process could be simplified similar
to the process depicted in Figure 5.
There were simplifications and assumptions for the model:
(1) The delayed coking process was composed of many short
batch processes.
(2) The coking drum inlet amount and its molecular
composition were unchanged every time.
(3) All the reactions occurred in a coking drum.
(4) The reactant molecules could be vaporized, immediately,
in the coking drum.
(5) There were no reactions during the input of materials
and the output of products, and the output of products
was completed immediately.
(6) The molecular compositions of gas products leaving and
remaining in the coking drum were the same.
(7) The coking drum was an ideal reactor, and the gas in the
coking drum behaved as an ideal gas.
Figure 3. Method of the residue feedstock cutting.
(8) The temperature and pressure of the coking drum in the
reaction process was kept constant, and cooling occurred
when the reactions were totally finished.
(9) Molecules of recycled oil were wax oil molecules, and the
molecular compositions of each part of the recycled oil
were the same.
Table 2. Equations Used To Calculate E
reaction classes equation
carbon chain cracking
=
+
E 0.3139R 0.2096br 0.0845(R R )
0.0614IH 95.8311
0.8043 0.5137
1 2
0.0197
side chain breaking
=
+
+ +
+

+

+

| |

( )
( )
( ) ( )
( )
E 0.2074 0.334
0.1495 0.1199
0.0172 92.781
A6 A4
Cores Ni V
N6 N4
Cores Ni V
R
Cores Ni V
0.7023
br me
Cores Ni V
0.3974
IH
Cores Ni V
dehydrogenation
=
+
+ +
+

( )
( ) ( )
( )
( )
E 0.0774 0.2927
0.0072 0.3585
0.0018 99.7853
me
Cores Ni V
N6 N4
Cores Ni V
R
Cores Ni V
0.3977
IH
Cores Ni V
br
Cores Ni V
0.1599
0.1039
molecular cracking
= +
+ +
+
+ +

( ) ( )
E 0.5472cc1 0.2772(Cores Cores )
0.0057 0.0042
0.0027 Cores 98.0873
R
1.5102
1 2
0.0039
A2 A6 A4
Cores Ni V
0.0081
Cores Ni V
0.0024
0.0031
1 1 1
ring opening
= +
+ +
+

| |

( )
( ) ( )
E 0.1742 0.0137
0.3248 100.7336
A6 A4
Cores Ni V
R
Cores Ni V
0.0649
IH
Cores Ni V
polycondensation
= +
+ + +
+

E 0.1885(A6 A4 ) 0.1876
0.0312R 0.0321 106.4872
1 1
0.5089
A6 A4
Cores Ni V
0.4953
1
0.1719
R
Cores Ni V
0.1833
2 2
2 2 2
2
2 2 2
DielsAlder
=
+ +
+

E 0.1737R 0.5179
0.2842 95.7364
1
0.2178
N6 N4
Cores Ni V
0.3113
R
Cores Ni V
0.2106
2 2
2 2 2
2
2 2 2
desulfuration
= +
+ +
+ +

( ) ( )
( )
E 0.2284 0.4805
0.0057 96.1871
N6 N4 N1
Cores Ni V
0.7471
R
Cores Ni V
0.5244
me
Cores Ni V
0.0078
decarboxylation
= +
+ +
+

+

( )
( ) ( )
E 0.0199 0.0099
0.0073 102.7983
N6 N4
Cores Ni V
0.8033
R 1
Cores Ni V
0.1386
br me
Cores Ni V
0.0061
4.2. Routinization of the Reaction Process. Only the batch
process could be disposed with the SOL method; therefore, it was
necessary to assume that the delayed coking process was composed
of many short batch processes. At the same time, an imaginary
coking drum was needed. This coking drum was an operating unit
that had two valves (for the inlet and outlet, respectively).
Table 3. Equations Used To Calculate S
reaction classes equation
carbon chain cracking
=
+
0.0369R 0.0087br 0.6745(R R )

0.0049IH 25.8387
S
R
0.8942 0.1394
1 2
0.0289
side chain breaking
=
+
+ +
+

+

+

| |

( )
( ) ( )
( )
0.0218 0.0299
0.0151 0.0123
0.0018 24.5755
S
R
A6 A4
Cores Ni V
N6 N4
Cores Ni V
R
Cores Ni V
0.8072
br me
Cores Ni V
0.4011
IH
Cores Ni V
dehydrogenation
=
+
+ +
+

( )
( ) ( )
( )
( )
0.0164 0.0602
0.0019 0.0798
0.0004 26.0377
S
R
N6 N4
Cores Ni V
R
Cores Ni V
0.4122
IH
Cores Ni V
br
Cores Ni V
0.1604
me
Cores Ni V
0.1113
molecular cracking
=
+
+ +

( )
( )
0.0015Cores 0.1311
0.0772 27.2086
S
R
0.0019
A2 A6 A4
Cores Ni V
0.3917
R
Cores Ni V
0.2299
1 1 1
ring opening
=
+
+

| |

( )
( ) ( )
0.0369 0.0049
0.0429 26.9285
S
R
A6 A4
Cores Ni V
R
Cores Ni V
0.0517
IH
Cores Ni V
polycondensation
= + +
+
+

0.0318 A6 A4 0.0303
0.0052R 0.005 29.1078
S
R
1 1
0.4873
A6 A4
Cores Ni V
0.5015
1
0.1476
R
Cores Ni V
0.1604
2 2
2 2 2
2
2 2 2
DielsAlder
= +
+
+

0.0399R 0.1195
0.0668 25.3282
S
R
1
0.2977
N6 N4
Cores Ni V
0.3075
R
Cores Ni V
0.2073
2 2
2 2 2
2
2 2 2
desulfurization
=
+
+ +

( ) ( )
( )
0.0459 0.1307
0.0016 25.8764
S
R
R N6 N4 N1
Cores Ni V
0.7713
Cores Ni V
0.5766
me
Cores Ni V
0.008
decarboxylation
=
+
+

+

( )
( ) ( )
0.0424 0.0031
0.0009 25.7382
S
R
N6 N4
Cores Ni V
0.7979
R 1
Cores Ni V
0.1291
br me
Cores Ni V
0.0011
The simulation of the delayed coking process proceeded as
described in Figure 6.
4.3. Product Division. The main products of delayed
coking were gas, gasoline, diesel, wax oil, and coke; the
results of the SOL model gave the molecular composition
of the products. To compare the simulated results and
experimental results efficiently, it is necessary to separate
the molecules. The molecular carbon number, the boiling
point, the carbon content, and the carbon residue value
were the main factors that were used to separate the
products. The molecules whose carbon numbers were <4
were defined as gas. In the remaining molecules, those
whose boiling points were <205 C were defined as
gasoline. In the rest of the molecules, those whose boiling
points were <365 C and had carbon numbers of <24 were
defined as diesel. Of the remaining molecules, those whose
carbon content was >90 mass %, had boiling points that
Figure 4. Residual error distributions of extrapolated prediction.
Table 4. Rate Revision Index for Each Reaction Class
reaction class rate revision index,
carbon chain cracking 0.0632
side chain breaking 0.1364
dehydrogenation 0.0337
molecular cracking 0.1194
ring opening 0.0708
polycondensation 0.039 (1 + Ni + V)
DielsAlder 0.0244
desulfurization 0.0102
decarboxylation 0.0469
were >450 C, or had carbon residue values of >5% were
defined as coke. The rest of the molecules were defined as
wax oil.
5. MODEL PREDICTION RESULTS
5.1. Simulation of Feedstock. The composition and
proportion of two types of residue samples from Sinopec as
depicted in Figure 7.
After calculating the contents of the 7004 types of molecular
lumps in these two residues respectively, the bulk properties of
these two residues could be calculated. Calculation and experi-
mental bulk properties are shown in Tables 5 and 6.
Tables 5 and 6 show that the 7004 types of molecular
lumps mainly reflected the bulk properties of residue samples;
the calculated results were in good agreement with the experi-
mental results.
Figure 5. Delayed coking process simplified diagram.
Figure 6. Simulation diagram of the delayed coking SOL model.
Figure 7. Composition of residue samples.
Table 6. Calculation and Experimental Bulk Properties of
Residue Sample 2
index calc exp index calc exp
C (wt %) 87.09 86.23 Sa. 21.98 22.90
H (wt %) 10.94 11.54 Ar. 46.22 44.18
S (wt %) 0.61 0.47 fA 0.22 0.21
N (wt %) 0.34 0.42 H/C 1.51 1.61
O (wt %) 1.02 1.34 SG 909 962
V (g/g) 5.80 5.10 CCR 14.04 13.87
Ni (g/g) 76.30 79.60 MW 917 995
Table 5. Calculation and Experimental Bulk Properties of
Residue Sample 1
index calc exp index calc exp
C (wt %) 87.54 87.36 Sa. 10.80 10.57
H (wt %) 11.14 10.81 Ar. 50.34 50.52
S (wt %) 0.57 0.41 fA 0.28 0.29
N (wt %) 0.49 0.61 H/C 1.53 1.48
O (wt %) 0.26 0.81 SG 994 1004
V (g/g) 5.20 7.90 CCR 23.21 26.15
Ni (g/g) 6.10 9.10 MW 1109 1197
5.2. Simulation of Delayed Coking. Experiments and model
calculations of delayed coking for the two aforementioned residues
has been performed. The operating conditions of experiments and
model calculations are as given in Table 7.
Calculated and experimental results of the delayed coking
product distribution are shown in Table 8.
Figure 8 includes the calculated and experimental results of
delayed coking for the same residue under different operating
conditions.
Table 8 and Figure 8 show that the calculated results agreed
with the experimental results well. The proposed model had
good accuracy for product distribution prediction of the
delayed coking process.
6. CONCLUSION
Some changes of structure vectors were made and their
contents were calculated. A total of 7004 types of molecular
lumps were proposed. Based on this, a reaction kinetic model
to predict the product distribution of delayed coking process
was built using the structure oriented lumping (SOL) method.
The model used 92 types of reaction rules to describe the
reaction behaviors of delayed coking and estimated reaction
rate constants as equations of structure vectors. Different from
other SOL works, the proposed model could predict the
product distribution of delayed coking. From the comparison of
calculated results and experimental results of product
distribution, it could be proven that the proposed model had
good accuracy for product distribution prediction of delayed
coking process.
AUTHOR INFORMATION
Corresponding Author
*Fax: 0086-21-64252851. E-mail: sbx@ecust.edu.cn.
REFERENCES
(1) Quann, R. J.; Jaffe, S. B. Structure-Oriented Lumping: Describing
the Chemistry of Complex Hydrocarbon Mixtures. Ind. Eng. Chem. Res.
1992, 31, 24832497.
(2) Quann, R. J.; Jaffe, S. B. Building useful models of complex
reaction systems in petroleum refining. Chem. Eng. Sci. 1996, 51 (10),
16151635.
(3) Yang, B.; Zhou, X.; Chen, C.; et al. Molecule Simulation for the
Secondary Reactions of Fluid Catalytic Cracking Gasoline by the
Method of Structure Oriented Lumping Combined with Monte Carlo.
Ind. Eng. Chem. Res. 2008, 47, 46484657.
(4) Tian, L.; Wang, J.; Shen, B.; et al. Building a Kinetic Model for
Steam Cracking by the Method of Structure-Oriented Lumping.
Energy Fuels 2010, 24, 43804386.
(5) Jaffe, S. B. Extension of Structure Oriented Lumping to Vacuum
Residua. Ind. Eng. Chem. Res. 2005, 44, 9840.
(6) Quann, R. J. Modeling the Chemistry of Complex Petroleum
Mixtures. Environ. Health Perspect. 1998, 106 (Supplement 6), 1441
1448.
(7) Liang, C.; Shen, B. Delayed Coking; Sinopec Press: Beijing, 2007.
Table 7. Operating Conditions of Delayed Coking
a
sample temperature (C) pressure (MPa) recycle ratio feeding flow (g/min) steam flow (g/min) feeding time gas stripping time (min)
1 480 0.181 0.29 15.69 0.21 191 111
2 480 0.177 0.30 16.01 0.40 190 118
a
Note that the volume of the coking drum in the small test device is 4 L.
Table 8. Calculation and Experimental Results of Delayed Coking Product Distribution
Gaseous Composition (mass %) Solids Composition (mass %) Liquid Composition (mass %)
sample gas coke gasoline diesel wax oil total yield of liquids
1
exp 6.06 32.63 20.13 28.52 12.66 61.31
calc 6.16 32.99 20.00 28.61 12.24 60.85
2
exp 7.13 28.32 21.06 27.83 15.66 64.55
calc 7.31 27.68 19.77 28.02 17.22 65.01
Figure 8. Calculated and experimental results for different operating conditions: (a) different temperatures, (b) different pressures, and (c) different
recycle ratios.
(8) Belohlav, Z.; Zamostny, P.; Herink, T. The kinetic model of
thermal cracking for olefins production. Chem. Eng. Process. 2003, 42,
461473.
(9) Allara, D. L.; Shaw, R. A compilation of kinetic parameters for the
thermal degradation of n-alkane molecules. J. Phys. Chem. Ref. Data
1980, 9 (3), 523559.
(10) Hammet, L. P. The effect of structure upon the reactions of
organic compounds. J. Am. Chem. Soc. 1937, 59, 96103.
(11) Gould, E. S. Mechanism and Structure in Organic Chemistry;
Holt, Rinehart, and Winston: New York, 1960.

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