Journal Pre-proof

Process simulation and optimization of propane dehydrogenation

combined with selective hydrogen combustion

Rui Hu, Xin Li, Zhijun Sui, Guanghua Ye, Xinggui Zhou

PII: S0255-2701(19)30440-4
DOI: https://doi.org/10.1016/j.cep.2019.107608
Article Number: 107608
Reference: CEP 107608

To appear in: Chemical Engineering and Processing

Received Date: 14 April 2019

Revised Date: 17 June 2019
Accepted Date: 23 July 2019

Please cite this article as: Hu R, Li X, Sui Z, Ye G, Zhou X, Process simulation and
optimization of propane dehydrogenation combined with selective hydrogen combustion,
Chemical Engineering and Processing - Process Intensification (2019),
doi: https://doi.org/10.1016/j.cep.2019.107608

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 Process simulation and optimization of propane
dehydrogenation combined with selective
hydrogen combustion

Rui Hu, Xin Li, Zhijun Sui, Guanghua Ye*, Xinggui Zhou†

State Key Laboratory of Chemical Engineering, East China University of Science and

of
Technology, Shanghai 200237, China

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* Co-corresponding author. Email address: guanghuaye@ecust.edu.cn

*
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Co-corresponding author. Email address: xgzhou@ecust.edu.cn
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Graphical Abstract
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 of
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Highlights:

 A co-fed process of propane dehydrogenation is proposed.

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 The co-fed process shows a propylene yield 6.0-46.1% higher than that of Oleflex.

 The co-fed process saves 2.86-7.24×106 kJ for every ton of propylene.

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 The operation conditions of the co-fed process are optimized.

ABSTRACT

2
 A co-fed process combining propane dehydrogenation (PDH) with selective hydrogen

combustion (SHC) is proposed, simulated, and optimized. The co-fed process uses adiabatic

moving bed radial flow reactors as PDH reactors and adiabatic fixed bed reactors as SHC

reactors. This co-fed process is proven to be very advantageous over the Oleflex process in

some aspects, showing a propylene yield 6.0-46.1% higher and saving 2.86-7.24×106 kJ per

ton of propylene under different operating conditions. These advantages are attributed to the

utilization of SHC reactors: they consume some hydrogen in the process, which shifts the

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reaction equilibrium towards propylene; they also provide much heat to drive the highly

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endothermic PDH reaction. For the co-fed process, a feed temperature of 873 K, a total pressure

of 1 bar, and using four PDH reactors are preferable; the optimal oxygen input is significantly
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affected by feed temperature and number of PDH reactors. Besides, under these preferable
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conditions, a SHC catalyst should have a minimum hydrogen combustion selectivity of 60.4%

to reproduce and exceed the Oleflex efficiency. This work should provide useful guidelines for
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the development of co-fed processes for propane dehydrogenation.

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Keywords: propane dehydrogenation; selective hydrogen combustion; simulation;

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optimization; co-fed process; Oleflex process

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1. Introduction

Propylene is a key intermediate in the petrochemical industry, which is used for the

3
production of polypropylene, acrylonitrile, propylene oxide, and other propylene derivatives.

Propylene is produced as a byproduct in traditional processes, including steam cracking and

fluid catalytic cracking [1–4]. These traditional processes cannot meet the ever-growing

demand for propylene driven by economic growth. Thus, some on-purpose techniques, such as

propane dehydrogenation and methanol-to-olefins, have been developed to produce propylene.

Among them, propane dehydrogenation is very economically favorable due to the large price

difference between propane and propylene [5–8].

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At present, several propane dehydrogenation processes have been commercialized,

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including Oleflex, Catofin, and Steam Active Reforming (STAR) [8]. These commercial

processes have been widely used around the globe and produce millions tons of propylene
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every year. However, these processes still can be largely improved in some aspects. Propane
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dehydrogenation reaction is reversible and highly endothermic (ΔH298K = +124 kJ/mol). To

achieve a high propane conversion, a high reaction temperature (>973 K) [9] is required to
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overcome the thermodynamic limitation. Thus, a large quantity of heat needs to be input to the
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propane dehydrogenation reactor aiming to meet the high energy consumption by the

endothermic reaction and to maintain a high reaction temperature. Besides, as the propane
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dehydrogenation reaction proceeds, hydrogen accumulates in the reactor, which is adverse to

achieving a high propane conversion due to the thermodynamic limitation.

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To resolve the above problems, some approaches have been used in the commercial propane

dehydrogenation processes. For example, the Oleflex process places preheaters before propane

dehydrogenation reactors to supply heat for these reactors. In the Catofin process, some of the

heat is provided by preheating the feed and the rest is input by burning the coke during catalyst

4
regeneration. In the STAR process, most of the heat is supplied by the oven and the rest comes

from the combustion of hydrogen [1,10]. The above approaches employed in commercial

processes can resolve the problems of heat input and thermodynamic limitation, but it is at the

cost of large energy consumption and capital investment. Therefore, some new designs are

needed to improve propane dehydrogenation processes.

Combining propane dehydrogenation with hydrogen combustion could be a favorable design

in two aspects: (i) the reaction heat of hydrogen combustion can be used to drive the strongly

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endothermic propane dehydrogenation reaction; (ii) the depletion of hydrogen can shift the

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reaction equilibrium towards the product. Much effort has been devoted to developing some

approaches to combine propane dehydrogenation with hydrogen combustion. One approach is

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using catalytic membrane reactors, and both experiments and simulations have been carried
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out [9,11–15]. The commonly used membrane reactor consists of propane dehydrogenation

zone and hydrogen combustion zone, and the two zones are separated by hydrogen selective
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permeation membrane (e.g., Pd, Pd-Ag, and Pd-Ni) [16–18]. As the membrane reactor
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integrates the functions of dehydrogenation, hydrogen depletion, and heat supply, this approach

exhibits a great potential to improve propane dehydrogenation processes. However, due to the
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high cost of membrane, membrane reactors for propane dehydrogenation have not been applied

in the industry.
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Another approach is adopting redox reactors in which propane dehydrogenation and redox

catalysts are physically mixed [19–22]. The lattice oxygen [OL] in redox catalysts (e.g., Bi2O3,

In2O3, and Sb2O4) is the oxidizing agent that can selectively combust the hydrogen

dehydrogenated from propane. The major problem of applying redox reactors is the lack of

5
metal oxides with high stability. For instance, the activity of Bi2O3 can be greatly reduced after

only 10 redox cycles, as the catalyst is exposed to the strong reduction atmosphere and some

active sites are deactivated due to their irreversible restructuring [19].

A third approach is employing a co-fed process mode, in which PDH, SHC and PDH reactors

are connected in series [23,24]. Specifically, the product in a PDH reactor and oxygen are co-

fed into a SHC reactor, in which hydrogen is selectively combusted. To achieve a high propane

conversion, more than one SHC reactor is required. Compared to the above two approaches,

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this approach does not need to change the commercial PDH reactors and therefore is very

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promising to be applied in the industry. UOP’s SMART technology has applied this process

principle for many years at the commercial level for dehydrogenation of ethylbenzene to
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styrene [8]. Besides, with the great progress in the catalysts for selective hydrogen combustion,
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the co-fed process is increasingly feasible [20,22,25,26]. For example, Shan et al. [27] designed

a Pt@KA catalyst with Pt clusters encapsulated in the Linde type A zeolite, and this catalyst
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exhibits an excellent hydrogen combustion selectivity of 98.5% as well as high activity and
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stability. However, the co-fed process receives much less attention than it deserves, and the

simulation and optimization of this process have not been reported to the best of our knowledge.
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In this work, we simulate and optimize a co-fed process with propane dehydrogenation

combined with selective hydrogen combustion. In this co-fed process, the moving bed radial
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flow reactor is used as the PDH reactor and the fixed bed reactor is taken as the SHC reactor.

The effects of operating conditions (i.e., feed temperature, total pressure, and feed composition)

on the performance of co-fed process are investigated, and this co-fed process is also compared

with the Oleflex process under these operating conditions. Besides, the oxygen input in the co-

6
fed process is optimized by using a genetic algorithm, under different feed temperatures and

numbers of PDH reactors. Eventually, the effect of hydrogen combustion selectivity on the

performance of co-fed process is probed.

2. Modelling

2.1. Co-fed process and reaction systems

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The co-fed process is illustrated in Fig. 1. PDH-R-01, PDH-R-02, PDH-R-03, and PDH-R-

04 are propane dehydrogenation reactors, which are adiabatic moving bed radial flow reactors;

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SHC-R-01, SHC-R-02, and SHC-R-03 are selective hydrogen combustion reactors, which are
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adiabatic fixed bed reactors. The gas mixture of propane and hydrogen is fed into PDH-R-01

where heat is consumed during the propane dehydrogenation reaction. The outlet gas mixture
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of PDH-R-01 and oxygen are co-fed into SHC-R-01 where hydrogen is partially combusted
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and the gas mixture is heated up, and then the gas mixture is fed into PDH-R-02. Several stages

of selective hydrogen combustion are required to achieve a high propane conversion, and
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oxygen is equally input in each SHC stage. It should be noted that the catalyst regeneration

process is not considered, as this process has been extensively investigated [4,16,28] and the
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co-fed process is the focus of this work. Besides, the Oleflex process is also displayed in Fig.
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1. The co-fed process is similar to the Oleflex process except replacing heaters with SHC

reactors, and the co-fed process applies the same PDH reactors as the Oleflex process.

Fig. 1 should be placed here.

There are two reaction systems in the co-fed process: propane dehydrogenation and selective
7
hydrogen combustion reactions. The propane dehydrogenation reaction (Eq. (1)) is assumed to

be catalyzed by Pt-Sn-K/Al2O3 catalyst, and the side reactions, including propane cracking (Eq.

(2)) and ethylene hydrogenation (Eq. (3)), occur simultaneously.

C3H 8  C3H 6  H 2  r H 298 K  1 2 4 k J / m o l (1)

C3H 8  C H 4  C 2H 4  r H 298 K  8 1 k J / m o l (2)

C2H 4  H 2  C2H 6  r H 298 K   1 3 7 k J / m o l (3)

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The reaction rates for propane dehydrogenation (r1), propane cracking (r2), and ethylene

hydrogenation (r3) are taken from the literature [29]:

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 PC H PH 
k 1  PC H  3 6 2

 3 8 K eq 
 -p 
 r1  (4),
PC H
1 3 6

KC H
3 6
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 r2  k 2 PC (5),
3H 8

 r3  k 3 PC PH (6),
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2H 4 2

where k1, k2, and k3 are the reaction rate constants of the three reactions; PC 3H 8
, PC 3H 6
, PH ,
2
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and PC 2 H 4
are the partial pressures of propane, propylene, hydrogen, and ethylene; Keq and

KC
3H 6
are the equilibrium constant and adsorption constant of propylene. It should be noted
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that ethylene hydrogenation is far away from equilibrium as the concentration of hydrogen is

much higher than that of ethane in this reaction system [30]. Thus, the kinetic of ethylene
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hydrogenation can be well approximated by Eq. (6), as reported in the literature [9,12,29]. The

kinetics parameters in Eqs. (4)-(6) are obtained from elsewhere.[29]

The hydrogen combustion reaction (Eq. (7)) can be catalyzed by metal catalysts, e.g., Pt

and Rh. The metal particles can be encapsulated into zeolites to achieve a very high selectivity

8
of hydrogen combustion (>98.5%) [27].However, the kinetics of such SHC catalysts has not

been reported in the literature. The selectivity of hydrogen combustion is assumed to be 100%

in Sections 3.1 and 3.2, and the kinetics of Rh/Al2O3 catalyzed hydrogen combustion is used.

1
H2  O 2  H 2O ( g ) rH 298 K
 243 kJ / m ol (7)
2

The reaction rate of hydrogen combustion ( rH ) is obtained elsewhere [31]:

2

 r H  k o x PH  O (8),
2 2 2

of
PO
 O2
 6
2
(9),
10  PO
2

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where kox is the reaction rate constant of hydrogen combustion that is obtained from the same

literature [31], and PO is the partial pressure of oxygen.

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2.2. PDH reactor model

A one-dimensional homogeneous reactor model is employed to describe the gas flow and
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reaction processes in the PDH reactor. Some assumptions are made to simplify this reactor
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model: back-mixing is negligible, distribution of catalyst activity is uniform, pressure drop is

negligible, and ideal gas approximation is satisfied.

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The mass balance equation of the PDH reactor is described by [32]:

d ni
  B ri
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(10),
dVR

where ni is the molar flow rate of component i, VR is the catalyst bed volume of PDH reactor,

ρB is the bed density of the PDH reactor, ri is the net reaction rate of component i. For a

cylindrical moving bed reactor, Eq. (10) can be changed into:

9
 d ni 2 rL
  B ri (11),
dr nt

where r is the radial position of the PDH reactor, and L is the length of the PDH reactor. Taking

C3H6, CH4, and C2H6 as key components, their mass balance equations are:

d yC
3H 6
2 rL  B
 [ (1  y C ) r1  y C r2  ( 2  y C ) r3 ] (12),
3H 6 3H 6 3H 6
dr nt

dyCH 2 rL  B
4
 [  y C H r1  (1  y C H ) r2  y C H r3 ] (13),
4 4 4
dr nt

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dyC H 2 rL  B
 [ yC r1  y C r2  (1  y C (14).
2 6

H H
) r3 ]
2 6 2 6 2H 6
dr nt

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The detailed derivation of Eqs. (12)-(14) is given in Section S1 in the Supplementary

Information. The mass balance equations for C3H8, H2, and C2H4 are obtained according to the

stoichiometric relation:
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( yC  yC  yCH ) n t , in
3H 8 , in 3H 6 , in , in
  yC  yCH (15),
4
yC
3H 8 3H 6 4
nt
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( yH , in
 yC  yC ) n t , in
3H 6 , in H 6 , in
yH   yC  yC (16),
2 2

2 3H 6 2 H 6
nt

 yCH  yC
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( yC H , in , in
) n t , in
2H 6 , in
  yCH  yC (17).
2 4 4
yC
2H 4 4 2H 6
nt

Here, yi,in is the molar fraction of component i in the reactor inlet, and nt,in is the total molar
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flow rate in the inlet. O2 and H2O are regarded as the inert components in the PDH reactor, and
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their mass balance equations are:

yO , in
n t , in
yO  2
(18),
2
nt

yH O , in
n t , in
yH  2
(19).
2O
nt

The total molar flow rate (nt) in the PDH reactor is calculated by:
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 yC  yH  2 yC  yC  yO  yH
nt 
3H 8 ,in 2 ,in 3H 6 ,in 2 H 4 ,in 2 ,in 2O ,in
n t ,in (20).
1  yC  yCH  yC
3H 6 4 2 H 6

The energy balance equation of the PDH reactor is:

dT 2 r L  B
 [(  r H 1 r1 )  (  r H 2 r2 )  (  r H 3 r3 )] (21).
dr n t C p , m ix

Here, T is the temperature, Cp,mix is the specific heat capacity of the gas mixture, and ∆rH1, ΔrH2,

and ΔrH3 are the reaction enthalpies of propane dehydrogenation (Eq. (1)), propane cracking

(Eq. (2)), and ethylene hydrogenation (Eq. (3)). The specific heat capacity of the gas mixture

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is calculated by:

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C p , m ix  C p ,i
yi (22),
i

where Cp,i is the molar heat capacity of component i and it is a function of temperature [33].

∆rH1, ΔrH2, and ΔrH3 in Eq. (22) are temperature-dependent and can be calculated by the
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Kirchhoff’s law [35]:

T  Tr
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rH j
 rH j ,298 K
  T  298 K
 i
C p ,i
dT (23),
i

where Tr is the reaction temperature and υi is the stoichiometric number of component i.

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For the first PDH reactor, the initial conditions for Eqs. (11) and (21) are:

y i  y i ,0 T  T0 (24),
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where yi,0 is the molar fraction of component i in the feed of the first PDH reactor, and T0 is the
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feed temperature. For other PDH reactors, the initial conditions for Eqs. (11) and (21) are:

y i  y i ,o T  To (25),

where yi,o is the molar fraction of component i in the outlet of the SHC reactor before the PDH

reactor, and To is the outlet temperature of this SHC reactor.

2.3. SHC reactor model

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 A one-dimensional homogenous reactor model is adopted to simulate the coupled gas flow

and reaction processes in the SHC reactor [35]. The model assumptions are the same as the

ones for the PDH reactor model. The mass balance equation for hydrogen is:

dyH Ab
2
  (1  0 .5 y H ) rH (26),
2 2
dl nt

where rH 2
is calculated by Eq. (8), A is the cross-sectional area of the SHC reactor, and ρb is

the bed density of the SHC reactor. The mass balances for O2 and H2O are acquired according

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to the stoichiometric relation:

yO , in
n t , in  0 .5 ( y H , in
n t , in  y H n t )

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yO  2 2 2
(27),
2
nt

yH n t , in  ( y H n t , in  y H n t )
yH
2O
 2O , in
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nt
2 , in 2
(28).

C3H8, C3H6, C2H6, C2H4, and CH4 are regarded as inert components in the SHC reactor, and
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their mass balance equations are:
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y i , in n t , in
yi  (29).
nt
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The total molar flow rate (nt) in the SHC reactor is calculated by:

yC  yCH  yC  yC  0 .5 y H  yH  yC
3H 8 , in , in H , in H , in , in 2O , in 3H 6 , in
nt 
4 2 6 2 4 2
n t , in (30).
1  0 .5 y H
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The energy balance equation is described by:

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dT Ab
 [   r H 4 rH ] (31),
2
dl n t C p , m ix

where Cp,mix is determined by Eq. (22), and ∆rH4 is the reaction enthalpy of hydrogen

combustion (Eq. (7)) that is calculated by Eq. (23). The initial conditions for Eqs. (26) and

(31) are:

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 yH n t ,o
yH 
2 ,o
(32),
2
n t ,o  n O ,o
2

n t ,o C To  nO C TO
T 
p ,o 2 ,o p ,O 2 2
(33).
( n t ,o  n O ,o
)C p , m ix
2

Here, yH
2 ,o
, nt,o, and Cp,o are the molar fraction of hydrogen, the total molar flow rate, and the

molar heat capacity of gas mixture in the outlet of the PDH reactor before the SHC reactor; To

is the outlet temperature of this PDH reactor; nO

2 ,o
is the molar flow rate of oxygen input into

the SHC reactor; TO

2
is the feed temperature of oxygen; Cp,mix is the molar heat capacity of

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the gas mixture in the inlet of the SHC reactor.

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2.4. Process simulation and optimization

To simulate the co-fed process, the PDH reactor model is connected with the SHC reactor
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model by setting their initial conditions. For example, the initial conditions for SHC-R-01 are

determined by the outlet conditions of PDH-R-01, and the initial conditions of PDH-R-02 are
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equal to the outlet conditions of SHC-R-01. The model equations are simultaneously solved by
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using the commercial software MATLAB R2014b, which yields the concentration and

temperature profiles. The simulation parameters are summarized in Table 1.

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After obtaining the concentration profiles, the propane conversion (X), propylene selectivity

(S), and propylene yield (Y) can be determined by:

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n t ,o u t y C
3H 8 ,o u t
X 1 (34),
n t ,0 y C
3 H 8 ,0

n t ,o u t y C
3H 6 ,out
S  (35),
1 - n t ,o u t y C
3 H 8 ,o u t

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 n t ,o u t y C
3H 6 ,o u t
Y  (36),
n t ,0 y C
3H 8 ,0

where nt,0 and nt,out are the total molar flow rates in the inlet and outlet of the process, yC
3H 8 ,0

is the molar fraction of propane in the inlet, and yC

3H 8 ,out
and yC
3H 6 ,out
are the molar fractions

of propane and propylene in the outlet.

Table 1 should be placed here.

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The oxygen input is the key factor that affects the performance of the co-fed process.

Thus, the feed molar fraction of oxygen ( x O ) of the process is optimized by using a genetic

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2

algorithm, which is implemented by using the function “ga” in MATLAB. The utilization of
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‘ga’ can guarantee global optimum of functions [36]. The objective function is the production

rate of propylene:
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P  Y  xC (37),
3H 8
lP

where Y is determined by Eq. (36) and xC

3H 8
is the feed molar fraction of propane of the co-

fed process. Since the propane dehydrogenation catalyst can be quickly deactivated at high
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temperature, the maximum operation temperature in the co-fed process should be lower than

973 K [1]:
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Tm ax  9 7 3 K (38)
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3. Results and discussion

3.1. Comparison of the co-fed and Oleflex processes

The co-fed and Oleflex processes are compared to show the advantages of the co-fed process.

14
Both co-fed and Oleflex processes contain four PDH reactors. To compare the two processes

on the same basis, they have the same molar flow rates of propane and hydrogen in the feed,

and the inlet temperatures of the PDH reactors in the Oleflex process are the same to the ones

in the co-fed process. The typical simulation results of the two processes are compared in Fig.

2. Besides, the two processes are compared under different feed temperatures, total pressures,

and feed compositions in Figs. 3-10.

3.1.1. Comparison in a Typical Case

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In Fig. 2, for the first PDH reactor, the propane conversion, propylene yield, temperature,

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and molar fraction of hydrogen of the co-fed process are identical to the ones of the Oleflex

process, because their reaction conditions are the same. In the subsequent PDH reactors, the
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propane conversion and propylene yield of the co-fed process become higher than these of the
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Oleflex process. The final propane conversion and propylene yield of the co-fed process are

8.0% and 10.4% higher than the ones of the Oleflex process. Besides, as more heat is consumed
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in the co-fed process due to its higher propane conversion, the temperature of the co-fed process
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is lower than the one of the Oleflex process and the largest temperature difference is 11 K.

In the co-fed process, hydrogen is partially combusted in the SHC reactors, and thus the
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molar fraction of hydrogen experiences sudden drops and keeps within a relative low value; in

the Oleflex process, the molar fraction of hydrogen increases with the progression of the
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dehydrogenation reaction (see Fig. 2d). Removing hydrogen can shift the reaction equilibrium

towards propylene, which explains the higher propane conversion and propylene yield of the

co-fed process. Moreover, as the co-fed process requires no heaters that are used in the Oleflex

processes, much energy is saved. In this typical case, the Oleflex process requires additional

15
3.14 109 kJ of energy per day, which is equivalent to 107 tons of standard coal per day [37].

It should be noted that the volume fraction of the combustible gas mixture (82.6-96.1%) in

the co-fed process is well above the upper explosive limit (62.7%) calculated by the Le

Chatelier’s rule [38], indicating no risk of explosion. Besides, there is also no danger of

explosion when changing the feed temperature (section 3.1.2), total pressure (section 3.1.3),

molar ratio of propane to oxygen (section 3.1.4), and molar fraction of feed hydrogen (section

3.1.5).

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Fig. 2 should be placed here.

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3.1.2. Comparison under different feed temperatures
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Fig. 3 compares the co-fed process with the Oleflex process when changing the feed
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temperature from 723 to 1173 K. The final propane conversion and propylene selectivity in the

co-fed process are higher than the ones in the Oleflex process, resulting in the final propylene
lP

yield in the co-fed process 8.2-15.2% higher. This is because hydrogen is partially combusted
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with the progression of the dehydrogenation reaction in the co-fed process (see Fig. 2d) and

the reaction equilibrium is shifted towards propylene. The similar comparison results on the
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propane conversion, propylene selectivity, and propylene yield can also be found when varying

the total pressure and changing the oxygen input in the co-fed process, and these results can be
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explained in the same way.

In the co-fed and Oleflex processes, the final propane conversion increases with the feed

temperature changing from 723 K to 1173 K, and the final propylene selectivity decreases with

the feed temperature because side reactions are favorable at high temperatures. Thus, there is

16
a maximum propylene yield for the two processes. For the co-fed process, the maximum

propylene yield is 60.0%, which corresponds to the feed temperature of 1073 K; for the Oleflex

process, the maximum propylene yield is 55.5%, which corresponds to the feed temperature of

1073 K. However, with the increase of the feed temperature, the maximum temperature in the

PDH reactors can exceed the upper temperature limit (i.e., 973 K), above which the PDH

catalyst can be quickly deactivated. Therefore, the preferable feed temperature of the co-fed

process is 873 K (see Fig. 3d), which is the trade-off between propylene yield and maximum

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temperature.

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Fig. 3 should be placed here.
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Fig. 4 shows the additional heat input into the Oleflex process at different feed temperatures.
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This heat input is not sensitive to the change of the feed temperature, keeping around 3.1×109

kJ per day. Since the inlet temperatures of the PDH reactors in the Oleflex process are equal to
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the ones in the co-fed process, this heat input is dependent on the reaction heat released by
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hydrogen combustion in the co-fed process. In the co-fed process, oxygen is completely

consumed and oxygen input is the same at different feed temperatures, which explains the result
ur

in Fig. 4. The similar results on the heat input are also found when varying the total pressure

(see Fig. 6), and these results can be explained in the same way.
Jo

Fig. 4 should be placed here.

3.1.3. Comparison under different pressures

Fig. 5 compares the co-fed and Oleflex processes in the total pressure range of 0.5-3 bar. The

17
final yield of the co-fed process is 6.0-46.1% higher than the one of the Oleflex process, which

further proves the advantages of the co-fed process. The final propane conversion and

propylene selectivity decrease with the total pressure, leading to the final propylene yield

decreasing from 51.5% to 32.5% for the co-fed process and from 48.6% to 22.2% for the

Oleflex process. At a high pressure, the reaction equilibrium is shifted towards propane and the

side reaction (i.e., ethylene hydrogenation) becomes favorable. Besides, the maximum

temperature in the PDH reactors is not sensitive to the change of total pressure (see Fig. 5d).

of
Considering the final propylene yield and the production capacity of the PDH reactors, it is

ro
preferable to operate the co-fed process at a moderate total pressure (~1 bar).

-p
Fig. 5 should be placed here.
re
Fig. 6 should be placed here.
lP

3.1.4 Comparison under different molar ratios of propane to oxygen

Fig. 7 compares the co-fed and Oleflex processes when varying the feed C3H8/O2 molar ratio
na

from 2:1 to 8:1. The final propylene yield of the co-fed process is 9.9-21.6% higher than the

one of the Oleflex process. The final propane conversion decreases with the feed C3H8/O2
ur

molar ratio, while the final propylene selectivity increases. When less oxygen is input into the
Jo

co-fed process, the reaction temperature is reduced, which leads to the reduced propane

conversion and increased propylene selectivity. There is a maximum propylene yield for the

co-fed (70.4%) and Oleflex (59.9%) processes, corresponding to the feed C3H8/O2 molar ratio

of 3:1. The maximum temperature decreases from 1286 to 947 K when changing the feed

C3H8/O2 molar ratio from 2:1 to 8:1, and this temperature is lower than the upper temperature
18
limit (i.e., 973 K) when the feed C3H8/O2 molar ratio is higher than 7:1. Considering final

propylene yield and maximum temperature, the preferable feed C3H8/O2 molar ratio is 7:1.

Fig.7 should be placed here.

Fig. 8 displays the additional heat input into the Oleflex process. The heat input decreases

significantly from 2.82×109 to 7.74×109 kJ per day, when changing the feed C3H8/O2 molar

ratio from 2:1 to 8:1. The inlet temperatures of the PDH reactors in the Oleflex process are the

of
same to the ones in the co-fed process. When more oxygen is input into the co-fed process and

ro
more hydrogen is combusted, the inlet temperatures of the PDH reactors in the Oleflex process

increase, and thus more heat is required to heat up the reaction mixture.
-p
Fig. 8 should be placed here.
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3.1.5 Comparison under different molar fractions of hydrogen
lP

Fig. 9 compares the co-fed and Oleflex processes when varying the feed H2 molar fraction
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from 0 to 50%. The final propylene yield of the co-fed process is 5.3-11.2% higher than the

one of the Oleflex process. The final propane conversion and propylene selectivity for both
ur

processes decrease with the increase of the feed hydrogen fraction, resulting in the decreased

final propylene yield. The presence of hydrogen suppresses propane dehydrogenation and
Jo

promotes ethylene hydrogenation. However, adding a proper amount of hydrogen in the feed

can effectively suppress catalyst deactivation by coking [1]. Thus, the preferable hydrogen

fraction is the trade-off between propylene yield and catalyst stability.

Fig. 9 should be placed here.

19
 Fig. 10 displays the additional heat input into the Oleflex process. The heat input decreases

significantly from 3.99×109 to 2.05×109 kJ per day, when changing the feed H2 molar fraction

from 0 to 50%. The oxygen fraction in the co-fed process decreases with the increase of

hydrogen fraction, and thus the heat release by hydrogen combustion is reduced. This explains

the significant decrease of heat input in the Oleflex process, as the heat release by hydrogen

combustion in the co-fed process directly relates to the heat input in the Oleflex process.

of
Fig. 10 should be placed here.

ro
3.2. Optimization of the co-fed process

The performance of the co-fed process can be significantly affected by the number of PDH
-p
reactors and the oxygen input, which are optimized in this section. With different numbers of
re
PDH reactors in the co-fed process, the PDH reactors have the same length and the total length

of these PDH reactors (20 m) keeps constant. The total length of the SHC reactors (4.5 m) also
lP

keeps unchanged, and they have the same length. Besides, oxygen is equally input into each
na

SHC reactor.

3.2.1. Optimization of number of PDH reactors

ur

Fig. 11 shows the changes in final propane conversion, propylene selectivity and propylene

yield with the number of PDH reactors changing from 2 to 10. The final propane conversion
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only slightly decreases with the number of PDH reactors. Besides, the final propylene

selectivity increases largely with the number of PDH reactors changing from 2 to 4, and then

increases very slowly. Thus, the final propylene yield only slightly increases with the number

of PDH reactors when it is larger than 4. Fig. 11d shows the maximum temperature in the co-

20
fed process. This maximum temperature decreases with the number of PDH reactors. With

more PDH reactors in the co-fed process, the oxygen input in each SHC reactor is reduced and

thus the inlet temperature of the PDH reactor is reduced, which explains the increased

propylene selectivity and the decreased maximum temperature. Considering final propylene

yield, maximum temperature, and capital investment, using four PDH reactors in the co-fed

process is preferable in this case. It should be noted that there is no danger of explosion

according to the explosive limit calculated by the Le Chatelier’s rule [38], when varying the

of
number of PDH reactors. Besides, there is also no risk of explosion when using the optimal

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oxygen input in section 3.2.2.

-p
Fig. 11 should be placed here.
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3.2.2. Optimization of oxygen input

The oxygen input is optimized by using the genetic algorithm under different feed
lP

temperatures and numbers of PDH reactors, as seen in Tables 2 and 3. The molar fraction of
na

hydrogen is fixed at 20% and the maximum temperature in the co-fed process is limited below

973 K. Table 2 shows that the optimal molar ratio of propane to oxygen increases from
ur

0.681:0.119 to 0.709:0.091 with the feed temperature increasing from 723 to 973 K, the optimal

propane conversion increases from 48.8% to 60.1%, the optimal propylene selectivity
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decreases from 92.5% to 87.7%, and the optimal propylene yield increases slightly from 45.2%

to 52.7%. When the feed temperature is high, less heat is required from combusting hydrogen

in the co-fed process, which explains the increased optimal molar ratio of propane to oxygen.

Table 3 shows that the optimal ratio of propane to oxygen decreases from 0.747:0.053 to

21
0.656:0.144 with the number of PDH reactors increasing from 2 to 10, the optimal propane

conversion increases from 30.0% to 73.0%, the optimal propylene selectivity increases slightly

from 89.4% to 90.8%, and the optimal propylene yield increases from 26.8% to 66.3%. With

more PDH reactors in the co-fed process, more oxygen can be input into the process under the

constraint of upper temperature limit, and a higher propylene yield can be achieved. However,

the capital investment increases largely with the number of PDH reactors. Therefore, both

propylene yield and capital investment should be taken into consideration when choosing the

of
number of PDH reactors.

ro
Table 2 should be placed here.
-p
Table 3 should be placed here.
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3.3. Effect of hydrogen combustion selectivity
lP

In Sections 3.1 and 3.2, we assume the hydrogen combustion selectivity of SHC catalyst is

100%. One may develop this SHC catalyst with a hydrogen combustion selectivity close to
na

100% in the future. But, at present, SHC catalysts cannot achieve such high hydrogen

combustion selectivity, and some hydrocarbons are inevitably combusted. Thus, it becomes
ur

very meaningful to investigate how hydrogen combustion selectivity affects the performance
Jo

of co-fed process.

In our reaction system, propane and propylene are the dominant hydrocarbons, and propylene

is much more reactive to oxygen [39, 40]. Thus, besides hydrogen combustion reaction, only

propylene combustion reaction is accounted for:

22
 2 2 2
C3H 6
 O2  CO2+ H 2O  rH 298 K
 428 kJ / m ol (39).
9 3 3

The kinetic of propylene combustion can be described by [41]:

rC O  k p PC
p n
2 3H 6
PO
2
(40),

where kp is the reaction rate constant; p and n are reaction orders. The hydrogen combustion

selectivity SHC can be calculated by:

n t ,o u t y C O
S HC  1  2 ,o u t
(41),
n t ,0 y O ,0
- n t ,o u t y O ,o u t
2 2

of
where yO
2 ,0
is the molar fraction of oxygen in the inlet, and yCO
2 ,o u t
is the molar fraction of

carbon dioxide in the outlet. To achieve different hydrogen combustion selectivities, the kinetic

ro
parameters in Eq. (40) are adjusted, and these kinetics parameters are displayed in Table S1 in

the Supplementary Information. Besides, the mass balance and heat balance equations for the
-p
co-fed process are displayed in Section S2 in the Supplementary Information.
re
Fig. 12 compares the co-fed and Oleflex processes under different hydrogen combustion
lP

selectivities. In Fig. 12a, the final propane conversions of the two processes increase with the

hydrogen combustion selectivity changing from 30% to 100%. The heat released by hydrogen
na

combustion is higher than that by propylene combustion when consuming the same amount of

oxygen, and thus more heat is generated when the hydrogen combustion selectivity is higher.
ur

This explains the result in Fig. 12a. In Fig. 12b, the final propylene selectivity of the Oleflex
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process slightly decreases with the hydrogen combustion selectivity, while the one of the co-

fed process increases remarkably from 83.4% to 90.6% when increasing the hydrogen

combustion selectivity from 30% to 100%. At the hydrogen combustion selectivity of 87.4%,

the final propylene selectivity of the co-fed process equals to the one of the Oleflex process.

As more heat is generated with a higher hydrogen combustion selectivity, the maximum
23
temperature slightly increases (see Fig. 12d), resulting in the decreased final propylene

selectivity in the Oleflex process. Less propylene is combusted with a higher hydrogen

combustion selectivity, which explains the significantly increased final propylene selectivity in

the co-fed process. In Fig. 12c, the final propylene yield of the co-fed process is larger than the

one of the Oleflex process when the hydrogen combustion selectivity is larger than 60.4%,

indicating the SHC catalyst must have the minimum hydrogen combustion selectivity of 60.4%

to reproduce and exceed the Oleflex efficiency.

of
Fig. 12 should be placed here.

ro
Fig. 13 displays the additional heat input into the Oleflex process. The heat input increases
-p
from 2.65×109 to 3.19×109 kJ per day, when increasing the hydrogen combustion selectivity
re
from 30% to 100%. As more heat is generated in the co-fed process when the hydrogen

combustion selectivity is higher, which explains the increased heat input in the Oleflex process.
lP

Fig. 13 should be placed here.

na
ur
Jo

24
4. Conclusions

In this work, a co-fed process combing propane dehydrogenation with selective hydrogen

combustion is proposed. In this co-fed process, adiabatic moving bed radial flow reactors are

taken as the PDH reactors, and adiabatic fixed bed reactors are used as the SHC reactors that

combust the hydrogen generated in the PDH reactors and supply heat for the PDH reactors.

This co-fed process is compared with the Oleflex process under different feed temperatures,

total pressures, and feed compositions. The effect of the number of PDH reactors on the

of
performance of co-fed process is investigated. Besides, the oxygen input of this co-fed process

ro
is optimized by using the genetic algorithm. Eventually, the effect of SHC catalyst selectivity

on the performance of co-fed process is investigated. -p

The proposed co-fed process is advantageous in boosting propylene yield and saving much
re
energy. Under different operation conditions and with four PDH reactors in the processes, the
lP

co-fed process has a propylene yield 6.0-46.1% higher than the one of the Oleflex process and

also saves 2.86-7.24×106 kJ per ton of propylene. Considering propylene yield, maximum
na

temperature, and capital investment, a feed temperature of 873 K, a total pressure of 1 bar, and

using four PDH reactors are preferable. The optimization of oxygen input shows that the
ur

optimal molar ratio of propane to oxygen increases with the feed temperature and decreases
Jo

with the number of PDH reactors. The optimized propylene yield can be as high as 66.3% at

the expense of requiring 10 PDH reactors and 9 SHC reactors. Besides, under the preferable

conditions, a SHC catalyst must have a minimum hydrogen combustion selectivity of 60.4%

to reproduce and exceed the Oleflex efficiency. The simulation and optimization results in this

work should serve to design co-fed processes for industrial use.

25
Acknowledgements
This work was supported by the China Postdoctoral Science Foundation (2018T110358), the

“Chenguang Program” supported by Shanghai Education Development Foundation and

Shanghai Municipal Education Commission (17CG29), the Fundamental Research Funds for

the Central Universities (222201714004 and 222201718003), and the National Basic Research

Program of China (2012CB720501).

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31
List of Table Captions
Table 1. Simulation parameters in this work.

Table 2. Optimized molar ratios of propane to oxygen under different feed temperatures, and

the corresponding optimal propane conversions, propylene selectivities, and propylene yields.

The fixed parameters: nt,0 = 850 mol/s and Pt,0 = 1 bar. The other fixed parameters are given in

Table 1. There are four PDH reactors in the co-fed process.

Table 3. Optimized molar ratios of propane to oxygen under different numbers of PDH reactors,

of
and the corresponding optimal propane conversions, propylene selectivities, and propylene

ro
yields. The fixed parameters: nt,0 = 850 mol/s, Pt,0 = 1 bar, and T0 = 873 K. The other fixed

parameters are given in Table 1.

-p
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lP
na
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Jo

32
Table 1. Simulation parameters in this work.

Parameter Value

Length of the PDH reactor ( L p ) 5m

Length of the SHC reactor ( L s ) 1.5 m

Inner radius of the catalyst bed in the PDH reactor ( R i ) 1.0 m

Outer radius of the catalyst bed in the PDH reactor ( R e ) 2.0 m

Inner radius of the SHC reactor ( R s ) 0.15 m

of
Bed density of the PDH reactor (  B ) 1000 kg/m3

Bed density of the SHC reactor (  b ) 1000 kg/m3

ro
Inlet temperature of the co-fed process ( T 0 ) 723-1173 K

Inlet total pressure of the co-fed process ( Pt , 0 )

-p 0.5-3 bar
re
Feed molar fraction of H2 of the co-fed process ( x H ) 2
20%

Feed ratio of C3H8 molar fraction to O2 molar fraction ( x C 3H 8

: xO
2
) 2:1-8:1
lP
na
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Jo

33
Table 2. Optimized molar ratios of propane to oxygen under different feed temperatures, and

the corresponding optimal propane conversions, propylene selectivities, and propylene yields.

The fixed parameters: nt,0 = 850 mol/s and Pt,0 = 1 bar. The other fixed parameters are given in

Table 1. There are four PDH reactors in the co-fed process.

xC : xO
3H 8
Feed temperature 2

Conversion Selectivity Yield

(K) ( xH 2
= 0.200)

723 0.681:0.119 0.488 0.925 0.452

773 0.686:0.114 0.508 0.919 0.467

of
823 0.692:0.108 0.529 0.912 0.483
873 0.697:0.103 0.553 0.903 0.500

ro
923 0.703:0.097 0.575 0.893 0.513
973 0.709:0.091 0.601 0.877 0.527

-p
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lP
na
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Jo

34
Table 3. Optimized molar ratios of propane to oxygen under different numbers of PDH reactors,

and the corresponding optimal propane conversions, propylene selectivities, and propylene

yields. The fixed parameters: nt,0 = 850 mol/s, Pt,0 = 1 bar, and T0 = 873 K. The other fixed

parameters are given in Table 1.

xC : xO
3H 8
Number of PDH 2

Conversion Selectivity Yield

reactors ( xH 2
= 0.200)

2 0.747:0.053 0.300 0.894 0.268

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3 0.722:0.078 0.432 0.904 0.390
4 0.697:0.103 0.553 0.903 0.500

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5 0.683:0.117 0.616 0.905 0.558
6 0.674:0.126 0.660 0.906 0.598
7 0.667:0.133 0.690 0.907 0.625
8
9
10
0.662:0.138
0.659:0.141
0.656:0.144
0.708
0.721
0.730
-p 0.907
0.908
0.908
0.642
0.654
0.663
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lP
na
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Jo

35
List of Figure Captions
Fig. 1. Schematic diagrams of the co-fed process that combines propane dehydrogenation with

selective hydrogen combustion and the Oleflex process. Four PDH reactors are used in each

process.

Fig. 2. Comparison of the co-fed and Oleflex processes in a typical case. (a) Propane

conversion, (b) propylene yield, (c) temperature, and (d) molar fraction of hydrogen in the PDH

reactors. The simulation parameters for the co-fed process: xC

3H 8
: x H : xO
2 2
=

of
0.700:0.200:0.100, nt,0 = 850 mol/s, Pt,0 = 1 bar, and T0 = 873 K. The simulation parameters for

ro
the Oleflex process: xC
3H 8
: xH
2
= 0.778:0.222, nt,0 = 765 mol/s, Pt,0 = 1 bar, and T0 = 873 K.

The other parameters are given in Table 1.

-p
Fig. 3. Comparison of the co-fed and Oleflex processes under different feed temperatures. (a)
re
Final propane conversion, (b) final propylene selectivity, (c) final propylene yield, and (d)

maximum temperature. The simulation parameters for the co-fed process: xC : x H : xO =

lP

3H 8 2 2

0.700:0.200:0.100, nt,0 = 850 mol/s, and Pt,0 = 1 bar. The simulation parameters for the Oleflex
na

process: xC
3H 8
: xH
2
= 0.778:0.222, nt,0 = 765 mol/s, and Pt,0 = 1 bar. The other parameters are

given in Table 1.
ur

Fig. 4. Additional heat input into the Oleflex process under different feed temperatures. The

simulation parameters: xC : xH = 0.778:0.222, nt,0 = 765 mol/s, and Pt,0 = 1 bar. The other
Jo

3H 8 2

parameters are given in Table 1.

Fig. 5. Comparison of the co-fed and Oleflex processes under different total pressures. (a) Final

propane conversion, (b) final propylene selectivity, (c) final propylene yield, and (d) maximum

temperature. The simulation parameters for the co-fed process: xC

3H 8
: x H : xO
2 2
=

36
0.700:0.200:0.100, nt,0 = 850 mol/s, and T0 = 873 K. The simulation parameters for the Oleflex

process: xC
3H 8
: xH
2
= 0.778:0.222, nt,0 = 765 mol/s, and T0 = 873 K. The other parameters are

given in Table 1.

Fig. 6. Additional heat input into the Oleflex process under different total pressures. The

simulation parameters: xC
3H 8
: xH
2
= 0.778:0.222, nt,0 = 765 mol/s, and T0 = 873 K. The other

parameters are given in Table 1.

Fig. 7. Comparison of the co-fed and Oleflex processes under different feed molar ratios of

of
propane to oxygen. (a) Final propane conversion, (b) final propylene selectivity, (c) final

ro
propylene yield, and (d) maximum temperature. The simulation parameters for the co-fed

process: nt,0 = 850 mol/s, Pt,0 = 1 bar, and T0 = 873 K. The simulation parameters for the Oleflex
-p
process: nt,0 = 765 mol/s, Pt,0 =1 bar, and T0 = 873 K. The other parameters are given in Table
re
1.

Fig. 8. Additional heat input into the Oleflex process under different feed molar ratios of
lP

propane to oxygen. The simulation parameters: nt,0 = 765 mol/s, Pt,0 =1 bar, and T0 = 873 K.
na

The other parameters are given in Table 1.

Fig. 9. Comparison of the co-fed and Oleflex processes under different feed molar fraction of
ur

hydrogen. (a) Final propane conversion, (b) final propylene selectivity, (c) final propylene yield,

and (d) maximum temperature. The simulation parameters for the co-fed process: nt,0 = 850
Jo

mol/s, Pt,0 = 1 bar, xC

3H 8
: xO
2
= 7:1 and T0 = 873 K. The simulation parameters for the Oleflex

process: Pt,0 =1 bar, and T0 = 873 K. The other parameters are given in Table 1.

37
Fig. 10. Additional heat input into the Oleflex process under different feed molar fraction of

hydrogen. The simulation parameters: Pt,0 =1 bar, and T0 = 873 K. The other parameters are

given in Table 1.

Fig. 11. Effects of the number of PDH reactors in the co-fed process. (a) Final propane

conversion, (b) final propylene selectivity, (c) final propylene yield, and (d) maximum

temperature. The simulation parameters: xC

3H 8
: x H : xO
2 2
= 0.700:0.200:0.100, nt,0 = 850 mol/s,

Pt,0 = 1 bar, and T0 = 873 K. The other parameters are given in Table 1.

of
Fig. 12. Comparison of the co-fed and Oleflex processes under different final hydrogen

ro
combustion selectivities (a) Final propane conversion, (b) final propylene selectivity, (c) final

propylene yield, and (d) maximum temperature. The simulation parameters for the co-fed

process: xC
3H 8
: x H : xO
2 2
-p
= 0.700:0.200:0.100, nt,0 = 850 mol/s, Pt,0 = 1 bar, and T0 = 873 K.
re
The simulation parameters for the Oleflex process: xC
3H 8
: xH
2
= 0.778:0.222, nt,0 = 765 mol/s,

Pt,0 =1 bar, and T0 = 873 K. The other parameters are given in Table 1.
lP

Fig. 13. Additional heat input into the Oleflex process under different final hydrogen
na

combustion selectivities. The simulation parameters: xC

3H 8
: xH
2
= 0.778:0.222, nt,0 = 765

mol/s, Pt,0 =1 bar, and T0 = 873 K. The other parameters are given in Table 1.
ur
Jo

38
 of
ro
-p
re
Fig. 1. Schematic diagrams of the co-fed process that combines propane dehydrogenation with

selective hydrogen combustion and the Oleflex process. Four PDH reactors are used in each
lP

process.
na
ur
Jo

39
 of
ro
-p
re
Fig. 2. Comparison of the co-fed and Oleflex processes in a typical case. (a) Propane
lP

conversion, (b) propylene yield, (c) temperature, and (d) molar fraction of hydrogen in the PDH
na

reactors. The simulation parameters for the co-fed process: xC

3H 8
: x H : xO
2 2
=

0.700:0.200:0.100, nt,0 = 850 mol/s, Pt,0 = 1 bar, and T0 = 873 K. The simulation parameters for
ur

the Oleflex process: xC

3H 8
: xH
2
= 0.778:0.222, nt,0 = 765 mol/s, Pt,0 = 1 bar, and T0 = 873 K.

The other parameters are given in Table 1.

Jo

40
 of
ro
-p
re
Fig. 3. Comparison of the co-fed and Oleflex processes under different feed temperatures. (a)
lP

Final propane conversion, (b) final propylene selectivity, (c) final propylene yield, and (d)
na

maximum temperature. The simulation parameters for the co-fed process: xC

3H 8
: x H : xO
2 2
=

0.700:0.200:0.100, nt,0 = 850 mol/s, and Pt,0 = 1 bar. The simulation parameters for the Oleflex
ur

process: xC
3H 8
: xH
2
= 0.778:0.222, nt,0 = 765 mol/s, and Pt,0 = 1 bar. The other parameters are

given in Table 1.
Jo

41
 of
ro
Fig. 4. Additional heat input into the Oleflex process under different feed temperatures. The

simulation parameters: xC
3H 8
: xH
2
-p
= 0.778:0.222, nt,0 = 765 mol/s, and Pt,0 = 1 bar. The other
re
parameters are given in Table 1.
lP
na
ur
Jo

42
 of
ro
-p
re
lP

Fig. 5. Comparison of the co-fed and Oleflex processes under different total pressures. (a) Final

propane conversion, (b) final propylene selectivity, (c) final propylene yield, and (d) maximum
na

temperature. The simulation parameters for the co-fed process: xC

3H 8
: x H : xO
2 2
=

0.700:0.200:0.100, nt,0 = 850 mol/s, and T0 = 873 K. The simulation parameters for the Oleflex
ur

process: xC
3H 8
: xH
2
= 0.778:0.222, nt,0 = 765 mol/s, and T0 = 873 K. The other parameters are
Jo

given in Table 1.

43
 of
ro
Fig. 6. Additional heat input into the Oleflex process under different total pressures. The

simulation parameters: xC
3H 8
: xH
2
-p
= 0.778:0.222, nt,0 = 765 mol/s, and T0 = 873 K. The other

parameters are given in Table 1.

re
lP
na
ur
Jo

44
 of
ro
-p
re
lP

Fig. 7. Comparison of the co-fed and Oleflex processes under different feed molar ratios of

propane to oxygen. (a) Final propane conversion, (b) final propylene selectivity, (c) final
na

propylene yield, and (d) maximum temperature. The simulation parameters for the co-fed

process: nt,0 = 850 mol/s, Pt,0 = 1 bar, and T0 = 873 K. The simulation parameters for the Oleflex
ur

process: nt,0 = 765 mol/s, Pt,0 =1 bar, and T0 = 873 K. The other parameters are given in Table
Jo

1.

45
 of
ro
Fig. 8. Additional heat input into the Oleflex process under different feed molar ratios of
-p
propane to oxygen. The simulation parameters: nt,0 = 765 mol/s, Pt,0 =1 bar, and T0 = 873 K.
re
The other parameters are given in Table 1.
lP
na
ur
Jo

46
 of
ro
-p
re
lP

Fig. 9. Comparison of the co-fed and Oleflex processes under different feed molar fractions of
na

hydrogen. (a) Final propane conversion, (b) final propylene selectivity, (c) final propylene yield,

and (d) maximum temperature. The simulation parameters for the co-fed process: nt,0 = 850
ur

mol/s, Pt,0 = 1 bar, xC

3H 8
: xO
2
= 7:1 and T0 = 873 K. The simulation parameters for the Oleflex

process: Pt,0 =1 bar, and T0 = 873 K. The other parameters are given in Table 1.
Jo

47
 of
ro
Fig. 10. Additional heat input into the Oleflex process under different feed molar fractions of
-p
hydrogen. The simulation parameters: Pt,0 =1 bar, and T0 = 873 K. The other parameters are
re
given in Table 1.
lP
na
ur
Jo

48
 of
ro
-p
re
lP

Fig. 11. Effects of the number of PDH reactors in the co-fed process. (a) Final propane

conversion, (b) final propylene selectivity, (c) final propylene yield, and (d) maximum
na

temperature. The simulation parameters: xC

3H 8
: x H : xO
2 2
= 0.700:0.200:0.100, nt,0 = 850 mol/s,

Pt,0 = 1 bar, and T0 = 873 K. The other parameters are given in Table 1.
ur
Jo

49
 of
ro
-p
re
lP

Fig. 12. Comparison of the co-fed and Oleflex processes under different final hydrogen

combustion selectivities (a) Final propane conversion, (b) final propylene selectivity, (c) final
na

propylene yield, and (d) maximum temperature. The simulation parameters for the co-fed

process: xC
3H 8
: x H : xO = 0.700:0.200:0.100, nt,0 = 850 mol/s, Pt,0 = 1 bar, and T0 = 873 K.
ur

2 2

The simulation parameters for the Oleflex process: xC

3H 8
: xH
2
= 0.778:0.222, nt,0 = 765 mol/s,
Jo

Pt,0 =1 bar, and T0 = 873 K. The other parameters are given in Table 1.

50
 of
ro
Fig. 13. Additional heat input into the Oleflex process under different final hydrogen

combustion selectivities. The simulation parameters:

-p xC
3H 8
: xH
2
= 0.778:0.222, nt,0 = 765
re
mol/s, Pt,0 =1 bar, and T0 = 873 K. The other parameters are given in Table 1.
lP
na
ur
Jo

51