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naphtha reforming process in the presence of the catalyst

deactivation

D. Iranshahi, E. Pourazadi, K. Paymooni, A.M. Bahmanpour, M.R. Rahimpour*, A. Shariati

Department of Chemical Engineering, School of Chemical and Petroleum Engineering, Shiraz University, Shiraz 71345, Iran

article info

abstract

Article history:

Improving the octane number of the aromatics compounds has always been an important

matter in refineries and lots of investigations have been made concerning this issue. In this

15 July 2010

reforming process in the presence of catalyst deactivation. Model equations are solved by

the orthogonal collocation method. The AF-SPBR results are compared with the plant data

of a conventional tubular packed-bed reactor (TR). The effects of some important param-

Keywords:

eters such as pressure and temperature on aromatic and hydrogen production rates and

Axial-flow

catalyst activity have been investigated. Higher production rates of aromatics can

successfully be achieved in this novel reactor. Moreover, results show the capability of flow

augmentation in the proposed configuration in comparison with the TR. This study shows

Dynamic modeling

Hydrogen production

2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.

Aromatic production

1.

Introduction

a boiling temperature between 30 C and 200 C, and constitutes typically 15e30% by weight of the crude oil. The catalytic

naphtha reforming reactions are carried out over commercial

Pt/Re/Al2O3 catalyst (0.3% Platinum, 0.3% Rhenium). Naphtha

and reformate are complex mixtures of paraffins, naphthenes, and aromatics in the C5eC12 range [1,2]. Naphtha

reforming plays a major role in improving the aromatic and

hydrogen production in petroleum refineries [3,4]. In order to

have an improved process its better to revamp naphtha

reforming strategies due to its impact on overall refinery

profits [5].

2.

Literature review

various hydrocarbons and related isomers. It is too complex to

consider a detailed kinetic model taking into account all

components and reactions [6]. Studies on the catalytic

naphtha reforming process have been categorized in two basic

groups. The first group involves studies on the kinetics of

catalytic naphtha reforming process. Various attempts have

been made to find better lumped groups of reactions to

represent the catalytic reforming reactions. In this regard,

the first significant attempt to model a reforming system has

been made by Smith [7]. He considered naphtha to consist of

three basic components including paraffins, naphthenes, and

E-mail address: rahimpor@shirazu.ac.ir (M.R. Rahimpour).

0360-3199/$ e see front matter 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.

doi:10.1016/j.ijhydene.2010.08.124

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 5 ( 2 0 1 0 ) 1 2 7 8 4 e1 2 7 9 9

extensive attempts have been made to model reforming

reactions. Juarez and Macias [3] developed a new kinetic

model in which the most important reactions in terms of

isomers of the same nature (paraffins, naphthenes and

aromatics) were taken into account. The average deviation of

the new kinetic model from experimental data was reported

to be less than 3%. Weifeng et al. [8] developed a new kinetic

model including 20 lumped components and 31 reactions.

Boyas and Froment [9] studied a fundamental chemistry of

naphtha. The current model imposed the equilibriums of

hydrogenation and dehydrogenations. Stijepovic et al. [10]

recommended a semi-empirical kinetic model for catalytic

reforming. Their lumping strategy was based on paraffins,

olefins, naphthenes and aromatics (PONA) analyses. Similar

studies in this field were carried out by Ramange et al. [11,12],

Krane et al. [13], Kmak [14] and Marin et al. [15]. The second

group involves studies on the modeling and improvement of

aromatics and hydrogen yields of the conventional reactors. Li

et al. [16] modeled and optimized a semi-regenerative catalytic naphtha reformer by considering most of its key constitutes. Taskar and Riggs [17] done a similar study as Li et al. But

they have used a reaction network composed of 35 reactions

for 35 pseudo components. Juarez et al. [18] modeled and

simulated four serially catalytic reactors for naphtha reforming. Weifeng et al. [6] considered 18-lumped kinetic models to

simulate and optimize a whole industrial catalytic naphtha

reforming process by Aspen Plus platform. Stijepovic et al. [19]

introduced a new simulation and optimization approach for

CRs. They applied a new proposed objective function in which

economical and environmental performance was taken into

consideration. Khosravanipour and Rahimpour [4] presented

a membrane catalytic bed concept for naphtha reforming in

the presence of catalyst deactivation. Weifeng et al. [20]

examined a multi objective optimization strategy for a CR

process in order to obtain aromatic products. Rahimpour [21]

proposed a novel fluidized-bed membrane reactor (FBMR) for

naphtha reforming in the presence of catalyst deactivation.

He shows that the FBMR increases catalyst activity, aromatic

and hydrogen production rates.

In order to enhance the octane number of aromatic

compounds, the reaction conditions have to be improved.

Aromatics are enhanced by shifting the reactions (using

a hydrogen permeselective membrane) or decreasing the

pressure drop. In industrial plants, the pressure drop is

a serious problem in unit operations such as reactors. The

configurations which have much lower pressure drop than the

conventional fixed-bed reactors are radial flow spherical

packed-bed reactors (RF-SPBR) and radial flow tubular packedbed reactors (RF-TPBR). A complete literature review on the

RF-SPBR and RF-TPBR has been prepared by Iranshahi et al.

[22] have recently modeled the RF-SPBR for naphtha reforming

process in the presence of catalyst deactivation. They have

shown that in addition to pressure drop reduction through the

catalytic bed, the amount of aromatic production increases.

The AF-SPBR is an alternative configuration for pressure drop

reduction in high pressure processes such as naphtha

reforming. This novel configuration is not as well known as

the previous ones and little studies have been done on it.

Fogler has modeled the dehydrogenation of paraffins turning

12785

spherical reactor decreases significantly [23]. Zardi et al. have

modeled the ammonia synthesis in an axial-radial reactor [24].

Moreover, Brumbaugh has patented a modified novel axialflow spherical reactor for naphtha reforming process [25].

The main goal of this work is to investigate the production

yield of aromatics in the AF-SPBR. A comparison between the

AF-SPBR and the TR are carried out in this study. The dynamic

modeling of this novel reactor is done by considering the

catalyst deactivation.

The AF-SPBR configuration is superior to the previous ones

(AF-TPBR and RF-SPBR) briefly as follows:

The AF-SPBR in comparison with the AF-TPBR:

Lower pressure drop is encountered in this configuration.

Lower required material thickness (Material thickness for

a spherical and a tubular pipe of the same radius, subjected to

action of an internal pressure, P, are tsph P$r=2s and

ttub P$r=s respectively. Where t is the wall thickness, s is the

tensile stress and r is the radius of the tube and the sphere [26]).

Consequently the required surface has been decreased

which reduces effectively the costs of investment and

maintenance during the operation (this is a wise decision to

use membranes with lower costs of maintenance).

Smaller catalytic pellets with higher effectiveness factor can

be applied owing to the reduction of pressure drop in this

configuration.

Higher molar flow rate can be applied (due to lower pressure

drop) which increases the production rate.

Lower power supply of recompression is needed.

The AF-SPBR in comparison with the RF-SPBR:

The feed distribution has been improved (Utilizing the radial

flow pattern to distribute the feed stream is not easily

applicable).

Modifications have been done on the reactor structure to

provide an effective contact between the reactant gas and

the catalytic bed when the quantity of the applied catalyst is

only a fraction of the designed quantity of catalyst [25].

Membrane technologies can be easily introduced in the AFSPBR while it is hard to apply the membrane concept in

radial flow spherical packed-bed reactor (RF-SPBR).

A homogeneous one-dimensional model has been

considered. The basic structure of the model consists of heat

and mass balance equations. These equations must be

coupled with the deactivation model, and also thermodynamic and kinetic equations, as well as auxiliary correlations

for predicting physical properties.

The effect of various parameters such as reactor length,

time, variable physical properties, and operating conditions

on the performance of the reactor has been investigated.

3.

Smith [7]. He assumed some pseudo components in order to

12786

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 5 ( 2 0 1 0 ) 1 2 7 8 4 e1 2 7 9 9

dominant idealized reactions can be used to simplify the

catalytic reforming system. The following four reactions are

considered in the model:

(1)

(2)

(3)

(4)

Dehydrocyclization of paraffins to naphthenes.

Hydrocracking of naphthenes to lower hydrocarbons.

Hydrocracking of paraffins to lower hydrocarbons.

OF

(1)

(2)

(3)

(4)

order to achieve higher aromatics production, the naphtha

reforming process should be carried out at higher temperatures.

The rate equations of these reactions are as follows:

kf 1

ke1 pn pa p3h

Ke1

(5)

kf 2

ke2 pn ph pp

Ke2

(6)

r2

(

m

X

3

2 X

2

NA cal NA plant

TOut cal TOut plant

i1

r1

and the observed values of outlet temperature and aromatic

yield of bed simultaneously. A constrained optimization

procedure is used to find the activation energies. The activation energies are adjustable parameters. The objective function to be optimized is:

r3

kf 3

pn

pt

(7)

r4

kf 4

pp

pt

(8)

equilibrium constant, respectively. Rase [27] reported the

following equations for these constants.

E1

kf 1 9:87exp 23:21

1:8T

(9)

E2

kf 2 9:87exp 35:98

1:8T

(10)

E3

kf 3 kf 4 exp 42:97

1:8T

(11)

46; 045

Ke1 1:04 103 exp 46:15

1:8T

(12)

8000

Ke2 9:87exp 7:12

1:8T

(13)

where E is the activation energy of each reaction. The activation energies depend on the catalyst which is used.

According to the previous works, the activation energy is

)

(14)

i1

temperature of each bed and m is the number if data sets are

used, so the results are:

E1 36,350

E2 58,550

E3 63,800

4.

Process description

4.1.

Conventional configuration

petroleum refineries and the petrochemical industry to

convert paraffins and naphthenes into aromatics. A simplified

flow diagram of continuous catalytic reforming process is

shown in Fig. 1. The fresh naphtha feedstock (middle distillate

of atmospheric distillation column) is combined with a recycled gas stream containing 60e90% (by mole) hydrogen.

Hydrogen can adjust the H2/HC molar ratio through the

reactors to prevent coking and also it sweeps the products

through the catalyst pores. The total reactor charges are

heated and passed through the catalytic reformers which are

designed with three adiabatically operating reactors and three

heat exchangers between the reactors to maintain the reaction temperatures at designed levels. The effluent from the

3rd reactor is cooled, and then it enters the separators. Off

gases and reformates are separated from the top and the

bottom of the separator [28]. Table 1 shows the specific

properties and operating conditions of the conventional

naphtha reactors. Boiling point ranges are determined by

Distillation Petro Test D86.

4.2.

industry [29], due to some disadvantages of this type of reactors the spherical packed-bed reactors attract more attentions. Some potential disadvantages of tubular reactors are

the pressure drop along the reactor, high manufacturing costs

and low production capacity. In order to avoid serious pressure drop in the TR, the effective diameters of the catalyst

particles are usually considered more than 3 mm which lead

to a certain inner mass transfer resistance. In this study, the

AF-SPBR is proposed for naphtha reforming process.

Fig. 2(a) shows the schematic diagram of the spherical

configuration setup. In the AF-SPBR, catalysts are situated

12787

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 5 ( 2 0 1 0 ) 1 2 7 8 4 e1 2 7 9 9

Off Gas

R: Reactor

EX: Heat

Exchanger

S-1: Separator

S-2: Stabilizer

R-1

R-3

R-2

S-2

EX-1

S-1

Reformate to Storage

Naphtha Feed

EX-2

EX-3

Compressor

Fig. 1 e A simple process flow diagram for conventional catalytic naphtha reforming (TR).

naphtha feed enters the top of the reactor and flows steadily

to the bottom of the reactor. Attempts should be made to

have a continuous flow without any channeling in the

reactor. The goal is to achieve a uniform flow distribution

through the catalytic bed, because the flow is mainly occurring in an axial direction. The two screens in upper and lower

parts of the reactor hold the catalyst and act as a mechanical

support. Since the cross-sectional area is smaller near the

inlet and the outlet of the reactor, the presence of catalysts in

these parts would cause substantial pressure drop and

The other advantage of these screens is to balance the free

zones (free catalyst zones) to find a desirable pressure drop

during the process. The radial flow is assumed to be negligible in comparison with the axial flow. As a result, the

equations in the axial coordinate are being taken into

account exclusively.

5.

Reactor modeling

5.1.

Axial- flow spherical packed-bed reactor model (AFSPBR model)

catalyst of plant for fresh catalyst.

Parameter

Naphtha feed stock

Reformate

H2/HC mole ratio

LHSV

Mole percent of hydrogen in recycle

Diameter and length of 1st reactor

Diameter and length of 2nd reactor

Diameter and length of 3rd reactor

Numerical

Value

30.41 103

24.66 103

4.73

1.25

69.5

1.25, 6.29

1.67, 7.13

1.98, 7.89

Unit

Kg/h

Kg/h

e

h1

e

m

m

m

TBP

Naphtha feed

( C)

IBP

106

10%

113

30%

119

50%

125

70%

133

90%

144

FBP

173

Reformate

( C)

44

73

105

123

136

153

181

dp

Pt

Re

sa

rB

3

mm

wt%

wt%

m2/g

Kg/l

e

1.2

0.3

0.3

220

0.3

0.36

spherical packed-bed reactors [30]. In this study, a homogeneous one-dimensional model has been considered. The flow

pattern in the AF-SPBR is assumed to be axial. The basic

structure of the model consists of heat and mass balance

equations. These equations must be coupled with the deactivation model, and also thermodynamic and kinetic relations

as well as auxiliary correlations for predicting physical properties. In order to solve the equations, an element with the

length dz (as shown in Fig. 3) has been considered and the

material and energy balances are written upon this element.

The mass and energy balance equations for fluid phase can be

formulated as follows:

Dej

m

X

vCj

vCj

1 v

1 v

nij ri 3

Ac

Ac uz Cj rB a

vz

vt

Ac vz

Ac vz

i1

j 1; 2; .; n

m

X

1 v

vT

1 v

DHi ri

Ac

rAc uz cp T Tref rB a

Ac vz

vz

Ac vz

i1

v rcps T Tref

3

vt

15

keff

(16)

number and j represents the component number, Dej is the

effective diffusivity of component j, C is the gas phase

concentration, rB is the catalyst bulk density, vij is the

12788

R: Reactor

EX: Heat Exchanger

S-1: Separator

S-2: Stabilizer

Off Gas

R-3

S-2

R-2

R-1

EX-1

S-1

EX-2

Compressor

EX-3

Reformate to Storage

Hydrogen Rich Gas

Naphtha Feed

Naphtha Feed

Screen z=0

F1

L1

Z

dz

z+dz

L2

F1

Screen z=L1+L 2

Product

Fig. 2 e (a) Spherical axial-flow configuration for catalytic naphtha reforming and (b) conceptual Flow pattern and

specifications for spherical reactor in the catalytic naphtha reforming process.

the reaction rate, keff is the thermal conductivity of the gas

phase, T is the temperature, r is the density of gas phase, CP is

the heat capacity of the gas phase, 3 is the void fraction and DH

is the heat of the reaction.

Its worth mentioning that the cross-section area, Ac, in the

AF-SPBR is a function of reactor length. Therefore it must

remain between the parentheses of the derivative equation of

mass and energy balances. The formulation of cross-section

area, Ac, is described as follows [23]:

i

h

Ac p R2 z L1 2

The boundary and initial conditions are as follows:

(17)

z 0; Cj Cjo ; T To

(18)

vCj

vT

0;

0

vz

vz

(19)

ss

ss

t 0; Cj Css

j ; T T ; Ts Ts ; a 1;

(20)

z L1 L2 :

of the reactor to the top and bottom screens in the axial

coordinate. The superscript ss represents the steady state

condition. The steady state mass and energy balance equations are the same when the accumulation term is set to zero.

Mass and heat transfer coefficients are estimated by several

Fz

6.

da

Ed 1

1

a7

Kd exp

R T TR

dt

Fz+dz

Fig. 3 e Schematic for differential element along the flow

direction.

auxiliary correlations. These auxiliary correlations are presented in Appendix B. The heat of reactions is reported as

follows (kJ/kmol of H2):

71; 038:06

36; 953:33

51; 939:31

56; 597:54

5.2.

general fluid-phase balance is a model with the balances

typically accounting for accumulation, convection, and reaction. The energy and mass balances for the gas phase can be

written as Eqs. (21) and (22):

Dej

m

X

v2 Cj v uCj

vCj

rB a

nij ri 3

vz

vz2

vt

i1

j 1; 2; .; n

i 1; 2; .; m

keff

21

m

X

v2 T v

v

DHi ri 3

rucp T Tref rB a

rcp T Tref

2

vz

vz

vt

i1

(22)

The boundary and initial conditions are as follows:

z 0 : Cj Cj0 ; T T0

(23)

vCj

vT

0;

0

vz

vz

(24)

ss

t 0 : Cj Css

j ; T T ; a 1

(25)

ZL:

5.3.

based on the Ergun equation. This equation covers the entire

range of flow rates by assuming that the viscous losses and

the kinetic energy losses are additive [23]. This equation for

Cartesian systems is derived as below:

2

work which was presented by Rahimpour [31].

dz

DH1

DH2

DH3

DH4

12789

dP 150m 1 3 Q 1:75r 1 3 Q

33

Ac

33

dz f2s d2p

Ac

fs dp

(27)

where TR, Ed and Kd are the reference temperature, the activation energy and the deactivation constant of the catalyst,

respectively. The numerical values of TR, Ed and Kd, are 770 K,

1.642 105 J mol1 and 5.926 105 h1, respectively.

7.

Numerical solution

In order to solve the set of coupled partial differentialalgebraic equations a two steps procedure is used. Firstly,

the steady state simulation is carried out to obtain the

initial conditions of the dynamic simulation. In the steady

state simulation all the time variations are considered to be

zero and activity will be considered to be one. Secondly,

the results of the steady state simulation are used as the

initial conditions for the time-integration of the dynamic

state equations in each node through the reactor. The

deactivation model and the conservation rules are ordinary

and partial differential equations, respectively. Moreover,

there would be algebraic equations due to the auxiliary

correlations, kinetics and thermodynamics of the reaction

system. These equations constitute a set of dynamic

equations.

The set of aforementioned equations of the model of

spherical and tubular reactors are solved by means of the

orthogonal collocation method [32,33]. Inner collocation

points are chosen as a root of a Jacobi polynomial. The

orthogonal collocation method is discussed further in

Appendix A. The system of PDEs is transformed into an

ordinary differential equation (ODE) system by means of this

numerical method. An energy balance is developed for each

collocation point, as well as a mass balance for each species.

The energy and mass balance equations of the spherical

reactor are systems of ODEs with initial conditions. The

system of ODEs is integrated by a modified Rosenbrock

formula of order two. It is noted that this method is well

suited for the systems of stiff equations [34]. In addition,

Gears method can be used for solving the set of such stiff

ODEs.

8.

Model validation

8.1.

Model validation with the presence of catalyst

deactivation

(26)

dp is the particle diameter, fs is the sphericity (for spherical

particles fs equals one), m is the fluid viscosity and r is the fluid

density.

[28] with the proposed configuration over 800 operating days.

The predicted results of the production rate, the corresponding observed data and the residual error are presented in

Table 2. Good agreements between the daily observed plant

12790

Time (day)

Plant (kmol/h)

AF-TPBR (kmol/h)

AF-SPBR (kmol/h)

30.41

30.41

31.00

30.78

31.22

31.22

28.55

30.33

31.22

30.67

30.76

42.35

42.32

42.32

42.32

42.32

42.54

42.54

37.86

38.51

225.90

224.25

229.65

229.65

229.65

229.65

211.60

222.75

233.05

228.65

227.64

317.30

317.94

317.94

317.94

313.09

317.94

313.90

286.15

282.10

221.5802

222.5122

227.9313

226.7749

230.7985

231.2730

209.8377

224.7291

232.1821

228.1752

229.0932

324.5555

324.4826

324.6987

324.8622

325.0433

327.0586

327.2581

289.3742

294.9026

221.4080

222.3432

227.7559

226.6038

230.6220

231.0971

209.6965

224.5558

232.0072

228.0081

228.9246

324.2907

324.2216

324.4426

324.6099

324.7952

326.8164

327.0210

289.1475

294.6767

1.91

0.77

0.75

1.25

0.50

0.71

0.83

0.88

0.37

0.21

0.64

2.28

2.05

2.12

2.17

3.81

2.86

4.25

1.12

4.53

0

34

62

97

125

160

188

223

243

298

321

398

425

461

490

524

567

610

717

771

satisfy successfully the industrial conditions. The related

deviations from the plant reported values are due to the fact

that the kinetics and models used for reaction system of

naphtha reforming underestimated the true reaction rate.

Also using the average molecular weights and such other

physical properties for the three groups of pseudo components (PNA), heat transfer coefficients maybe increase the

uncertainties.

8.2.

demonstrated at the steady state condition in Table 3. As seen,

there is a good agreement between the plant data and predicted mole fractions of components at the output of the

system. Analyses of components (paraffin, naphthene and

aromatic) are performed by PONA Test in Stan Hop Seta

apparatus. The aromatic is tested especially by ASTM 2159

equivalent to UOP 273 method [28].

9.

number of interior collocation points has been evaluated.

According to Fig. 4, the aromatic molar flow rate is plotted

versus the mass of catalysts with different number of interior

collocation points. In Fig. 4(a) one, two and three and in Fig. 4

(b) one, five, and seven interior collocation points have been

used. As it is shown in Fig. 4(a), when the number of interior

collocation points is not enough, the diversity appears

between the curves. But by increasing the number of interior

collocation points as shown in Fig. 4(b), the discrepancy

disappears between the curves. The curves with 5 and 7

interior points cover each other thoroughly. Therefore, the

N 5 is the most accurate choice.

Results of modeling involve the following main issues:

9.1 Changes of parameters along the spherical reactors.

9.2 Changes of parameters as a function of time.

Table 3 e Comparison between model prediction and plant data for fresh catalyst.

Reactor number

1

2

3

777

777

775

3703

3537

3401

20

30

50

Reactor number

1

2

3

Paraffin

Naphthene

Aromatic

49.3

36.0

14.7

Plant

NPBR

SPFR

Plant

NPBR

SPFR

722

753

770

727.38

751.03

770.54

727.45

751.66

770.75

e

e

57.7

34.78

47.28

56.26

34.77

47.12

56.18

12791

90

80

75

Paraffin

70

65

one interior collocation point

Ninterior=1

60

55

Ninterior=2

50

Ninterior=3

45

40

140

120

85

100

Aromatic

80

800th Day

1st Day

60

40

Naphthene

20

0.1

0.2

0.3

0.4

0.5

0.6

0.7

Mass of catalyst (Dimensionless)

0.8

0.9

1

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

0.8

0.9

0.8

0.9

90

85

1500

80

75

70

65

60

Ninterior=1

55

Ninterior=5

50

Ninterior=7

45

40

0.1

0.2

0.3

0.4

0.5

0.6

0.7

Mass of catalyst (Dimensionless)

0.8

0.9

1450

1st Day

1350

1300

1250

(a) with1, 2 and 3 and (b) and 1, 5 and 7 interior orthogonal

collocation points.

800th Day

1400

0.1

0.2

0.3

0.4

0.5

0.6

0.7

780

Temperature (K)

770

3750

L=0.10R

L=0.30R

3700

L=0.50R

3650

Pressure (kPa)

L=0.70R

760

750

TR

SR

740

3600

L=0.90R

3550

730

3500

720

3450

L=0.95R

3400

3350

3300

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

Fig. 5 e Pressure profile along the mass of catalyst (solid

line: tubular reactor, dotted line: spherical reactor).

0.1

0.2

0.3

0.4

0.5

0.6

0.7

TR

SR

of catalyst (solid line: the 1st day of production, dotted line:

the 800th day of production), (b) hydrogen molar flow rate

versus mass of catalyst (solid line: the 1st day of

production, dotted line: the 800th day of production) and (c)

the temperature profiles of TR and SR.

12792

0.95

1st reactor

4000

3500

2nd reactor

3rd reactor

Pressure (kPa)

Catalyst activity

0.9

0.85

3000

2500

0.8

2000

0.75

1500

0.7

100

200

300

400

500

Time (Day)

600

700

1000

0.1

800

operation for the 1st, the 2nd and the 3rd reactors.

FR=1.0

FR=2.0

FR=2.5

FR=3.0

0.2

0.3

0.4

0.5

L/R

0.6

0.7

0.8

0.9

0.6

0.7

0.8

0.9

0.6

0.7

0.8

0.9

0.36

0.35

the yield and quality of reformate are time, feedstock properties, reaction temperature, space velocity, reaction pressure,

and hydrogen per hydrocarbon ratio [35].

FR=1.0

FR=2.0

FR=2.5

FR=3.0

0.34

Aromatic yield

tubular and spherical reactors in this regard.

0.33

0.32

0.31

0.3

0.29

0.1

0.2

0.3

0.4

0.5

L/R

0.88

0.87

0.86

Hydrogen yield

0.85

0.84

0.83

FR=1.0

FR=2.0

FR=2.5

FR=3.0

0.82

0.81

0.8

0.79

0.78

0.1

0.2

0.3

0.4

0.5

L/R

versus L/R, (b) the aromatic yield versus L/R and (c) the

hydrogen yield versus L/R.

9.1.

Fig. 8 e (a) Aromatic and paraffin and (b) light end and

hydrogen mole productions during 800 days of operation.

reactors in the 1st and the 800th days of operation will be

investigated in the first section.

12793

1505

0.36

0.35

P=2703 kPa

0.34

Aromatic yield

0.33

0.32

0.31

0.3

TR

SR

0.29

0.28

P=3070 kPa

1495

TR

SR

1490

0.55

0.6

0.65

0.7

0.75

0.8

0.85

0.9

0.95

1480

2000

2200

2400

2600

(B)

2800

3000

3200

3400

3600

3800

4000

(A)

1485

P=1703 kPa

0.27

0.26

0.5

1500

for spherical and tubular reactor.

0.37

0.36

0.35

Aromatic yield

0.34

P=3703 kPa

a 4000

0.33

3500

0.32

3000

0.3

P=4703 kPa

TR

SR

0.29

0.5

0.55

0.6

0.65

0.7

0.75

0.8

0.85

0.9

0.95

Pressure (kPa)

0.31

2500

SR

TR

2000

1500

1000

reactor (a) for operating pressures 1703 and 2703 kPa and

(b) for operating pressures 3703 and 4703.

500

0

0.4

0.38

0.36

SR

TR

0.34

Aromatic yield

dimensionless mass of catalysts of three reactors for various

L/Rs. it can be seen, by increasing L/Rs the pressure drop

increases. Thus, for L/R 0.95 the greatest pressure drop is

achieved. At higher L/Rs, a huge bulk of feed encounters less

empty zones at the inlet and the outlet of the reactor. As

a result, a sudden pressure drop happens in the pressure

profile. The steps indicate the pressure drop in each reactor.

The dimensionless mass of catalyst for the 1st, the 2nd and

the 3rd reactors is in the range of 0e0.2, 0.2e0.5 and 0.5e1,

respectively. The dimensionless mass of catalyst 0 shows

the inlet of the 1st spherical reactor and the dimensionless

mass of catalyst 1 implies the outlet of the 3rd reactor. On

the other hand, if L/R decreases to lower than 0.7, the pressure

drop would decrease too. However, working with the L/R 0.5

is useless because most of the reactor space is empty without

any catalyst. Thus, the L/R 0.7 is chosen not only to reduce

the useless fabrication of materials for free zone but also to

have a little pressure drop. The reason which makes this ratio

a proper choice will be discussed later.

In previous works, the total molar flow rate was assumed

to be constant while it increases throughout the reactor in

0.32

0.3

0.28

0.26

0.24

0.22

0.2

and (b) aromatic yield versus feed flow rate scale up ratio at

3703 kPa for tubular and spherical reactors(solid line:

tubular reactor, dotted line: spherical reactor).

12794

b

4000

0.45

3500

0.4

Aromatic yield

Pressure (kPa)

3000

2500

2000

0.35

0.3

0.25

1500

15

0.2

15

6

10

10

2

0

4

3

2

1

c

0.9

Hydrogen yield

0.8

0.7

0.6

0.5

0.4

15

6

10

5

4

0

2

1

Fig. 13 e 3-D figure which shows the effect of flow scale up ratio and catalyst scale up ratio on (a) pressure and (b) aromatic

yield.

plants. In this study, the total molar flow and also all physical

properties such as heat capacity and thermal conductivity are

assumed to be variable along the reactors.

A scheme of components molar flow rates versus the

mass of catalyst along the reactor for the 1st and the 800th

days of operation is depicted in Fig. 6(a). As seen, the aim of

naphtha reforming is satisfied, because the molar flow rate

of aromatics increases along the reactor and fortunately

the molar flow rates of naphtha and paraffin decrease.

Each break point in this figure indicates the inlet temperature of the following reactor. Because the temperature

increases by using pre heaters at the inlet of each reactor,

the reaction rates change and discontinuities appear in the

figure.

Also, Fig. 6(b) illustrates hydrogen molar flow rate versus

the mass of catalyst along the reactor. Fig. 6(c) presents

the temperature distribution through the TR and SR. As the

naphtha reforming is predominantly endothermic, the

temperature decreases in the reactors.

9.2.

proceed, the catalyst activity decreases. The catalyst activity

has an inverse relationship with the temperature, in other

words, as the temperature decreases the catalyst activity

increases.

Fig. 8(a) illustrates the effect of catalyst deactivation on the

product and reactant production rates. By decreasing the

catalyst activity, the aromatic production rate decreases and

hence the amount of unreacted paraffin increases due to

lower reaction rate. As a result of catalyst deactivation, both

the reaction rate and the production rate decrease. The light

end (off gas) production rate as a function of time is depicted

in Fig. 8(b). As seen, this product also decreases in the course

of time due to the catalyst deactivation. An unpredictable

behavior is observed in Fig. 8(b) for hydrogen production. The

catalyst aging acts in a way that hydrogen produces more after

the 800th day of operation compared with the 1st day.

9.3.

Effect of operating conditions and a comparison

between tubular and spherical reactors in this regard

time will be discussed. Fig. 7 reveals the average catalyst

(FR), operating pressures and other parameters are studied in

the following section.

12795

versus L/R for different FRs is shown in Fig. 9(a). FR indicates

that the flow rate of fresh naphtha feed in spherical reactor is

more compared with the feed stream in TR. As seen,

increasing the FR increases the pressure drop and this will be

more significant for higher L/Rs. The slope of curves starts to

change at the L/R 0.7 and the variation of pressure drop

experiences a new trend in spherical reactors. At the L/R 0.7,

the pressure drop increases by increasing the FR. But, the

pressure drop augmentation at this ratio is approximately less

than higher values of L/Rs. Therefore, the L/R 0.7 is an

appropriate choice, due to observation of considerable pressure drop after this point. This is an evidence to show that the

L/R 0.7 is a proper choice. The aromatic yield versus L/R for

different FRs is illustrated in Fig. 9(b). According to the Le

Chateliers principle, for FRs equal to 1e2 the pressure drop at

L/R 0.7e0.9 shifts the reaction to the aromatics and

hydrogen production. The residence time decreases in higher

FRs owing to providing a larger quantity of reactants per unit

of catalyst. Consequently, it decreases the products yield (see

Fig. 9(b)e(c)). Higher pressure drop at FRs of 2.5e3 reduces the

reactants partial pressures and this affects the reaction rates.

It should be mentioned that all the previous results in this part

have been achieved at the constant inlet compressor pressure

of 3703 kPa.

reactor (SR) and tubular reactor (TR) based on the dimensionless mass of catalyst for various operation pressures. As

seen from Fig. 10(a), when the operating pressure equals

1703 kPa, the aromatic yield in the SR is considerably higher

than the TR. As the operating pressure increases, the difference between the aromatic yields in two reactor configurations decreases (see the graph for Pressure of 2703 kPa). The

intersection of tubular and spherical curves is named

the turning junction point. However, the arrangement of the

curves will change at the turning junction point and the

aromatic yield in TR becomes more than the one in SR (see

Fig. 10(b)). In other words, the TR unlike the SR is incapable of

operating satisfactorily at low pressures. In spite of SR

advantages (lower pressure drop, lower construction material,

lower surface area and lower related maintenance costs), the

operating pressure should be wisely determined when

compared with the TR. The same trend is observed for

hydrogen production rate versus the operating pressure for SR

and TR configurations in Fig. 11.

9.3.3.

in comparison with the tubular ones is clearly represented by

Fig. 12(a). If the feed flow ratio in TR is doubled, the pressure

decreases drastically. On the other hand if the feed flow ratio

in spherical reactor equals to 7, the pressure declines.

Therefore, if the feed flow ratio in spherical reactor increases

more products would be achieved. The effect of flow rate

augmentation on quality is investigated by considering the

product yields. According to Fig. 12(b), the peak is observed for

low feed flow rate in both reactors. Due to low feed flow rate

0.45

CMR=1

CMR=2

CMR=3

CMR=4

0.4

Aromatic yield

9.3.2.

and high catalyst loading, the sufficient time exists for converting the feed to aromatics. Therefore the peak is seen in

low feed flow rates (less than 1). When the feed flow rate scale

up ratio equals to 1, the aromatic yield in the tubular reactor is

slightly higher than the yield in the spherical reactor. By

increasing the scale up ratio in two reactors the aromatic yield

decreases in both reactors but the slope is sharper in TR. The

pressure drop has a strongly negative effect on the aromatic

production in tubular reactors due to the FR. It should be

mentioned that Fig. 12(a, b) are depicted in the constant inlet

pressure of 3070 kPa for tubular and spherical reactors.

The simultaneous effect of catalyst and FRs on pressure,

aromatic and hydrogen yields is investigated in the following

3-D plots. The various catalyst distributions in SR in comparison with the TR are identified by catalyst scale up ratio.

Fig. 13(a) illustrates the simultaneous effect of catalyst and

FR on pressure. For all catalyst scale up ratios the pressure

decreases by increasing the FR. Especially for lower catalyst

scale up ratios, the pressure drop is higher due to lower

reactor diameter and high viscose loss in higher velocities.

When, the catalyst scale up ratio increases to 5, the flux

decreases due to the increase in the reactor diameter. Therefore the pressure becomes approximately constant. In low

0.35

0.338

0.3

0.25

0.2

1

0.9

0.876

0.8

Hydrogen yield

9.3.1.

0.7

0.6

0.5

CMR=1

CMR=2

CMR=3

CMR=4

0.4

0.3

0.2

Fig. 14 e The effect of CMR and the flow scale up ratio on (a)

aromatic yield and (b) hydrogen yield.

12796

increasing the FR. Fig. 13(b) illustrates the simultaneous effect

of catalyst and FRs on the aromatic yield. In each FR, if the

catalyst scale up ratio increases, the aromatic yield will

increase. In general, the catalyst scale up ratio causes higher

aromatic yield for each FR. However, increasing FR decreases

the aromatic yield in each catalyst scale up ratio. The simultaneous effect of catalyst and FR is considered on hydrogen

yield in Fig. 13(c).

The effect of FR on aromatic yield for different catalyst

mass ratios (CMRs) is depicted in Fig. 14(a) for SR. The

aromatic yield is considered to be 0.338 in industry and the

industry data for CMR 1 is depicted as solid line. If the FR

equals 2, in order to achieve the same (0.338) aromatic yield

the CMR should be a little less than 2 (1.9 times). Similarly, if

the FR equals 3, the CMR should be a little less than 3(2.85

times) in fixed aromatic yield. In high CMRs, as FR increases,

the difference between the fixed aromatic yield (0.338) and the

obtained aromatic yield increases. In general, in order to have

a specific flow (FR) a little less than the specified value is

needed for catalyst loading. The difference between these two

values is larger for higher FRs. The effect of FR on hydrogen

yield in different CMRs is depicted in Fig. 14(b). In CMR 1, as

0.9

0.85

Hydrogen yield

0.8

0.75

0.7

T1=777, T2=777

T1=777, T3=775

0.65

0.6

T2=777, T3=775

0.55

0.5

0.45

650

700

750

800

850

0.5

0.45

in the figure. Hydrogen yield becomes constant for the CMRs

higher than 3. If higher FRs is desired, the CMR should be more

than 3. In order to achieve the fixed hydrogen yield (0.87),

when the FR is less than 3, it is satisfactory to work with

minimum CMR which equals to 2.

9.3.4.

temperatures of two reactors out of three is considered to be

constant and the inlet temperature of the other reactor

changes to examine the effect of temperature. Fig.15(a, b)

illustrates the effect of temperature on hydrogen and

aromatic yield, respectively. As the temperature exceeds,

hydrogen is consumed and the yield decreases. The results

show that increasing the 1st reactor temperature (dotted lines

in Fig.15(a, (b)) is more efficient in order to hydrogen and

aromatic production.

10.

Conclusion

In any process, a significant incentive to minimize the pressure drop has led to developing a number of alternatives on

the flow configurations. According to this concept, one

potentially interesting idea for catalytic naphtha reforming

process is the application of AF-SPBR. The pressure drop

problem is successfully overcome in this new configuration. In

this study, the AF-SPBR is proposed for catalytic naphtha

reforming process. The effect of several parameters on

aromatic and hydrogen yields is investigated. Most of the

parameters of the system are considered to be variable such as

heat capacity, viscosity, molecular weight, pressure, density

and the total molar flow. Optimum pressure and L/R are

determined. The dynamic model is solved by the orthogonal

collocation method and the results are much better in

comparison with the other conventional methods such as

finite difference method. Results show that the AF-SPBR can

be properly applied instead of TR. This study shows that for

naphtha reforming process the AF-SPBR configuration is more

efficient than the previous ones. The practical operating

conditions data together with the mathematical model can be

used to develop the AF-SPBR model for new plant setups and

revamps of process in future.

Aromatic yield

0.4

0.35

Acknowledgement

0.3

T1=777, T2=777

T1=777, T3=775

0.25

The authors would like to thanks gratefully to Samira Hafeziyeh for her helpful recommendation to improve the English

language of the manuscript.

T2=777, T3=775

0.2

650

700

750

800

850

and (b) aromatic yields.

Jacobi polynomials

a;b

orthogonal with respect to the weighting function xb 1 xa .

follow:

N

X

a;b

JN x

1Ni gN;i xi

(A e1)

i0

The evaluation of coefficients is done by using the

following recurrence formula

gN; i

Ni1 Niab

$

gN; i1

i

ib

T

y y1 ; y2 ; y3 ; .; yN ; yN1

y0 A$y

y00 B$y

characterizing the polynomials.

For a given set of data points (x1, y1), (x2, y2),.,(xN, yN) and

(xN1, yN1) an interpolation formula passing through all

(N 1) points is an Nth degree polynomial. A suitable interpolation polynomial for the orthogonal collocation method is

Lagrange interpolation polynomial, which passes through the

interior collocation points, roots of Jacobi polynomials, and it

is expressed as

yN x

yj lj x

(A e4)

j1

li x

j1

jsi

x xj

xi xj

Furthermore,

0 isj

1 ij

li xj

(A e5)

are:

N1

dlj xi

dyN xi X

yj

dx

dx

j1

(A e7)

N1 2

d lj xi

d2 yN xi X

yj

dx2

dx2

j1

(A e8)

For i 1; 2.; N; N 1:

The first derivative vector, composed of (N 1) first derivatives at the (N 1) interpolation points is:

y0N

T

dyN x1 dyN x2

dyN xN dyN xN1

;

; .;

;

dx

dx

dx

dx

(A e9)

y00N

#T

"

d2 yN x1 d2 yN x2

d2 yN xN d2 yN xN1

;

;

.;

;

dx2

dx2

dx2

dx2

(A e10)

collocation points as

)

d2 lj xi

bij

; i; j 1; 2; .; N; N 1

dx2

(A e13)

(A e14)

Once the (N 1) interpolation points are chosen, then all the

Lagrangian building blocks, li(xi), are completely known, and

thus the matrices A and B are also known [36].

B.1.

following formula:

C1 TC2

C3 C4

1

T T2

(B e1)

Viscosities are at 1 atm [37].

B.2.

(A e6)

dlj xi

; i; j 1; 2; .; N; N 1

aij

dx

(

the point xi, and li(x) is defined as

N

1

Y

(A e12)

(A e2)

(A e3)

N1

X

(A e11)

vectors, the first and second derivative vectors can be written

in terms of the function vector y using matrix notation

Starting with

gN;0 1

12797

is obtained from the following formula:

2

2

32

32

C3

C5

6

6

7

7

6

6

T 7

T 7

(B e2)

Cp C1 C2 6

7 C4 6

7

4

4

C3 5

C5 5

sin h

cos h

T

T

where cp is in J/(kmol K) and T is in K [37].

To complete the simulation, extra correlations should be

added to the model. In the case of heterogeneous model,

because of transfer phenomena, the correlations for estimation of heat and mass transfer between two phases should be

considered. It is because of the concentration and heat gradient

between bulk of the gas phase and the film of gas on the catalyst

surface, which caused by the resistance of the film layer.

B.3.

following equation [38]:

1=2

kci dp 3 1

u

m

(B e3)

Dim 1 3 g

m1 3g

rDim

where dp is particle diameter (m), 3b is void fraction of packed

bed, is shape factor of pellet, u is superficial velocity through

12798

fluid density (kg/m3).

Diffusivity of component i in the gas mixture is given by

Ref. [39].

Dim

1 yi

P

yi =Dij

B.4.

(B e4)

(B e5)

The heat transfer coefficient between the gas phase and solid

phase is obtained by the following correlation [41]:

hf cp m2=3 0:458 rudp 0:407

cp rm K

m

3b

kf3

kf4

SchetterGiddins equation which is reported by Reid et al.

[40]. In the following FullerSchetterGiddins correlation, vci,

Mi are the critical volume and molecular weight of component

i which are reported in.

1=2

107 T3=2 1=Mi 1=Mj

Dij

2

Pt vci3=2 vcj3=2

kf2

(B e6)

and the other parameters are those of bulk gas phase, dp is the

equivalent catalyst diameter, K is the thermal conductivity of

gas, r, m are density and viscosity of gas, respectively and 3 is

void fraction of catalyst bed. To see the constants which are

used in these equations please see reference [22].

Appendix C. Nomenclature

Parameter description

a

catalyst activity, e

element of matrix A, e

aij

A

moles of aromatic formed, kmol h1

A

matrix defined in Eq. (Ae12), e

cross-section area of reactor, m2

Ac

B

matrix is defined in Eq. (Ae12), e

element of matrix B, e

bij

C

concentration, kmol m3

Ci

coefficient of Eqs. (B-1) to (B-2), e

inlet concentration of component j, kmol m3

Cj0

cp

specific heat capacity, kJ kmol1 K1

dp

particle diameter, m

effective diffusivity, m2s1

De

Dim

diffusivity of component i in the gas mixture, m2 s1

Ed

activation energy of catalyst, J mol1

Ei

activation energy for ith reaction, kJ kmol1

hf

heat transfer coefficient, W m2 K1

HC

hydrocarbon, kmol h1

H2

hydrogen, kmol h1

J

jacobi function, e

effective thermal conductivity, W m1 s1

keff

kci

mass transfer coefficient for component i, m h1

kf1

forward rate constant for reaction (1), kmol h1

kg cat1 M Pa1

Ke1

Ke2

Kd

L

lj

m

m

mc

Mi

Mw

n

n

N

NA

Ni

p

Pi

P

Q

r

ri

R

Ri

Ro

sa

t

T

Tref

TR

ur

x

yN

yi

yis

vc

y0N

y00N

a

b

g

3

m

vij

r

rB

s

fs

DH

a

cal

h

i

j

kgcat1 MPa2

forward rate constant for reactions (3), kmol h1

kg cat1

forward rate constant for reactions (4), kmol h1

kg cat1

equilibrium constant, MPa3

equilibrium constant, MPa1

deactivation constant of the catalyst, h1

length of reactor, m

building block of jacobi polynomial, e

number of data sets used, e

number of reaction, e

mass of catalyst, kg

molecular weight of component i, kg kmol1

average molecular weight of the feedstock, kg kmol1

average carbon number for naphtha, e

number of component, e

degree of Jacobi function, e

molar flow rate of aromatic, kmol h1

molar flow rate of component i, kmol h1

moles of paraffin formed, kmol h1

partial pressure of ith component, kPa

total pressure, kPa

volumetric flow rate, m3 s1

radius, m

rate of reaction for ith reaction, kmol kg cat1 h1

gas constant, kJ kmol1 K1

inner radius of spherical reactor, m

outer radius of spherical reactor, m

specific surface area of catalyst pellet, m2 kg1

time, h

temperature of gas phase, K

reference temperature, K

reference temperature, K

radial velocity, m s1

variable represent length of reactor, m

jacobi polynomial of degree N, e

mole fraction for ith component in gas phase, e

mole fraction for ith component on solid phase, e

critical volume, cm3 kmol1

first derivative of jacobi Equation, e

second derivative of jacobi Equation, e

characteristic parameter of Jacobin equation, e

characteristic parameter of Jacobin equation, e

coefficient of equation (Ae1), e

void fraction of catalyst bed, e

viscosity of gas phase, kg m1 s1

stoichiometric coefficient of component i in

reaction j, e

density of gas phase, kg m3

reactor bulk density, kg m3

tensile stress, Nm2

sphericity, e

heat of reaction, kJ kmol1

aromatic, e

calculated, e

hydrogen, e

numerator for reaction, e

numerator for component, e

n

naphthene, e

out

outlet, e

p

paraffin, e

ss

steady state, e

T

transpose, e

AF-SPBR axial-flow spherical packed-bed reactor, e

AF-TPBR axial-flow tubular packed-bed reactor, e

FBP

final boiling pint, C

IBP

initial boiling pint, C

LHSV

liquid hourly space velocity, hr1

OF

objective function, e

Pt

platinum, e

RF-SPBR radial flow spherical packed-bed reactor, e

RF-TPBR radial flow tubular packed-bed reactor, e

Re

rhenium, e

RON

research octane number, e

Sph.

spherical reactor, e

tub

tubular reactor, e

TBP

true boiling point, K

WHSV weight hourly space velocity, h1

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