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Liang et al. / J Zhejiang Univ SCI 20056B(6):590-596

Journal of Zhejiang University SCIENCE ISSN 1009-3095 http://wwwzju.edu.cnijzus E-mail: [email protected]

JZUs
simulation and analysis
(~i1~Hi1~)I,PAN Shi-wei (mYtltfl1)2

A study on naphtha catalytic reforming reactor

LlANG Ke-min (~5'U~,)tl, GUO Hai-yan

('School of Petrochemical Engineering, Shenyang University of Technology, Liaoyang 111003, China) (,School of Advanced Professional Technology, Shenyang University of Technology, Liaoyang 111003, China) lE-mail: [email protected] Received Sept. 22,2004; revision accepted Dec. 17,2004

Abstract: A naphtha catalytic reforming unit with four reactors in series is analyzed. A physical model is proposed to describe the catalytic reforming radial flow reactor. Kinetics and thermodynamics equations are selected to describe the naphtha catalytic reforming reactions characteristics based on idealizing the complex naphtha mixture by representing the paraffin, naphthene, and aromatic groups by single compounds. Key words: Naphtha, Catalytic The simulation results based above models agree very well with actual operation unit data. and analysis CLC number: TE624A2

reforming,

Kinetics, Simulation Document code: A

doi: IO.163I1jzus.2005.B0590

INTRODUCTION Catalytic reforming of naphtha or mixture of naphtha with a certain amount of cracking oil is a process of great interest to the petrochemical industry for the production of aromatic compounds that are raw materials for plastics, elastomers and resins manufacture. Catalytic reforming unit uses naphtha or cracking oil as feed stock to produce rich aromatic compounds and high octane value liquid products through reactions such as aromatization, cyclization, and hydrocracking. At the same time, it produces hydrogen (H) and liquified petroleum gas (LPG) as its by-products. The design or simulation of the catalytic reforming reactor is very difficult because of complicated components of catalytic reforming feedstock, higher operating temperature of the system, and the complicated reactions in the reactor. Much research (Pontes et al., 1999) on this subject had been carried out. Results have been published on the process, reactions and kinetics. A conventional naphtha catalytic reforming unit consists of 3 or 4 radial flow reactors in series operated under adiabatic conditions. The temperature and the H2IHC

molar ratio are the most important process variables. A bifunctional catalyst with Pt and a second metal is generally used. In addition, some novel processes (Melnikov and Makarova, 1998; Smith, 1960; Bolz et al., 1999) of catalytic reforming had been developed. The kinetics of catalytic reforming has been attracting the attentions of many researchers. A successful kinetic analysis proposed by Smith (1959), was based on idealizing the complex naphtha mixture by representing the paraffin, naphthene, and aromatic groups by single compounds. The nature of the reforming reactions in which the number of carbon atoms was the same for the precursor and product justified this procedure. Reaction rates were derived from the assumption of a homogeneous system. Jorge and Eduardo (2000) proposed a lumped kinetic model for the naphtha catalytic reforming process. The model utilizing lumped mathematical representation of the reactions taking place was in terms of isomers of the same nature. Arrhenius-type variation was added to the model in order to include the effect of pressure and temperature on the rate constants. Many other kinetic models (Jerzy, 1999) are not described here.

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Liang et al. I J Zhejiang Univ SC! 200568(6):590-596

591

A catalytic reforming unit with 4 reactors in series was analyzed and simulated in this paper. Kinetics proposed by Smith was adopted to describe the reactions occurring during catalytic reforming. Simulation results were compared with the actual data.

called model reactions. tions are as follows

The chemical

reaction

equa-

Cycloalkane s=e= Arene (A)+3H2 (H) Cycloalkane (E)+H2 ~ Alkane (P) Hydrocracking of alkane Hydrocracking of cycloalkane

(I) (2) (3) (4)

MATHEMA

TICAL MODEL According to Smith (1959), hydrocracking produces nearly the same amounts of moles of C1-C6 cuts. Therefore, the model reaction Eq.(3) and Eq.(4) can be represented by the following formula:

Basic assumption The structure of a catalytic reforming reactor is shown in Fig.l. The following assumptions are proposed forming tions: I. The temperature along the axial direction (S) of the radial flow reactor is homogeneous, that is on the basis of the features reactions, reactor of catalytic reand its operation condi-

CnH2n+2

+ ( --

n-3) 3

H2 ~-CJ

n IS

+-C2 15

+-C3

n IS

.!2..C+.!2..C 15 4 15 s C H2 + ( - H2 ~-CJ n n 3 IS +-Cs

(5)

dTs=O.
2. The concentration along the axial direction of the radial flow reactor is homogenous, that is dNs=O. 3. Reactions are in homogenous phase. Based on the above hypothesis, the temperature and concentration gradients along the axial direction can be neglected and only radial direction variables is conare considered. In fact, the fixed bed reactor sidered as a homogeneous reactor.
Catalyst inlet

n)

+-C2

n IS

+-C3

n IS

+-C4 15 (6)

n IS

where, n is the number of carbon atoms. For a certain reforming feedstock, the n value can be obtained through the average mole weight Mf (kg/kmol) of the feedstock and the family of component Xp, XE, XA. Their relation is

n=Mr-2xp+6xA
Inside grid-plate Feed out -Outside grid-plate

(7)

where,xp+xE+xA=I
alkane, cycloalkane,

and xs, XE, XA are mole fractions of and aromatics, respectively.

The corresponding empirical reaction rate equations (Rase, 1977) are based on model reaction Eqs.(1 )-(4). Cycloalkane
Catalyst out Fig.l Structure Feed port reforming radial flow reactor

transformed

into arene:
A

rl=l1kpl(PE-P

P~ IKpl)

(8)
(9)

of catalytic

kpl= 9.87exp(23.2I-34750/l.81)

Dynamics If some pseudo ingredients used to simplify the feedstock reforming, four dominant 1959) can be used to describe process so that the catalytic simplified significantly.

Cycloalkane (i) are appropriately of naphtha catalytic reactions (Smith, Hydrocracking reforming are

transformed

into alkane: (10)

r2=l1kpz(PEPwPpl Kpz) kpz=9.87exp(35.98-59600/1.81)

(11)

idealized

the catalytic reforming four

system can be reactions

These

r3=l1kp3PplP

(12)

l'

592

Liang et al. / J Zhejiang Univ SCI 20056B(6):590-596

kp3=exp(42.97-62300/1.81) Hydrocracking of cycloalkane: r4=17kp4PdP kp4=exp(42.97-62300/1.81)

(13)

(14) (15)

where, 17is corrective coefficient of catalyst; kpl is reaction rate constant corresponding to rh krnol/th-kg cat-Ml'a); kp2is reaction rate constant corresponding to ri, kmol/Ih-kg cat-Ml'a'); kp3is reaction rate constant corresponding to rs, kmol/ih-kg cat); kp4 is reaction rate constant corresponding to r4, krnol/thkg cat); Kpl is equilibrium constant of cycloalkane transformed into arene, (MPa)3; Kp2 is equilibrium constant of cycloalkane transformed into alkane, MPa-l; P is pressure of system or component fractional pressure, MPa; rl is reaction rate of cycloalkane transformed into arene, kmol/rh-kg cat); r: is reaction rate of cycloalkane transformed into alkane, krnol/thkg cat); rs is reaction rate of hydrocracking of alkane, krnol/th-kg cat); rs is reaction rate of hydro cracking of cycloalkane, kmol/Ih-kg cat). Occurrence of hydrocracking reaction occurring in the catalytic reforming process is the main causative factor catalyst deactivation. For different periods of catalytic activity, the carbon accumulation extent are not the same. Therefore, the values 17 are different from each other. For new catalyst, 17=1and in other conditions, 0<17<1.The value of 17can be calculated based on working conditions and time span of the catalytic activity. Thermodynamics The most important reaction in the catalytic reforming is the transformation of cycloalkane into aromatics. It is a rapid reaction which approaches to equilibrium in very short time. For reactions of cycloalkane transformation into aromatics and alkane, their reaction equilibrium constants are as follows (Smith, 1959): Kpl=P
A P~ /PE=1.04x 10-3 exp(46.15-46045/1.81)

hydrogen consumed or released during the reaction, the reaction enthalpies based on the number of moles of hydrogen (I'1H1 reaction enthalpy of model reaction (I), kJ/(kmol H2); I'1H2 reaction enthalpy of model reaction (2), kJ/(kmol H2); I'1H3 reaction enthalpy of model reaction (3), kJ/(kmol H2); I'1H4 reaction enthalpy of model reaction (4), kJ/(kmol H2) are as follows: I'1H1=71038.06 kJ/(kmol H2) I'1H2=-36953.33 kJ/(kmol H2) I'1H3=-56597.54 kJ/(kmol H2) I'1H4=-51939.31 kJ/(kmol H2) (endothermic) (exothermic) (exothermic) (exothermic)

The reactants and products of a catalytic reforming unit can be considered as ideal gases. The relation between its heat capacity (Cp, kJ/(kmolC)) and temperature is
Cp=4.1868(a+bT

+cT2+dT3)

(18)

where, a, b, c and d can be obtained from physical properties manual and is listed in Table I (Lu, 1982; Reid et al., 1977).
Table 1 Coefficients of heat capacity equation of ideal gases cxl06 dxl09 ID bx 103 a 6.483 1.826 2.215 -3.298 H2 12.45 4.598 2.680 -2.703 Cl 1.292 C2 45.84 -16.57 2081 -1.009 C3 73.15 -37.89 7.678 -26.47 C4 2.266 79.13 -0.674 116.4 -61.63 13.67 -0.866 C5 p -1.456 21.15 184.2 -100.24 E -14.789 187.3 -106.0 22.37 122.4 11.73 A -5.817 -66.05

(16) (17)

Kp2=Pp/(PE,PH)=9.87exp(8000/1.8T

-7.12)

For the above four model reactions, considering the reaction enthalpy and the number of moles of

Model of reactor The physical model for catalytic reforming radial flow reactor is shown in Fig.2. The outer radius of the catalyst bed is R; and the inner radius of the catalyst bed is R; For a element dR at (R, R+dR), the inlet material stream into it is N, and the temperature is T. The outlet material stream is N,+dN; and the temperature is T+dT. With mass and enthalpy balances for the element combining kinetic and thermodynamic equations, the concentration and temperature distributions along the reactor radius can be derived as:

.
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Liang et al. /.1 Zhejiang Univ SCl 20056B(6):590-596

593

dNA/dR=2xRLPbrj dNE/dR=2xRLPb(-rl-rz-r4) dNp/dR=2xRLfJb(r2 - r3) dNH/dR=27rRLfJb(3rj-rz-n-3)/3)rr(nI3)r4) dTldR=(2xRLPb)/(J:.FiCpi) x {3rl(-tJi1)+r2(-I1H2) +[(n - 3)/3]r3(-tJi3)+(nI3)r4(-I1H4)}

(19) (20)

SIMULA nON OF THE REACTOR Fig.3 shows a flow diagram with four reactors in series. With conditions at the reactor inlet as boundary conditions, the concentration and temperature distributions can be calculated by solving grouped Eq.{l9) to Eq.(23) with fixed step, four order Runge-Kutta method. The computing diagram is shown in Fig.4. Four catalytic reforming radial flow reactors of the Chemical Plant No.1 of the Liaoyang Petrochemical Fiber Company were analyzed and simulated with this model.
Heaters

(21)
(22) (23)

Eq.( 19) to Eq.(22) describe changing rates of arene, cycloalkane, alkane, and hydrogen along the bed layer radius. For the adiabatic fixed bed radial flow reactor, its temperature distribution is represented by Eq.(23). F is feedstock, kmol/h; N is flow rate, kmol/h; L is height of catalyst bed in reactor,. m; Pb is bulk density of catalyst, kg/m '.
T+d T, N,+dN,

Reforming feedstockl'l

I~~~\~' ~
. :
!
;

[1'
\
:
r'.

Jl ..... \.. r J.
~!
~.

'.

R.efomlin. recycle hydrogen

Reactor ~~

h.

Knockout drum

T,N,

Reforming formation hydrogen

Compressor

Go to stale systems

Fig.2 Physical model of catalytic reforming radial flow reactor

Fig.3 Schematic flow diagram of four reactors in series of catalytic reforming

Start

r
I r
r
/?=/?-H

feedstock

I
data and a, b, c, d, NR etc.

Input reforming

Calculating

NI', NE, NA

I
1

i
Calculating carbon atom number n condition of reactor

Preset boundary

I
Input structural parameters

I!=I

I
l l l l

of reactor II such as Ro, R" L etc. -y

I
Material

R=Ro,H=O.Ol,N=1

I
Cp. etc.

collect and calculating reaction

......

partial pressure (P,) of components

N=.N+I

I I

r
r

Calculating

rate of rv-rs and heat capacities

w
Solve NA, NE, Np, NH, 1 with Runge-Kutta method

~
NO~ ~ R>R,""> N" I

PrintT,NA, NE, Np, NH

I I
I!=II+l

Fig.4 Computer simulation program blocks

,>

594

Liang et al. J Zhejiang Univ Se! 200568(6):590-596

Basic data Liaohe straight-run distillation naphtha (Liaohe Petroleum Field, China) was selected as reforming feedstock. Its distillation temperature range is 65 QC-145 QC, d!o=0.7314. Engler distillation data is listed in Table 2. The feedstock of catalytic reforming reactors and recycle hydrogen content data (Yong, 1995) is shown in Tables 3 and 4. The inlet temperatures of all reactor I, Il, III and IV were 521 QC. The operating pressure was 1.730-1.408 MPa and recycling hydrogen flow rate was 3.1372xI04Nm3/h. Simulation calculation Simulation calculation was carried out using data listed in Tables 2-4 and the results are listed in Table 5. Because people usually focus on the reactor production ability, conversion rate, hydrogen generated by reforming, temperature of catalyst bed, etc., the temperature, arene, cycloalkane, alkane, and hydrogen varying with the radius of the beds are listed in Table 5. Note that the data used in the simulation calculation is calibration data in the latest operation period. The catalyst correction coefficient 17=0.432at this period.

Table 4 Reforming forming reactors

feedstock

content

of catalytic

re-

ID
C4

Reforming

feedstock content (%, m) 0.02 0.15 4.55 31.56 18.~ 4.44 1.57 0.24 1.03 3.21 20.26 19.12 4.54 0.02 0.49 3.54 0.35 0.39 2.03 1.10 ~~

c,
C6

C7
~ C9

c;
CyC5 m-CyC5 CyC6 CyC7

c.c,
CyC9 Cy c; B
T EB PX

MX
OX ~A

RESUL TS AND DISCUSSIONS It obvious, from the data listed in Table 4, that in reactor I and Il, the main reaction happened is cycloalkane aromatization, is an endothermic reaction and the bed layer temperature drop of these two reactors is larger. In reactor III and IV, alkane dehydrogenization, cyclization, and hydrocracking reactions
Table 2 Engler Distillation fraction (%) b.p. (0C) distillation 10 85 50 114 data 90 135

Note: T: Toluene; EB: Eshylbenzene; PX: Parexylene; MX: Meta-xylene (I,3-dimethylbenzene); OX: Orthoxylene; C;A: Arene of C, and over

IBP
77

EBP
157

Table 3 Recycle ing reactors ID

hydrogen

content

of catalytic

reform-

Recycle hydrogen 84.94 5.85 3.88 2.93 2.17 0.19 0.04

content (%, v)

H2
Cl

C2 C3
~

c,
B Note: B: Benzene

are dominant there. At the same time, the cycloalkane produced there through cyclization continues to aromatize, but the amount is not large. Furthermore, a large amount of heat was released by cyclization and hydrocracking reactions. Therefore, the bed temperature drop in these two reactors, the last one especially, is smaller. It should be pointed out that under some suitable conditions the reversal reaction represented by Eq.(IO), alkane transformation into cycloalkane becomes more important. On the one hand, aromatic production yield can be increased. On the other hand, non-aromatic content in reforming arene can be decreased and aromatic compounds transformation rate can be increased. Based on data in Table 5, the temperature distribution curve in the catalyst bed, that is, the temperature variation within the radius of the catalyst bed, is shown in Fig.5 showing that at the inlet side (i.e. higher value of R) of the reactors I and Il, the bed temperature varies rapidly and at the outlet side (i.e. smaller R) the bed temperature varies slowly. Because

..

Liang et al. / J Zhejiang Univ SCI 2005 6B(6):590-596

595

Table 5 The simulation Reactor ID Bed Radius (mm) 510 460 410 360 310 260 210 170 Bed temperature

results Cycloalkane (kmol/h) 90.050 71.642 64.052 59.601 56.644 54.569 53084 52.213 52.213 39.260 33.255 29.608 27.136 25.363 24.055 23083 22.369 22.196 22.196 14.685 11.158 9090 7.744 6.811 6.138 5.640 5.262 4.979 4.762 4.599 4.501 4.501 4.447 4.227 3.977 3.743 3.537 3.361 3.213 3089 2.985 2.900 2.830 2.775 2.733 2.729 Alkane (kmo1/h) 76.630 76.650 76.603 76.565 76.535 76.513 76.496 76.486 76.486 75.398 74.850 74.500 74.251 74066 73.926 73.818 73.737 73.717 73.717 70.250 68.188 66.709 65.560 64.670 63.862 63.220 62.683 62.237 61.871 61.578 61.393 61.393 56.750 53094 50.175 47.756 45.767 44.105 42.708 41.533 40.547 39.726 39.050 38.507 38.085 38049 Hydrogen (kmo1/h) 1257.870 1300.845 1320.133 1331.804 1339.686 1345.276 1349.304 1351.676 1351.676 1382.185 1397.267 1406.714 1413.266 1417.946 1421.453 1424073 1426066 1426.474 1426.474 1445.538 1455.138 1461.024 1464.998 1467.839 1469.948 1471.551 1472.787 1473.748 1474.491 1475.058 1475.404 1475.404 1477.891 1480.240 1482.287 1484025 1485.487 1486.714 1487.743 1488.603 1489.319 1489.910 1490.393 1490.777 1491.074 1491.099

(0C)
521.00 496.88 486.04 479.48 47503 471.88 469.60 468.26 521.00 503.79 495.27 489.94 486.27 483.60 481.62 480.14 47904 478.78 521.00 510.04 504.52 501.13 498.83 497.17 495.94 495.00 494.27 493.71 493.27 492.93 492.72 521.00 519.26 517.69 516.33 515.19 514.24 513.44 512.77 512.20 511.74 511.35 511.03 510.78 510.59 510.57

Arene (kmol/h) 16.180 32.979 39.943 44096 46.879 48.843 50.254 51.084 51.084 62.982 68.681 72.194 74.589 76.334 77.619 78.579 79.286 79.457 79.457 87.774 91.956 94.556 96.345 97.652 98.643 99.412 100.017 100.495 100.872 101.163 101.342 101.342 103.680 105.670 107.329 108.708 109.859 110.822 111.630 112.308 112.875 113.346 113.732 114.041 114.280 114.301

II

585 535 485 435 385 335 285 235 185 170

III

760 710 660 610 560 510 460 410 360 310 260 210 170

IV

825 775 725 675 625 575 525 475 425 375 325 275 225 175 170

,~

596

Liang et at. .J Zhejiang Univ SC! 20056B(6):590-596

530 520

t
" E ~

510 500 490

IV

:; "
Cl.

480 ~ ~ 470 460 I00

----300

_ Simulation result o Data at inlet Data at outlet 900

500 700 Bed radius (mm)

Fig.S The temperature flow reactor

distribution of reforming radial

there was more catalyst in the inlet where the reactants content was higher than that at the outlet. Therefore, more aromatic compounds were generated and more heat was absorbed at the Inlet side. The situation at the outlet side was totally opposite. For reactor III and IV in spite of the trend being similar to that of reactors I and II, the temperature varied more gently because the reactions were exothermic. For comparison, the reactors calibration values are also shown in Fig.5. The simulation results and actual values of the reforming product are shown in Table 6. These results indicate that the model and simulation in the present paper are satisfactory.

Table 6 Comparison between actual values of reforming product and simulation results Item Actual (Yong, 1995) Simulation Error (%) Depentane oil 15585 15580.96 -0026 Flow rate of products (kg/h) Arene 11185 11258.49 0.657 Non-arene 4399.65 4322.47 -1.754 Productivity of arene (%, m) 57.96 58.33 0.638

CONCLUSIONS
1. The three assumptions in the present model are reasonable. The results indicate that the one-dimensional homogenous model is suitable for describing catalytic reforming radial flow reactor. 2. Once pseudo ingredients were selected suitably. The present empirical kinetics model can be well applied to catalytic reforming reactor for simulation and optimization. 3. This method can be used to predict aromatic capacity, yield, transformation rate, bed temperature, and so on for new operation conditions. Therefore, the optimum operating parameters can be obtained to yield maximum profit.

Jerzy, S., 1999. On the kinetics of catalytic reforming with the use of various raw materials. Energy Fuels, l3( I ):29-39. Jorge, Al, Eduardo, Y.M, 2000. Kinetic modeling of naphtha catalytic reforming reactions. Energy Fuels, 14(5): 1032-1037. Lu, H., 1982. Manual of Petrochemical Industry Fundamental Data. Chemical Industy Press, Beijing (in Chinese). Melnikov, V.H., Makarova, N.P., 1998. Modification of reforming: Without hydrogen circulation. Khim. Tekhno/.
Top/. Masel., 23(1):9-13.

References
Bolz, CR, Graziani, KK, Harandi, M.N., Ozawa, Y., Sorensen, CM., 1999. Radial-Flow Reactors Containing Multiple Catalyst Beds, Especially for Naphtha Reforming and Upgrading. PCT lnt. Appl. WO 9920384.

Pontes, LAM, Rangel, MD.C., Mario, DJ.M., 1999. Catalytic reforming of naphtha. An Assoc. Bras. Quim., 48(3): I69- I79. Rase, H.F., 1977. Chemical Reactor Design for Process Plants. Vol. 2, John Wiley & Sons, Inc. Reid, RC, Prausnitz, lM., Sherwood, TK., 1977. The Properties of Gases and Liquids. 3rd Ed., McGraw-Hill Co., p.108-109. Smith, RB., 1959. Kinetic analysis of naphtha reforming with platinum catalyst Chem. Eng. Progr., SS(6):76-80. Smith, RH., 1960. Reforming of naphtha in several stages. US 2,965,560. Yong, W., 1995. Calibration of E603 reforming catalyst. Liaohua Sci. and Tech., 16(4):16-19.

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