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CFD MODELING OF TRICKLE BED REACTORS: Hydro-processing Reactor

Prashant R. Gunjal, Amit Arora and Vivek V. Ranade


Industrial Flow Modeling Group National Chemical Laboratory Pune 411008 Email: vvranade@ifmg.ncl.res.in

OUTLINE

Trickle Bed Reactors


Applications/ flow regimes Experiments

CFD Modeling of Trickle Bed Reactors


Inter-phase momentum exchange/ capillary terms Estimation of fraction of liquid suspended in gas phase

Simulating Hydro-processing Reactor


Reaction kinetics/ other sub-models Influence of reactor scale

Concluding Remarks
CFD Modeling of Trickle Bed Reactors

TRICKLE BED REACTORS Wide Applications


Hydro-de-sulfurization Hydro-cracking/ hydro-treating Hydrogenation/ oxidation Waste water treatment

Key Characteristics
Close to plug flow/ Low liquid hold-up Suitable for slow reactions Poor heat transfer/ possibility of mal-distribution Difficult scale-up
CFD Modeling of Trickle Bed Reactors

TRICKLE BED REACTORS


Liquid Gas

Gas & Liquid Flow through Void Space = 26-48 %

CFD Modeling of Trickle Bed Reactors

FLUID DYNAMICS OF TBR

Characterization of Packed Bed Wetting of Solid Surface by Liquid , P, L, , RTD Mal-distribution, Channeling & Mixing Flow Regimes & Global Flow Characteristics

CFD Modeling of Trickle Bed Reactors

FLOW REGIMES

CFD Modeling of Trickle Bed Reactors

EXPERIMENTS AT NCL

Pressure Indicator
101

Hydrodynamics
Pressure Drop Liquid Hold-up

Column with 3mm or 6mm Glass Beads


Data Acquisition

Conductivity Probes
Residence Time Distribution

Liquid Distribution at Inlet


Uniform Non-uniform

From Compressor

Separator Conductivity Probe

Pump
Liquid Tank

Experimental Parameters
Bed Diameter: Particle Diameter: Liquid Velocity: Gas Velocity: Tracer : 0.1 & 0.2 m 3 & 6 mm < 24 mm/ s < 0.50 m/ s NaCl

CFD Modeling of Trickle Bed Reactors

TYPICAL PRESSURE DROP DATA


35 30
Pressure gradient, KPa/m
Trickle flow regime
Pulse flow regime

25 20 15 10 5 0 0

10 20 Liquid Flow Rate, Kg/m 2s

30

CFD Modeling of Trickle Bed Reactors

PUBLISHED EXPERIMENTAL DATA


2 1.8 1.6 1.4 1.2 1 0.8 0.6 0.4 0.2 0 0 5 10 15 20 25 Liquid Velocity VL, (Kg/m2s)
2 L= ? Trickle Flow 1 3 L L Spray Flow
1. Szady and Sundersan (1991) 2. Rao et. al (1983) 3. Specchia and Baldi (1977)

Superficial Gas Velocity Vg, (m/s)

Pulse Flow L= ? L=L Bubbly Flow

CFD Modeling of Trickle Bed Reactors

MODELING OF MACROSCOPIC FLOW

Bed Porosity: Scale of Scrutiny


Bed diameter/ length: overall Intermediate scale: Gaussian distribution Smaller than particle diameter: Bi-modal distribution

Approach Used:
Experimentally measured or estimated radial variation of axially averaged bed porosity Specify porosity by drawing a sample assuming Gaussian distribution with specified variance
CFD Modeling of Trickle Bed Reactors

CHARACTERIZATION OF PACKED BED Radial Variation of Porosity: Mueller (1991)


(r ) = B + (1 B )J o (ar * )e br 12.98 for 2.61 D/d P 13.0 a = 8.243 (D/d P 3.156 ) a = 7.383 2.932 for 13.0 D/d P (D/d P 9.864 )

0.724 b = 0.304 D/d P r * = r/D and J o is zero th order Bessel Function


CFD Modeling of Trickle Bed Reactors

CHARACTERIZATION OF PACKED BED Muellers Correlation


Three data sets from literature
0.8 0.7 0.6 0.5
Szady and Sundersan (1991) Rao et.al. (1983) Spacchia and Baldi (1977)

Our experiments
0.7 0.6 0.5
D=0.194m, dp=3mm D=0.194m, dp=6mm

Porosity
0 0.2 0.4 0.6 0.8 1

Porosity

0.4 0.3 0.2 0.1 0 0 0.2 0.4 0.6 0.8 1

0.4 0.3 0.2 0.1 0

Dimensionless Radius

Dimensionless Radius

CFD Modeling of Trickle Bed Reactors

VARIATION OF BED POROSITY


0.56

With std dev=0

With std dev=5%

With std dev=10%

r/R
0.70

Selection of appropriate value is not straight forward: RTD may help


CFD Modeling of Trickle Bed Reactors

CFD MODEL Multi-fluid Model (Eulerian-Eulerian) Continuity Equation


K K + K KU K = 0 t

Momentum Balance Equation


( K KU K ) + ( K K U KU K ) = K P + t ( K U ) + K K g + FK , R (U k U R )

CFD Modeling of Trickle Bed Reactors

CFD MODEL Inter-phase Coupling Terms (Attou & Ferschneider, 2000)


FGL E (1 ) 2 = G 1 2 2G G d p L (1 G )
0.667

E 2 P (U G U L )(1 G ) L + Gd p (1 G )
0.667

0.333

FGS

E (1 ) 2 = G 1 2 2G G d p

S (1 G )

E U (1 G ) S + 2 P G Gd p (1 G )

0.333

E1 s 2 E2 PU G S FLS = L 2 2 + d Ld p L p

CFD Modeling of Trickle Bed Reactors

CFD MODEL Capillary Terms


1 1 PG PL = 2 d d 2 1

Attou and Ferschneider (2000)


1 PG PL = 2 1 G
0.333

0.5416 G F d P L

PG PL 2 5.416 s = z z 3 d p 1 G

2 / 3

1 1 G

G s s z + (1 )2 z G

G F L

CFD Modeling of Trickle Bed Reactors

CFD MODEL Capillary Terms


F G L = 1 + 88.1 G L for

G < 0.025 L

Extent of Wetting, f (Jiang et al., 2002)


PG PL = (1 f ) Pc

Scalar Transport
K K Ci + K KU K Ci = ( K K Di.mCi ) + Si t
CFD Modeling of Trickle Bed Reactors

SIMULATED RESULTS
Distributions within the bed
45 40 35

No n-prewetted B ed

P rewetted B ed

Contours of Liquid Hold-up

30 25 20 1 5 1 0 5 0 0 0.02 0.04 0.06 0.08 0.1 V e lo c it y M a gnit ude , m / s e c

35 30 25 20 1 5 1 0 5
No n-prewetted B ed P rewetted B ed

Pre-wetted

Un-wetted

0 0 0.1 0.2 Liquid Holdup 0.3

VL= 6 mm/ s, VG=0.22 m/ s, D=0.114 m, dP= 3 mm, =5%

CFD Modeling of Trickle Bed Reactors

SIMULATED RESULTS

Column Diameter = 0.114 m

Particle Diameter = 3 mm, VG=0.22 m/ s

CFD Modeling of Trickle Bed Reactors

SIMULATED RESULTS

VG= 0.22 m /s, D = 0.114 m

VG= 0.22 m /s, D = 0.194 m

CFD Modeling of Trickle Bed Reactors

GAS-LIQUID FLOW IN TBR Estimation of Frictional Pressure Drop & Fraction of Liquid Supported by Gas
Solid

P P = f ( LL g ) L GL L GL Q L L

Liquid Gas

Fraction of Liquid Hold-up Supported by Gas Phase < 1

Simulate at two values of g (9.7, 9.9 m/s2)


Pf L = P P g1 g2 L 2 L 1 g1 g 2
L = P P L 2 L 1 L (g 1 g 2 )

CFD Modeling of Trickle Bed Reactors

SIMULATED RESULTS
14
Pressure Gradient KPa/m

12 10 8 6

Saez and Corbonell (1985)-Exp. data Szady and Sundersan (1991)-Increase in liquid Szady and Sundersan (1991)-decrease in liquid CFD Simulations w ithout Capillary Force CFD Simulations

Calibrate Model Parameters from P


0.60
Holub et. al. (1993) -Experimental data Szady and Sundersan (1991)-Exp. Data CFD Results Supported Liquid Saturation

0.50
L

4 2 0 0.00

Liquid Saturation and

0.40

0.30

0.20

0.40

0.60
-1 2

0.80

1.00

Liquid Flow Rate x10 , Kg/m s

0.20

Can Predict Total and Supported Liquid Volume Fraction

0.10

0.00 0.00

0.20

0.40 0.60 0.80 -1 2 Liquid Flow Rate x10 , kg/m s

1.00

Operating conditions:VG=0.22m/s, D/dp =55, dp=3mm, Std. Dev.=5%, E1=215, E2=1.75

CFD Modeling of Trickle Bed Reactors

SIMULATED RESULTS
50
Pressure Drop, (KPa/m)

40 30 20

CFD Results Experimental Data

Data of Spachio & Baldi (1977)


0.5
L

Liquid Saturation and

10 0 0 0.2 0.4 0.6 0.8 1


Gas Flow Rate, (Kg/m 2s)

0.4

Liquid Saturation- CFD Results Supported Liquid Saturation Liquid Saturation- Exp. Data

0.3

0.2

As gas velocity increases, more & more liquid is supported by gas

0.1

0 0 0.2 0.4 0.6 Gas Mass Velocity, kg/m2s 0.8 1

Operating conditions: VL=2.8x10-3 m/s, dp=3mm, D/dp=30, Std. Dev.=5%, E1=500, E2=3

CFD Modeling of Trickle Bed Reactors

SIMULATED RESULTS
200 Pressure Drop, (KPa/m) 160 120 80
L

Experimental Data CFD Results

Data of Rao et al. (1983)


0.2

40
Liquid Saturation and

0.16

Liquid Saturation- CFD Results Supported Liquid Saturation Liquid Saturation Exp. Data

0 0 2 4 6 8 Gas Mass Velocity, (kg/m2s)

0.12

0.08

As gas velocity increases, more & more liquid is supported by gas

0.04

0 0 2 4 6 8

Gas mass velocity, Kg/m2s

Operating conditions:VL=1x10-3m/s, D/dp =15.4, dp=3mm, Std. Dev.=5%, E1=215, E2=3.4

CFD Modeling of Trickle Bed Reactors

RESIDENCE TIME DISTRIBUTION


0.12 0.1 0.08 E(t), sec
-1

1 2 1 2 2

Pre-wetted Bed Non Pre-wetted Bed

Simulation Results Experimental Results

0.06 0.04

0.02 0 0 20 40 60 Time, (sec) 80 100 120

Operating conditions: VL=2.06x10-3m/s VG=0.22m/s, D/dp =18, dp=6mm, Std. Dev.=5%, E1=180, E2=1.75

CFD Modeling of Trickle Bed Reactors

MODELING OF HYDRO-PROCESSING REACTOR

Reaction and Kinetics (Chowdhury et al. 2002)


Hydro-desulfurisation (HDS)
Ar S + 2H2 Ar + H2S
rHDS =
0 56 6 k c L ,.H 2 c 1 .,S L

1 + K Ad c L ,H 2 S

De-aromatisation of Mono-, Di- and Poly- Aromatics


Mono Ar + 3H2 Napthenes Di Ar + 2H2 Mono Ar Tri Ar + H2 Di Ar

rMono = kMonoCMono + k _ MonoCNaph rDi = k Di C Di + k _ Di C Mono


rPoly = k Poly C Poly + k _ Poly C Di

CFD Modeling of Trickle Bed Reactors

SIMPLIFICATIONS/ ASSUMPTIONS
Pressure drop is insignificant compared to the operating pressure Trickle bed reactor is operated isothermally (efficient heat transfer) Ideal gas law is applicable Liquid phase reactants are non-volatile (negligible vapor pressure) Gas-liquid mass transfer is the limiting resistance. The catalyst particles are completely wetted
CFD Modeling of Trickle Bed Reactors

MODEL EQUATIONS
Mass Balance of Species i
k k Ck , i t + ( k kU k Ck ., i ) = ( k k Di , mCk , i ) + k k Si , k

Source Terms for Gas Phase


C S i = K GLi a GL Gi C Li Hi

Source Terms for Liquid Phase


j= nr CGi C Li + B rij S i = K GLi aGL Hi j=1

S i = B rij
j=1

j= nr

CFD Modeling of Trickle Bed Reactors

MODEL EQUATIONS Mass Transfer Coefficient (From Goto & Smith, 1975)
L G ki aL = 1 L DiL L

L DL L i

1/ 2

Solubility of Hydrogen/ H2S (Korsten et al. 1996)


Hi =
H2

N i . L

: molar gas volume


a 0 = 0.559729 a 1 = 0.42947 10 3 a 2 = 3.07539 10 3 a 3 = 1.94593 10 6 a 4 = 0.835783

T 1 = a 0 + a 1T + a 2 + a 3T 2 + a 4 . 2 20 20

H S = exp(3.3670 0.008470 .T )
2

CFD Modeling of Trickle Bed Reactors

CASE STUDIES Gas and Liquid Superficial Velocities Increase with Scale Wetting gets Better with Scale
Parameters Reactor Diameter, m Bed Length Particle Diameter, m Bed Porosity LHSV, h-1 Operating Pressure, Mpa Operating Temperature, K Initial H2S Conc., v/v % Laboratory Scale Reactor (Chowdhury et al. 2002) 0.019 0.5 m 0.0024 0.50 1-5 20-28 573-693 0.5-8 Commercial Scale Reactor (Bhaskar et al. 2004) 3.8 16 m 0.0015 0.36 1-5 20-80 573-693 0.5-8

CFD Modeling of Trickle Bed Reactors

KINETICS/ OIL COMPOSITION From Chowdhury et al. (2002)


Kinetic Constants
K Ad , m3/kmol

Values 50000 2.5 X 1012 exp(-19384/T) 6.04 X 102 exp(-12414/T) 8.5 X 102 exp(-12140/T) 2.66 X 105 exp(-15170/T) Percentage 1.67 2.59 8.77 17.96 19.25

K, Dimensionless k*mono, m3/kg.s k*Di, m3/kg.s k*poly, m3/kg.s Component Ar-S % Poly-Ar % Di-Ar % Mono-Ar % Naphthenes %

CFD Modeling of Trickle Bed Reactors

SIMULATED RESULTS-1

100

90

75

Varying Porosity

Conversion, Ar-S %

Ar-S Exp
50

Conversion, x

Uniform Porosity

60

30

25

0 573

0
583 593 603 613 623 633 643 653

Temp, K

Initial H2S Conc Gas Phase ( %, V/V)

Temperature

Initial Concentration of H2S

(P=4 MPa, LHSV=2.0 h-1, QGNTP/QL=200 m3/m3, TR=320oC, yH2S=1.4% ) Symbols denote experimental data of Chowdhury et al. (2002)

CFD Modeling of Trickle Bed Reactors

SIMULATED RESULTS-2

90 80 70 Conversion, % 60 50 40 30 20 10 0 573 593 613 Temperature, K 633 653

60

Ar-P total total poly


50

A r-D
A r-M
A r-Di-Expt

Conversion, %

A r-Mono-Exp

40

30

20

10

0 573 593 613 633 653

Temperature, K

(P=4 MPa, LHSV=2.0 h-1, QGNTP/QL=200 m3/m3, yH2S=1.4%) Symbols denote experimental data of Chowdhury et al. (2002)

CFD Modeling of Trickle Bed Reactors

SIMULATED RESULTS-3
60
Total-Ar

50

Ar-Poly Ar-Di Ar-Mono

Conversion, %

40 30 20 10 0 2 2.4 2.8 3.2 3.6


-1

LHSV, h

(P=4 MPa, TR=320 oC, QGNTP/QL=200 m3/m3, yH2S=1.4%, filled symbols are for experimental data of Chowdhury et al., 2002)

CFD Modeling of Trickle Bed Reactors

INFLUENCE OF REACTOR SCALE

1.6

35 1.6 7

1.4

30

1.4

Dimensionless Solid Hold-up

25 1 20 0.8 15 0.6 10

1.2 5 1 4 0.8 3 0.6 2

0.4

Solid hold-up Local Axial Velocity

0.4

Solid hold-up Local Axial Velocity

0.2

5 0.2 0 0 0.2 0.4 0.6 0.8 1

0 0 0.2 0.4 0.6 0.8 1

Dimensionless Radius

Dimensionless Radius

Laboratory (LHSV=3)

Industrial (LHSV=2)

(P=4 MPa, TR=320 oC, QGNTP/QL=300 m3/m3)

CFD Modeling of Trickle Bed Reactors

Dimensionless Local Axial Velocity

1.2

Dimensionless Local Axial Velocity

Dimensionless Solid Hold-up

INFLUENCE OF REACTOR SCALE

100

12000 Outlet Conc. Ar-S, ppm 10000 8000 6000 4000 2000
Lab S c ale Reactor

Com m ercial Reactor

Conversion, %

75

Lab-scale Reactor Commercial Reactor

50

25 573

0
593 613 633 653

573

593

Temperature, K

613 633 Temperature, K

653

(Plab & com=4 & 4.4 MPa, LHSVlab=2.0 h-1, QGNTP/QL=200 m3/m3, yH2S=1.4%)

CFD Modeling of Trickle Bed Reactors

INFLUENCE OF REACTOR SCALE

100 80 Conversion, % 60 40 20 0 -20 573


Poly-Ar Total Poly-Ar-Commercial Total-Commercial

100 95 90 Conversion, % 85 80 75 70 65 60 55 50
593 613 Temperature, K 633 653
Ar-S-Lab Scale Ar-S-Commercial

2.5

3 LHSV, h-1

3.5

(Plab & com=4 & 4.4 MPa, LHSVlab & com=2.0 & 3.0 h-1, (QGNTP/QL)lab & com= 200 & 300 m3/m3, yH2S=1.4%)

(Plab & com=4 & 4.4 MPa, Temperature= 593 K, (QGNTP/QL)lab & com= 200 & 300 m3/m3, yH2S=1.4%)

CFD Modeling of Trickle Bed Reactors

INFLUENCE OF REACTOR SCALE


120

100
Poly-Ar

90 80

Poly-Ar Di-Ar Mono-Ar Total

100

Di-Ar
Mono-Ar
Total

Conversion, %

Conversion, %

80

70 60 50 40 30 20

60

40

20

10
0 2 3 4 5 Pressure, MPa 6 7 8

0 2 2.5 3 -1 LHSV, h 3.5 4

(QGNTP/QL)lab & com= 200 & 300 m3/m3 T=593 K LHSVlab & com=2.0 & 3.0 h-1 ,yH2S=1.4%

Plab & com=4 & 4.4 Mpa, T=593 K yH2S=1.4% (QGNTP/QL)lab & com= 200 & 300 m3/m3

Continuous lines: commercial; Dotted lines: laboratory scale

CFD Modeling of Trickle Bed Reactors

CONCLUDING REMARKS Macroscopic CFD Model Reasonably Simulates Gasliquid Flow in Trickle Beds
Liquid hold-up Residence time distribution May be used to estimate fraction of suspended liquid

Further Work is Needed for Understanding Wetting/ Hysteresis to Make Further Progress Despite Limitations, CFD Models can be Used to Understand Key Issues in Reactor Engineering Including Scale-up & Scale-down
CFD Modeling of Trickle Bed Reactors

CFD Modeling of Trickle Bed Reactors

MODELING OF MESO-SCALE FLOWS Single Phase Flow through Packed Bed


Unit cell approach Simple cubic, FCC, rhombohedral .. Inertial flow structures, pressure drop, heat transfer

Interaction of Liquid Drop/ Film with Solid Surface


Regimes of interaction Dynamic contact angle/ surface characteristics VOF simulations Insight into capillary forces???

CFD Modeling of Trickle Bed Reactors

SINGLE PHASE FLOW Single Phase Flow through Packed Bed


Periodic Flow Periodic Flow

Wall Wall Wall

Operating Parameters
Cell Length Fluid Particle Reynolds Number 28mm, 3mm Water 12-6000

CFD Modeling of Trickle Bed Reactors

SINGLE PHASE FLOW


5

Experiments:
0

Suekane et al. AIChE J., 49, 1

4.5

Simulations

CFD Modeling of Trickle Bed Reactors

SINGLE PHASE FLOW


3
Experiment al Simulat ion-28mm Simulat ion-3mm

4
Experiment al
Simulat ion-28mm

Simulat ion-3mm

Vz/Vmean

Vz/Vmean

0 -1
5
Experimental

-1

-0.5

x/r

0.5

-1

-0.5

0.5

x/r
5
Experimental

4 3

Simulation-28mm Simulation-3mm

4 3 2 1 0 -1

Simulation-28mm Simulation-3mm

Vz/Vmean

2 1 0 -1 -1 -0.5 0 x/r 0.5 1

Vz/Vmean

-1

-0.5

x/r

0.5

CFD Modeling of Trickle Bed Reactors

SINGLE PHASE FLOW

Vz=8.66mm /s

S
Max arrow length : A=0.26 mm/s B=0.29 mm/s C=0.44 mm/s

A: z/r=0.14 (experimental)

B: z/r=0.28 (experimental)

C: z/r=0.42 (experimental)

CFD Modeling of Trickle Bed Reactors

SINGLE PHASE FLOW Inertial Flow Structures were Captured Accurately by CFD Models Velocity Distribution in Unit Cells Resembles that in a Packed Bed Ergun Parameters may be Obtained through Unit Cell Approach for Semi-structured Packed Bed Unit Cell Approach may be Extended to Simulate Two Phase Flows to Understand Wetting
CFD Modeling of Trickle Bed Reactors

LIQUID SPREADING ON SOLID SURFACES


Monitor Computer

Light Diffuser

Drop Rest on Flat Plate

Light

8.79mm 1mm

10.4mm

Drop Flow Over Pellet

CCD Camera

CFD Modeling of Trickle Bed Reactors

DROP IMPACT ON SOLID SURFACE

CFD Modeling of Trickle Bed Reactors

DROP IMPACT ON SOLID SURFACE

CFD Modeling of Trickle Bed Reactors

FLAT SURFACE

t=0ms

t=45ms

t=0ms t=36ms

(a)

(d)

t=10ms

t=45ms

t=16ms

t=48ms

(b) (e) t=25ms

t=210ms

t=20ms

t=240ms

(c) (f)

CFD Modeling of Trickle Bed Reactors

DYNAMICS OF DROP IMPACT

CFD Modeling of Trickle Bed Reactors

MODELS FOR INTERPHASE COUPLING?

Drop Shape at 12 ms

Wall Shear Stress on Solid Surface, red~100 Pa

Shear Strain on Gas-liquid Interface


CFD Modeling of Trickle Bed Reactors