1.

1 Saturator

1.1.1 Process Description

The purify gas (natural gas without sulphur) was enter the saturator unit and in same time the
steam inject was into saturator. This reactor using heterogeneous reaction where solid act as a
catalyst and liquid-gases as reactant. Saturator is basically to saturate the natural gas with water.
In this equipment, the fresh feed is natural gases (contain hydrogen, nitrogen and methane gas)
enter the vessel at temperature 25°C with total molar flow rate is 38627.52 mol per hours and at
pressure about 1 bar gauge (normal). Steam water temperature enter the 200°C comes from
distillation column process, pressure of the water is 20 bar gauge and the water molar flow rate is
8596.426 mol per hour. The natural gas feed in the separator by flow through process line 1.
Then it will suck by pump (P–112) and enter the reactor, after that it recycle for first time
without chemical reaction, however the natural gas been mixed with the water at stream line 3.
The mixture of water + natural gas been heated by heat exchanger and fed back into separator
where at this process (reactor), this gas been saturated with water and the saturated gas flow
through line 4. In this saturator, the operating condition is temperature 80°C and pressure
approximate about 20°bar.

1 2
SATURATOR 80°C
2
(FIXED BED REACTOR)
0
25°C 4

H2O from
distillation
column 3

200°C

Figure 7.1: Saturator (fixed bed reactor) schematic diagram

The chemical reactions occur in saturator are:

CH4 + H2O  CO + 3H2 (1)

CO + H2O  CO2 + H2 (2)

Table 7.1: Mass balance in saturator (in molar flow rate per hour)

Component Stream 1 Stream 2 Stream 3 Stream 4

H2 36004.64 35284.55 6351.218 6154.648474

CO 0 2160.278 1771.428 894.4209206

N2 222.5741 222.5741 222.5741 222.5741283

CH4 2400.309 240.0309 240.0309 240.0309227

CO2 0 0 0 239.7191942

CH3OH 0 0 0 0

H2O 0 8596.426 8596.426 0

TOTAL 38627.52 46503.86 17181.68 7751.39364

1.1.2 Type of reactor

The saturator in this project can categorized as plug flow reactor with the specific function as
Fluidized Bed Reactor (FBR). FBR it is has a lot of advantages such as excellent gas liquid
contacting, no hot spot even with highly exothermal reactions, good gas to particle and bed to
wall heat transfer and the ease of liquid handling. This reactor is design to produce carbon
monoxide and carbon dioxide through reaction with steam water (from the distillation column)
and with Zeolite Socony Mobil–5 (ZMS-5) as catalyst. Temperature of this reactor is
maintained at 80°C and pressure is approximately 20 bars. The process involved is highly
exothermic hence the cooling system is implemented to sustain the removal of heat because the
steam injected into reactor about 200°C.

Figure 7.2: Kvaerner’s Methanol Synthesis Plant

1.1.3 Gas and Catalyst Analysis

Gas and solid analysis is very important in the FBR design because its affect the fluid dynamic
behaviour of FBR. Particle and gas play as a key role in successful of designing fluidized bed
reactor. The critical pressure drop ratio, hole size, geometry and spacing.

Table 7.2: Properties of Natural gas

No Component Molecular Weight Viscosity Molar Flow Density

(kg/kmol) (kmol/h)
(N.s/m2) (kg/m3)

1 Nitrogen 28.01 0.0103 222.5741 0.0040

2 Methane 16.04 0.0073 2400.309 0.0001

3 Hydrogen 2.02 0.0010 36004.64 0.0007

Source: Perry Chemical Engineering Handbook, Prediction and Correlation of physical

Properties, Vol.2, Pg. 2-363

Refer at APPENDIX A

0.0095 0.0103 0.0703 0.001

μm = + + + =0.0088 N . s /m 2
1+0.622 1+ 4.139 1+104.55 1+2.876

Total Partial pressure = pressure of FBR = 200kPa

Total of gas mixture = 0.0088 N.s/m2

Table 7.3: The properties of solid (catalyst)

Variable Value

Density (kg/m3) 1245

 Diameter (m) 0.003
No Component Molecular Viscosity Pc (bar) Tc (°K) Tr (°K)
Shape Spherical
Weight
2
(N.s/m )
(kg/kmol)

1 Methane 28.01 0.0.073 46 190.6 1.403

2 Nitrogen 28.01 0.0103 33.9 348.15 1.403

3 Hydrogen 2.02 0.0010 13 348.15 1.403

Zeolite Socony Mobil-5 (ZMS-5) is in solid form.

Table 7.4: Properties of natural gas

Source: Perry Chemical Engineering Handbook, Prediction and Correlation of physical

Properties, Vol.2, Pg. 2-363

Appendix

Viscosity for each component

For prediction of the vapor viscosity of pure hydrocarbons at low pressure (below Tr of 0.6), the
method of Stiel and Thodos101 is themost accurate. Only the molecular weight, the critical
temperature, and the critical pressure are required. Equation (1.0) with values ofN from Eq.
(1.10) and (1.11) is used.

1 2

μ=4.6 ×10−4 (N)

( MW )( Pc )
2 3
(Eq 1. 0)
Tc 1/ 6
N = 0.0003400Tr0.94 for Tr <1.5 (Eq 1.10)

N = 0.0001778(4.58Tr - 1.67)0.625 for Tr >1.5 (Eq 1.11)

Assumption; Temperature (Tc) for all gases include ethylene, isobutene, nitrogen and hydrogen
are same which equal to 80°C to the reactor.

Viscosity for Gas Mixture

For prediction of the vapour viscosity of the gaseous mixture of hydrocarbons and non
hydrocarbons gases at low pressures below a Tr than 0.6, The method of Wilke and Bromley is
recommended

General equation from Perry Handbook’s (Bromley and Wilke)

μ n
μ1 μ1 μ1 μ1 μ1
m= ∑ n
= n
= n
= n
= n
x x x x xj
i=1
1+ ∑
j=1
j≠ 1
[ ]
Qij j
xi
1 +∑
j=1
[ ]
Q1 j j
x1
1+ ∑
j=2
[ ]
Q2 j j
x2
1+ ∑
j=3
[ ]
Q3j j
x3 [ ]
1+ ∑ Q 4 j
j=4 x4

Q 1 1 2

ij=¿
1+
[ ][ ]]
ui
uj
2 mj
mi
4

1/2
¿
mj
[ ]
√ 8 1+
mi

For Nitrogen, Let i=1

1 1 2
u m1 1 2

Q11 =
1+ 1
u1 [[ ] [ ] ] [ [ 2

m1
1 /2
4

=
1+
0.0095
0.0095
1

][
2 28.05
28.05
1/ 2
]]
4

=0.500
m 28.05
√8 1+ 1
m1 [ ] [
√ 8 1+
28.05 ]
 1 1 2
u1 m2 1 2

Q 12=
1+
[ ] [ ] ] [[
u2
2

m1
4

1/ 2
=
1+
0.0095
0.0103
1

][
2 58.12
28.05
1 /2
]]
4

=0.470
m 58.12
[ ]
√ 8 1+ 2
m1 [
√ 8 1+
28.05 ]
1 1 2
u m3 1 2

Q13=
[ [ ] [ ] ] [[
1+ 1
u3
2

m1
4

1/ 2
=
1+
0.0095
0.0073
1

][
2 28.01
28.05
1/2
]]
4

=0.575
m 28.01
[ ]
√ 8 1+ 3
m1 [
√ 8 1+
28.05 ]
1 1 2
u1 m4 1 2

Q 14=
1+
[ [ ] [ ] ] [[
u4
2

m1
4

1/ 2
=
1+
0.0095
0.0010
1

][
2 2.02
28.05
1/ 2
]]
4

=0.989
m 2.02
√ 8 1+ 4
m1 [ ] [
√ 8 1+
28.05 ]
n
x x1 x x x
j=1
[ ] [ ][ ][ ][ ]
∑ ¿ Qij x j
i
= Q11
x1
+ Q12 2 + Q13 3 + Q14 4
x1 x1 x1

n
x x1 x x x
j=1
[ ] [ ][ ][ ][ ]
∑ ¿ Q1 j x j
i
= Q 11
x1
+ Q 12 2 + Q 13 3 + Q 14 4
x1 x1 x1

n
x 0.84 0.1 0.01 0.05
j=1
[ ][
∑ ¿ Q1 j x j
i
= 0.500
0.84 ][
+ 0.470
0.84 ][
+ 0.575
0.84
+ 0.989
0.84 ][
= 0.622 ]

For Methane, Let i=2

1 1 2
u2 m1 1 2

Q 21=
1+
[ ] [ ] ] [[
u1
2

m2
4

1/ 2
=
1+
0.0103
0.0095
1

][
2 28.05
58.12
1 /2
]]
4

=0.366
m 28.05
[ ]
√ 8 1+ 1
m2 [
√ 8 1+
58.12 ]
 1 1 2
u2 m2 1 2

Q 22=
1+
[ ] [ ] ] [[
u2
2

m2
1/ 2
4

=
1+
0.0103
0.0103
1

][
2 58.12
58.12
1 /2
]]
4

=0.500
m 58.12
[ ]
√ 8 1+ 2
m2 [
√ 8 1+
58.12 ]
1 1 2
u m3 1 2

Q23=
[ [ ] [ ] ] [[
1+ 2
u3
2

m2
1/ 2
4

=
1+
0.0103
0.0073
1

][
2 28.01
58.12
1 /2
]]
4

=0.575
m 28.01
[ ]
√ 8 1+ 3
m2 [
√ 8 1+
58.12 ]
1 1 2
u2 m4 1 2

Q 24=
1+
[ ] [ ] ] [[
u4
2

m2
1/ 2
4

=
1+
0.0103
0.001
1

][
2 2.02
58.12
1 /2
]]
4

=1.015
m 2.02
[ ]
√ 8 1+ 4
m2 [
√ 8 1+
58.12 ]

n
x x1 x x x
j=1
[ ] [ ][ ][ ][ ]
∑ ¿ Q2 j x j
i
= Q21
x2
+ Q22 2 + Q 23 3 + Q24 4
x2 x2 x2

n
x 0.84 0.1 0.01 0.05
j=1
[ ][
∑ ¿ Q1 j x j
i
= 0.366
0.1 ][
+ 0.500
0.1
+ 0.575 ][
0.1
+ 1.015
0.1 ][
=4.139 ]

For methane, Let i=3

 1 1 2
u3 m1 1 2

Q 31=
1+
[ ] [ ] ] [[
u1
2

m3
1/ 2
4

=
1+
0.0073
0.0095
1

][
2 28.05
28.01
1 /2
]]
4

=1.130
m 28.05
[ ]
√ 8 1+ 1
m3 [
√ 8 1+
28.01 ]
1 1 2
u m2 1 2

Q32=
[ ] [ ] ] [[
1+ 3
u2
2

m3
1/ 2
4

=
1+
0.0073
0.0103
1

][
2 58.12
28.01
1 /2
]]
4

=0.407
m 58.12
[ ]
√ 8 1+ 2
m3 [
√ 8 1+
28.01 ]
1 1 2
u3 m3 1 2

Q 33=
1+
[ [ ] [ ] ] [[
u3
2

m3
1/ 2
4

=
1+
0.0073
0.0073
1

][
2 28.01
28.01
1 /2
]]
4

=0.500
m 28.01
[ ]
√ 8 1+ 3
m3 [
√ 8 1+
28.01 ]
1 1 2
u m4 1 2

Q34=
[ [ ] [ ] ] [[
1+ 3
u4
2

m3
1/ 2
4

=
1+
0.0073
0.001
1

][
2 2.02
28.01
1/2
]]
4

=1.012
m 2.02
[ ]
√ 8 1+ 4
m3 [
√8 1+
28.01 ]

n
x x1 x x x
j=1
[ ] [ ][ ][ ][ ]
∑ ¿ Q3 j x j
i
= Q 31
x3
+ Q 32 2 + Q 33 3 + Q 34 4
x3 x3 x3

n
x 0.84 0.1 0.01 0.05
j=1
[ ][
∑ ¿ Q1 j x j
i
= 1.130
0.01 ][
+ 0.407
0.01 ][
+ 0.500
0.01
+ 1.012
0.01 ][
= 104.55]
For hydrogen, Let i=4

1 1 2
u4 m1 1 2

Q 41=
1+
[ [ ] [ ] ] [[
u1
2

m4
1/ 2
4

=
1+
0.001
0.0095 ][
1
2 28.05
2.02
1/ 2
]]
4

=0.128
m 28.05
[ ]
√ 8 1+ 1
m4 [
√ 8 1+
2.02 ]
1 1 2
u m2 1 2

Q42=
[ [ ] [ ] ] [[
1+ 4
u2
2

m4
1/ 2
4

=
1+
0.001
0.0103 ][
1
2 58.12
2.02
1 /2
]]
4

=0.099
m 58.12
[ ]
√ 8 1+ 2
m4 [
√ 8 1+
2.02 ]
1 1 2
u4 m3 1 2

Q 43=
1+
[ ] [ ] ] [[
u3
2

m4
1/ 2
4

=
1+
0.001
0.0073 ][
1
2 28.01
2.02
1/ 2
]]
4

=0.138
m 28.01
[ ]
√ 8 1+ 3
m4 [
√ 8 1+
2.02 ]
1 1 2
u m4 1 2

Q44 =
[ ] [ ] ] [[
1+ 4
u4
2

m4
1 /2
4

=
1+ ][ ]]
0.001
0.001
1
2 2.02
2.02
1/ 2
4

=0.500
m 2.02
√ [ ]
[ ]
√ 8 1+ 4
m4
8 1+
2.02
 n
x 0.84 0.1 0.01 0.05
j=1
[ ][
∑ ¿ Q1 j x j
i
= 0.128
0.05 ][
+ 0.099
0.05
+ 0.138
0.05
+ 0.500 ][
0.05
=2.876 ][ ]

From general equation

μ n
μ1 μ1 μ1 μ1 μ1
m= ∑ n
= n
= n
= n
= n
x x x x xj
i=1
1+ ∑
j=1
j≠ 1
[ ]
Qij j
xi
1 +∑
j=1
[ ]
Q1 j j
x1
1+ ∑
j=2
[ ]
Q2 j j
x2
1+ ∑
j=3
[ ]
Q3j j
x3 [ ]
1+ ∑ Q 4 j
j=4 x4

0.0095 0.0103 0.0703 0.001

μm = + + + =0.0088
1+0.622 1+ 4.139 1+104.55 1+2.876

Total of gas mixture = 0.0088 N.s/m2

1.1.4 Reaction in Fluidized Bed Reactor

Basically, there are 2 steps occur during the reaction in FBR which includes initiation,
propagation and termination. All reaction occurs is highly exothermic.

CH4 + H20  CO + 3H2O

CO + H2O  CO2 + H2

−d C A
−r a = =K 1 P A PB + K 2 P A PB + K 3 P A PB
dt

−d C A
−r a = =( K 1+ K 2+ K 3) P A PB
dt

K T =K 1 + K 2

Table 7.5: Properties data of reaction

REACTION Kcal Kmol Kmol

Ei [ Kmol ] K0i
[ m . h .( KPa)2
3
] Kn
[ 3
m . h . KPa ]
1 15000 1.59 ×105 1.5 ×10−4

2 20000 8.83 ×105 8 ×10−7

Reaction rate constant please refer to APPENDIX B

Total of rate constant,

Kmol
K T =0.0001508 3
m . h . KPa
For the multiple reactions

−d C A
−r a = =K 1 P A PB + K 2 P A PB + K 3 P A PB
dt

−d C A
−r a = =( K 1+ K 2+ K 3) P A PB
dt

K T =K 1 + K 2 + K 3

−E1 Kmol
K 1=K o 1 exp [ ]
RT
=1.59 ×105 exp [
−15000
1.986(363.15)
=0.00015 3 ]
m . h . KPa

−E2 Kmol
K 2=K o 2 exp [ ]
RT
= 8.83× 105 exp [
−20000
1.986( 363.15)
= 8× 10−7 3]
m . h. KPa

Kmol
K T =K 1 + K 2=0.00015+ 8× 10−7 =0.0001508 3
m . h . KPa

1.1.5 Reactor Volume, Diameter and Height

This fluidized bed reactor is assumed as PFR (plug flow reactor) and at steady state condition.
From equation (H. Scott Fogler, Elements of Chemical Reaction Engineering, 3rd Edition)

Input = Output + Disappearance + Accumulatio (4.1)

Since accumulation is zero hence the equation 4.1 become equation 4.2

Input = Output + Disappearance (4.2)

Rearrange equation (4.2) to produce (4.3)

F A=( F A + d F A ) + (−r A ) dV F A=d [ F A 0 (1− X) ]+ ( −r A ) dV F A=d [ F A 0−F A 0 X ¿ ] + (−r A ) d

F A 0 dX=(−r A ) dV
Then integrate reaction (4.3) to (4.4) refer to APPENDIX C

CA
1 −d C A V
2 ∫ =
C A 0 k T ( RT ) CA 0 C B C A F A 0

Arrange equation (4.4) to (4.5)

XA
1 −d X A V
2∫
=
C A 0 k T ( RT ) 0 ( 1−X A ) ( M − X A ) F A0

Integrate equation (4.5) to (4.6)

1
2
[ (
1
C A 0 k T ( RT ) (M −1)
ln
(M −X A )
M ( 1− X A )
=
V
FA 0 )]
Integrate (4.6) to determine equation (4.7) volume of reactor

FA 0
V=
1
[ (
C A 0 k T (RT )2 ( M −1)
ln
(M −X A )
M ( 1−X A ) )]

1.1.5.1 Volume of the FBR

m3
402250.77
h 1
V= 2
( KPa ) . m 3
Kmol [ |−0.9964|
ln (|−179.845|)
]
( 48545882.78
Kmol )( 0.000151
m . h . ( KPa )2
3
)
V =285.935m3
1.1.5.2 Diameter of the FBR
3 285.935
D=
√ 2.356
=4.951 m

1.1.5.3 Height of the FBR

Height of Reactor=4.951 m× 3=14.853 m

1.1.5.4 Calculation of Diameter and Height of Reactor

According to Fluidized Bed Technology in Material Processing, the ratio of diameter to height is
1:3. Hence the reactor is in cylindrical shape.

C B 0 P B RT PB 0.578
M= = × = = =0.0036
C A 0 RT P A P A 160.789

M −1=0.0036−1=−0.9964

M − X A=−0.9964−0.84=−1.8364

1− X A=1−(−1.8364)=2.8364

FA 0
V=
1
[ (
C A 0 k T (RT )2 ( M −1)
ln
(M −X A )
M ( 1−X A ) )]
 m3
402250.77
V=

(
2
( KPa ) . m 3
)(
h
Kmol [ 1
ln (|
−1.8364
|−0.9964| 0.0036 ×2.8364 |)]
48545882.78
Kmol
0.000151 3
m . h . ( KPa )
2
)
m3
402250.77
h 1
V= 2
( KPa ) . m 3 Kmol [ |−0.9964|
ln (|−179.845|)
]
( 48545882.78
Kmol )( 0.000151 3
m . h . ( KPa )
2
)
V =285.935m3

π D2 3
Volume of cylinder = ×3 D=285.935 m
4

285.935 m3
D=
√
3

2.356
=4.951 m

Height of Reactor=4.951 m× 3=14.853 m

1.1.6 Residence Time

C A 0 V 160.785× 285.935 m3
τ= = =0.114 h=6.8575 min
F Ao m3
402250.77
h

1.1.7 Vapor Velocity

Basically, gas velocity is the main parameter that should be control in designing fluidized bed
reactor. There are three types superficial gas velocity which is at minimum fluidizing conditions
(Umf), terminal gas velocity (Ut) and superficial gas velocity (U0). The superficial gas velocity
should be between the other two in order to keep the solid fluidized smoothly.

1.1.8 Calculation of superficial gas velocity at minimum fluidizing conditions (Umf)

Generally Archimedes number given as (Fluidization Engineering, pg 69)

d p3 ρ g ( ρs− ρg ) g
Ar =
μ2

Kg Kg Kg m

Ar =
(
( 0.003 m )3 0.0211
m3 )( m m )
1350 3 −0.0211 3 9.81 2
s
=0.0974
2
N .s
(0.0088 2
m )
Reynolds number at minimum fluidizing conditions for coarse particle

1
2 2
ℜp ,mf = [ ( 28.7 ) +0.0494 Ar ] −28.7

1
2 2
ℜp ,mf = [ ( 28.7 ) +0.0494(0.0974) ] −28.7=8.38 ×10−5

( 8.38× 10−5 ) ×0.0088 N .2s

ℜ p ,mf × μ m m
U mf = = =0.0116
d p × ρg Kg s
0.003 m× 0.0211 3
m

1.1.8.1 Calculation superficial gas velocity (U0)

m m
U 0 =64 ×U mf =64 × 0.0116 =0.7424
s s

1.1.8.2 Calculation for terminal gas velocity (Ut)

Generally, Reynolds number at superficial gas velocity (Fluidization Engineering, page XXV).
 m Kg
0.003 m× 0.7424 ×0.0211 3
d p× Uo× ρg s m
ℜp = = =0.0053
μ N .s
0.0088 2
m

Drag coefficient for spherical particles (Haider and Levenspiel, 1986)

24 0.4607 ℜ p
C D = ℜ +3.3643 ℜ p0.3471 +
p ℜ p +2682.5

24 0.4607(0.0053)
CD= +3.3643( 0.0053)0.3471+ =4528.8476
0.0053 (0.0053)+ 2682.5

When a particle of size dp falls through a fluid, it’s terminal free fall velocity can be estimated
from fluids mechanics by the expression

1
Kg Kg m

[ ( )( )
]
2
1 4 ( 0.003 m ) 1350 3 −0.0211 3 9.81 2
4 d p ( ρs × ρg ) g 2 m m s
Ut=
[ 3 ρgC D ] =
( Kg
)
3 0.0211 3 ( 4528.8476 )
=0.5544
m
s
m
1.1.9 Heat Transfer Coefficient

1.1.9.1 Thermal Conductivity of Gases, Kg

Table 7.6: Properties of gas

Critical Critical Heat T

T r=
Temperature, Pressure, Pc(bar) capacity, Tc
Tc(°K) Cpg
(J/Kmol.°K
)

Methane 190.6 40.6 2475.8 0.8133

Nitrogen 126.2 33.9 1894.5 2.8776

Hydrogen 33.3 13 1875.7 10.9054

Methane

2/ 3
1/ 2 101.325
1/ 6
λ=( T c ) ( M ) ( Pc )
2 /3
101.325
1 /6
λ=( 190.6 ° K ) ( 16.04 mol /kg )
1 /2
( 4113.795 KPa ) =0.8133

K c =10−7 ( 14.52 T r−5.14 )

2 /3
( Cλ )
p

J
−7
K c =10 ( 14.52 ( 1.2828 )−5.14 )
2 /3
( 3065.7
Kmol . K
0.9933 )
=0.0017
W
m. K

Nitrogen
 1/ 2 2/ 3
Kg 101.325
λ=( 126.20 ° K )
1 /6
( 28.2
Kmol )( 3394.3875 KPa ) =1.1445

J
K c =10−7 ( 14.52 ( 2.8776 ) −5.14 )
2 /3
( 1894.5
Kmol . K
1.1445 )
=0.0018
W
m.K

Hydrogen

1 /2 2 /3
Kg 101.325
λ=( 33.3 ° K )
1 /6
( 2.016
Kmol )( 1296.96 KPa ) =0.4654

J
K c =10−7 ( 14.52 ( 10.9054 )−5.14 )
2 /3
( 1875.7
Kmol . K
0.4654
=0.0115 )W
m.K

1.1.9.2 Total thermal conductivity of the gases, Kg

W
K g=0.0017+ 0.0014+0.0018+0.0115=0.0164
m.K