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ChE 402
Group: 6(A1)




Experiment # 1

Influence of Catalyst Composition and Method of Preparation
on Rate of Methane Synthesis






Date of Performance: 17.04.2011



Date of Submission: 08.05.2011














Md. Abdus Sabuj


#0602028
L4 T-1


Department of Chemical Engineering, BUET


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Summary

The objective of this experiment was preparation of a solid catalyst and using it to methane
synthesis. Catalyst was prepared with a ratio of 3:7 of Nickel oxide-aluminum oxide (NiO-
Al
2
O
3
) by co-precipitation process from nickel nitrate and aluminum nitrate solution. Nickel
oxide is the active component and aluminum oxide is the support. KOH solution was used in
precipitation for changing the pH of the solution. Washing, filtration, calcinations, pellet
forming was performed. Then the prepared catalyst was used as catalyst in the reactor after
reduction by pure hydrogen for methane synthesis. From the gas chromatographic analysis of
the products, the output gas composition was obtained. The conversion of carbon mono-oxide
was 48.23 % and selectivity was 0.44 respectively.

































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Chemicals Used:

Nickel Nitrate, Ni (NO
3
)
2.
6H
2
O
Aluminum Nitrate, Al (NO
3
)
3.
9H
2
O
Potassium Hydroxide, KOH
Distilled water, H
2
O
Carbon dioxide, CO
2

Hydrogen, H
2



Reactions Involved:

In preparing Nickel catalyst supported on Alumina; Nickel Nitrate and Aluminum Nitrate

salts may be used.

Titration: Ni (NO
3
)
2
+ 2KOH Ni (OH)
2
+ 2KNO
3
Al (NO
3
)
3
+ 3KOH Al (OH)
3
+ 3KNO
3


Calcinations: Ni (OH)
2
NiO + H
2
O

2Al (OH)
3
Al
2
O
3
+ 3H
2
O

NiO + H
2
Ni + H
2
O, H
O
= - 0.8 kcal/ mole



The principal reactions which occur in the methanation process are:

CO
2
+ H
2

Ni
CO + H
2
O, H
O
= + 9.8 kcal/ mole

CO + 3H
2

Ni
CH
4
+ H
2
O, H
O
= - 49.3 kcal/ mole

CO
2
+ 4H
2

Ni
CH
4
+ 2H
2
O, H
O
= - 39.5 kcal/ mole







350
0
C
350
0
C

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Procedure:

Calculated amount of Ni(NO
3
)
2
salt and Al(NO
3
)
3
salt by using a digital balance was
weighed out.
Both the salts into a beaker containing 500 ml of distilled water were dissolved.
Calculated amount of 7(N) KOH weighed out and dissolved it to distilled water.
A motor driven stirrer was started.
The solution of nitrates was stirred continuously and slowly but the solution of KOH
was added steadily until the pH of the solution became 7.0
Continuously the pH of the solution was checked by using pH paper.
The solution was divided into 4 portions and distilled water was added to each portion
(500ml each).
The precipitate was allowed to settle and then filtered.
The filter cake was dried and then calcinated for 3 hours at 350
0
c under atmospheric
pressure.
The calcinated catalyst particles were crushed.
Pellets of catalyst particles were prepared with the help of hand press (about 400
bars).
Gas chromatography method was used to determine catalyst activity and selectivity.



















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BLOCK DIAGRAM OF CATALYST PREPARATION AND METHANE SYNTHESIS

Catalyst Preparation

Ni (NO
3
)
2


























Methanation Process














Figure 1.1: Block Diagram of Catalyst Preparation and Methane Synthesis



Gas Chromatograph
Separation through 16-25 mesh
Pellet Formation
Filter cake
Washing
Drying
(130-140
0
C)
Calcinations
Separation through 150 meshes
MTN
Reduction
Catalyst
N
2
, H
2
O
Gas outlet
KOH
Solution (pH 7)
Al (NO
3
)
3

Gas inlet
CO, N
2
, H
2

N
2
, H
2


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Observed Data:

Molecular weight of Al (NO
3
)
3
.9H
2
O = 375.13 g/ mol
Molecular weight of Ni (NO
3
)
2
.6H
2
O = 290.81 g/ mol

Basis:
10 g of catalyst
NiO: Al
2
O
3
= 3:7

Inlet gas flow:
H
2
= 20 L/ hr
N
2
= 25 L/hr
CO = 10 L/hr

Outlet gas flow = 4.8 x 100 cm
3
/ min

Catalyst weight = 4.2 g

Operating Condition:
Reactor pressure = 750 mm Hg
Vapor pressure of water at 750 mm Hg and 31.1
0
C = 31.824 mm Hg
Wet test meter temperature = 31
0
C


Weight of Ni (NO
3
)
2
.6H
2
O taken = 22.03 g
Weight of Al (NO
3
)
3
.9H
2
O taken = 27.25 g


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Calculated Data:

Inlet gas flow (at Operating Condition)
H
2 =
0.99 g-mole/hr
N
2 =
0.79 g-mole/hr
CO = 0.396 g-mole/hr
Outlet gas flow 2.37 g-mole/hr
Dry gas flow at NTP = 2.27 g-mole/hr

Outlet gas composition mole % from Gas Chromatographer:

Species Composition [mole %]
H
2
44.14
N
2
5.39
CH
4
12.32
CO 10.32
CO
2

27.83


Outlet gas flow rate from Gas Chromatographer:

Species Flow rate [g-mole/hr]
H
2
1
N
2
0.1223
CH
4
0.2797
CO 0.2343
CO
2
0.6317





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Sample Calculation:

Basis: 10 g of catalyst mixture having a ration of NiO: Al
2
O
3
= 3: 7

Now,
NiO+Al
2
O
3
=10 g
Amount of NiO in catalyst
100
10 30
= 3 g
Amount of Al
2
O
3
in catalyst
100
10 70
= 7 g

Determination of the amount of Ni(NO
3
)
2
. 6H
2
O

and Al(NO
3
)
3
.9H
2
O

required:
Mole of NiO = (wt of NiO) / (MW of NiO)
= 3 / 74.7
= 0.0401 mol

[1 mole of NiO 1 mole Ni (OH)
2
1 mole Ni (NO
3
)
2
]

Wt of Ni(NO
3
)
2
. 6H
2
O

= mole of Ni (NO
3
)
2
MW of Ni (NO
3
)
2
.6H
2
O

= 0.0401 290.7
= 11.65 g

Mole of Al
2
O
3
= (wt of Al
2
O
3
)/ (MW of Al
2
O
3
)
= 7 / 102
= 0.0241 mol

[1 mole of Al
2
O
3
2 mole of Al (OH)
3
2 mole of Al(NO
3
)
3
]

Wt of Al(NO
3
)
3
.9H
2
O

= mole of AL(NO
3
)
3
mw of AL(NO
3
)
3
.9H
2
O
= 2 0.0241 375.13
= 18.08 g



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Amount of KOH used= 55 ml

Inlet gas flow rate (Operating Condition)

H
2 =

22.4L 760mmHg 304K
mole . 1g 750mmHg 273K 25L/hr


= 0.99 g-mole/hr
N
2 =
22.4L 760mmHg 304K
mole . 1g 750mmHg 273K 20L/hr


= 0.79 g-mole/hr
CO =
22.4L 760mmHg 304K
mole . 1g 750mmHg 273K 10L/hr


= 0.396 g-mole/hr

Outlet gas flow rate

Outlet gas flow =
1hr 1min
60min 100 x 4.8

mL
=
22.4L 760mmHg 304K
mole . 1g 750mmHg 273K 28.8L/hr



= 2.37 g-mole/hr

Dry gas flow rate
Dry gas flow at NTP =
750
) 824 . 31 750 ( 37 . 2
= 2.27 g-mole/hr

Outlet gas composition mole% from GC
H
2
= 6006 48.47/ 13614 = 21.29 21.23/ 48.23 100% = 44.14 %

N
2
= 127144 5.43/ 264994 = 2.6 2.6/ 48.23 100% = 5.39 %

CH
4
= 226639 8.37/ 319340 = 5.94 5.94/ 48.23 100% = 12.32 %

CO = 253761 6.13/ 312507 = 4.98 4.98/ 48.23 100% = 10.32 %

CO
2
= 683957 1.4 / 71355 = 13.42 13.42/ 48.23 100% = 27.83 %


48.23 (Dry Basis) 100 %





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Outlet gas flow rate from GC at NTP
H
2
= 0.4414 2.27 = 1 g-mole/hr
N
2
= 0.0539 2.27 = 0.1223 g-mole/hr
CH
4
= 0.1232 2.27 = 0.2797 g-mole/hr
CO = 0.1032 2.27 = 0.2343 g-mole/hr
CO
2
= 0.2783 2.27 = 0.6317 g-mole/hr




Conversion, mole% = = = 40.83 %


44 . 0
6317 . 0
2797 . 0
CO
CH
Product Undesired
Product Desired
y Selectivit
2
4























) in ( CO
) out ( CO ) in ( CO
% 100
396 . 0
.2343 396 . 0

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Result and Discussion:

The conversion of the CO in the methane synthesis reaction =40.83 mole %
The selectivity of the methane based on carbon dioxide = 0.44

Form the result, it can be said that the catalyst prepared in this experiment was able to convert
most part of the Carbon Monoxide, but it was not very selective to Methane production. For a
industrially suitable catalyst, both activity and selectivity should be considered as major
criteria.

Catalyst required for methane synthesis solely depends on composition and method of
preparation.

Catalyst influence the rate of the reaction and catalyst activity can be determined from its
selectivity and percent conversion of reactants into the products.

Plant design usually requires that the catalyst be reduced at a temperature not higher than
reactor operating temperature. High activity is associated with high nickel surface area and
stability is obtained by maximizing strength and resistance to sintering.
The reaction rate was not calculated because of the unavailability of adequate data which
would have given a far better knowledge about the influence of catalyst composition on the
reaction rate.