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I. INTRODUCTION
The whole formaldehyde production amounts 32.5 million
tons per year in 2012, While demand increase similarly due to
the versatility of formaldehyde which is intermediate in
chemical synthesis such as the many resin product for example
urea formaldehyde, melamine formaldehyde, phenol
formaldehyde, polyoxymethylene and methylenediphenol
diiosocyanate etc. These resins are used to polywood
production and the property adaptation. Furthermore the
formaldehyde solution (formalin) can destroy bacteria and
fungi for conservation of dead creature.
[10]
(1)
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CH3OH CH2O H2
(2)
(3)
(4)
H2CO CO H
(5)
CH2 O + H2 O CH3O2 H
CH2O HO(CH2O) ; n=8-10
(6)
(7)
Step i
Reaction mechanism
O2 (g) + * O2*
O2* + * 2O*
H2CO* + O* H* + HCOO*
10
11
CO2* CO2 + *
The * signifies a surface site and X* is an adsorbed species.
1 Ct
(8)
gas
Ci
(1 p )ik rik
z
k
Ci
Ci
H rk (1 ) ik rik
z
k
Parameters
Ci
= Component i (mol/m3 void
Cpgas = Specific heat capacity of gas (kJ/kgK)
Cpsolid= Specific heat capacity of solid
or catalyst (kJ/kgK)
Ggas = Mass flux of gas (kg/m3s)
r ik = Rate of reaction K (kJ/s m3 catalyst)
t
= time (s)
T
= Temperature in reactor (K)
U
= Ggas / gas= Superficial velocity (m/s)
z
= Axial position (m)
(9)
space)
TABLE II.
Step i
elementary reaction
Hi (KJ/mol)
Si (J/molK)
-32.955
-82.317
-37.735
-120.500
-83.069
-44.969
42.843
-89.129
-52.856
71.413
19.324
75.059
51.250
132.15
47.478
103.27
-26.153
-78.897
10
-238.98
92.782
15.082
51.745
11
gas
solid
i
Hrk
1
1
1
CH3OH +
O2 H2CO + H2 + H2O
4
2
2
1
H2CO +
O2 CO2 + H2
2
k5KA (
r5
pCH3OH p H2 O
)( )
p
p
p
1
1
p
O
(1 K c2 ( 2 ) 2 ) 2
p
p O2
) (
p O2
1
2
p H CO p H
k10 K B ( ) ( 2 )( 2 )
p
p
p
r10
1
1
p
O
(1 K c2 ( 2 ) 2 ) 2
p
K i T exp (
df (x)
f (x) f (x)
lim
0
dx
x
x
f x
Lump
constant
(18)
Si (J/molK)
KA
-117
-18
KB
-171
-80
KC
-165
-121
f x f x h f x
(19)
1
f x h 2f x f x-h
h2
(20)
Using equation (23) and (24) apply to the fixed bed reactor
model in equation (10) - (11) following expression
( 1 p
(14)
1
f x h f x
h
TABLE III. THE ENTHALPY AND ENTROPY CHANGE FOR LUMP CONSTANT
f x
(13)
(17)
(12)
Si
H
) (exp ( i ))
R
RT
(11)
(16)
Cnj,i1 Cnj,i
t
n
n
u C j,i 1 C j,i 1
1 jk rki
z
2
k
(21)
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(22)
model in the adiabatic fixed-bed reactor under UHV condition
G gas Cpgas Tin1 Tin1
used many assumptions as flow pattern of fluid depends only
(H rk )(1 ) jk rki
z
2
z-direction and disregard mixed of fluid, property constant,
k
process has two reaction that is oxidation reaction of methanol
The simulation both component i and temperature used
and formaldehyde. The mathematic solution is fully explicit
feed and temperature inlets, process designs and operation
method that is simpler method for partial differential equation.
conditions that depend on time called dynamic simulation.
The simulation nearly evaluate with experiment data of
previous literature. The model can used in rang 500-975 K
III. Results and discussion
In this section refers formaldehyde synthetic process
simulative comparison with the previous literature for
demonstration of mathematics model can simulate nearly true
process. Figure 2, an expression of formaldehyde synthesis and
byproduct (carbon dioxide) that depends operation temperature
compares between the process simulation and [8], a few
increment of formaldehyde synthesis because of decomposition
to carbon dioxide. When temperature higher than 548 K, the
vary increment of formaldehyde synthesis and highest at 948
K, the temperature of formaldehyde synthesis decline due to
formaldehyde decomposition to carbon monoxide, in this work
doesnt explain to carbon monoxide because of complicated
formation mechanism.
The carbon dioxide synthesize at low temperature when
temperature higher than 548 K, carbon dioxide synthesis
decline of temperature so carbon dioxide synthetic reaction
occurs at low temperature. Figure 3, the comparison of process
simulation and the experiment data of [10], this expression as
figure 2. Thereby demonstrative simulation of mathematic
model can describes formaldehyde synthesis in reactor under
industrial conditions. Figure 2 and 3, results of simulation has
high accuracy at low temperature but lower accuracy in higher
temperature because rate of reaction in [1, 2] describes
formaldehyde synthesis at low temperature, an accuracy
describes by least square amount 10.01% and 8.49%
TABLE IV. ARRHENIUS PARAMETERS FOR TWO LIMITING STEPS
Step i
Arrhenius parameters
Ai (A-1)
Hi (J/molK)
-32.955
-82.317
-37.735
-120.500
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