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INTRODUCTION

Formaldehyde is an organic compound with the formula CH2O. It is representing the


simplest form of the aldehyde. Generally, formaldehyde is used to make resins, which are
used as adhesives and binders for plywood. They are also foamed to make insulation or cast
into moulded products.
In this project, we use the catalytic vapor-phase oxidation reaction involving methanol
and oxygen. Catalyst is also necessarily used for this reaction. The catalyst that we used in
this project is Fe-Mo oxide based catalyst which is a metal oxide catalyst. Fe-Mo oxide is
widely used in industry for water purification, as catalysts, for the preparation of advanced
materials and in nuclear reprocessing. The preliminary design of this plant is to produce
30,000 MTPA of formaldehyde from methanol by using this metal oxide catalyst.
According to the information given in the Appendix C, the reactions involved in the
process are as follows:
The yield and conversion of this reaction are defined as:
CH3OH + O2 CH2O + H2O
CH2O + O2 CO + H2O

The yield and conversion of this reaction are defined as:


Yield,Y

no .of moles of formaldehyde produced


no . of moles of methanol converted

Conversion, X

no . of moles methanol converted


no .of moles of methanol been fed

1) REACTOR DESIGN EQUATIONS


CH3OH + O2 CH2O + H2O
CH2O + O2 CO + H2O

A + B C + D (REACTION 1)
C + B E + D (REACTION 2)
Where:

A is methanol
B is oxygen
C is formaldehyde
D is water
E is carbon monoxide
I is nitrogen inert gas

2) MOLE BALANCE

dFA
rA
dW
dFB
rB
dW
dFC
rC
dW
dFD
rD
dW
dFE
rE
dW
dFF
rF
dW
3) RATE LAWS

r ' 1=k ' 1 P

0.75

y 0.75
m
0.5
(1+ y 0.75
m )

r ' 2=k ' 2 P f

Where

At pressure 1.5 atm and 473K


4) RELATIVE RATE LAW
reaction1=

rA1
r
r
r
= B1 = C 1 = D 1
1 1/2 1
1

reaction2=

rC 2
r
r
r
= B 2 = E 2 = D2
1 1 /2 1
1

r ' A =r ' A 1
r ' B =r ' B 1 +r ' B 2
r ' C =r ' C 1+r ' C 2
r ' D=r ' D 1 +r ' D 2
r ' E=r ' E 1

To evaluate the partial pressure of methanol, ideal gas law is needed in which:

pA CA . R.T
where:

CA is the molar concentration of ethanol in (kmol/m3)


T is in (K)
3

R is the gas constant = 0.082 (atm.m3/kmol.K)

5) STOICHIOMETRY
For the gas phase, the concentration can be found as follow:

Ci CT 0 (

CA CT 0 .(

FA T0 P
).( ).( )
FT T P0

CB CT 0 .(

FB T0 P
).( ).( )
FT T P0

CC CT 0 .(

FC T0 P
).( ).( )
FT T P0

CD CT 0 .(

FD T0 P
).( ).( )
FT T P0

CE CT 0 .(

FE T0 P
).( ).( )
FT T P0

CI CT 0 .(

kmole
)
m3

Therefore,

FT T0 P
).( ).( )
FT 0 T P0

FI T0 P
).( ).( )
FT T P0

Then, the inlet pressure P0 is 1.5 atm where the following parameters mean:

C T 0=

P0
=
R T 0

152kPa
kmol
=0.03865 3
3
m
m
8.314 kPa.
(473 K )
kmolK

FT (kmol /h) FA FB FC FD FE FFIF FI

yA 0

FA 0
FT 0

CA 0 y A 0 * CT 0

So the reaction rate expressions will be:

y 0.75
36785.728 0.75
m
r ' 1=0.282 exp(
)P
0.5
RT
(1+ y 0.75
m )
r ' 2=3.001 exp(

Methanol (A):

66412.632
)P f
RT

dF A
=r ' A 1
dW
dF B '
=r B 1 +r ' B 2
dW

Oxygen (B):

Formaldehyde (C):

Water (D):

dFC
=r ' C1 +r ' C 2
dW

dF D
=
dW

Carbon monoxide (E):

r ' D 1+ r ' D 2
dF E
=r ' E 1
dW

6) COMBINATION

METHANOL (A)
dF A
y 0.75
36785.728 0.75
m
=0.282 exp(
)P
0.5
dW
RT
(1+ y 0.75
m )

OXYGEN (B)

0.75

dF B 1
ym
36785.728 0.75
1
66412.632
= 0.282 exp(
)P
+ 3.001 exp(
)P f
0.75 0.5
dW 2
RT
2
RT
(1+ y m )

]
5

FORMALDEHYDE (C)
dFC
y 0.75
36785.728 0.75
66412.632
m
=0.282 exp(
)P
+3.001 exp(
) Pf
0.75 0.5
dW
RT
RT
(1+ y m )

WATER (D)
0.75

dF D
ym
36785.728 0.75
66412.632
=0.282 exp(
)P
+3.001 exp(
)P f
0.75 0.5
dW
RT
RT
(1+ y m )

CARBON MONOXIDE (E)


dF E
66412.632
=3.001 exp(
)Pf
dW
RT

CONVERSION EQUATION

Conversion

FA 0 FA
FA 0

LEVEL 1: DECISION

BATCH VS. CONTINUOUS

For the process synthesis and flow sheeting, this process is worth continuous
mode. The reasons of this decision are mainly based on the capacity and the nature of the
reaction. This process produces around 30,000 MTPA of formaldehyde and the raw materials
are only two, which is methanol and oxygen. The reactions are not too complex that would
not require the use of well-controlled batch reactors. The demand is considerably consistent
and do not change much with years as it is free from any seasonal difficulties.
At this level, the mole balance would be equated in algebraic terms and calculated
through the outmost boundary of the plant as can be seen in Figure 2.1 along with the gross
profitability analysis.

Figure 1: The overall mole balance of the production

ECONOMIC POTENTIAL 1
CH3OH + O2 CH2O + H2O
CH2O + O2 CO + H2O
The reactions need to be conducted with the Fe-Mo oxide catalyst. Based on the
stoichiometry of equation above, for 30,000 MTPA formaldehyde, at least 30,000 MTPA of
methanol and 15,000 MTPA of oxygen gas are required for as the raw material. The
production of side product CO and the price of catalyst needed can be neglected at this level
as compared to other species. The prices of products and raw materials based on their
available purities in global market are listed in Table 1

Table 1 Price Data for Production of Formaldehyde

Components

Price

Methanol
Formaldehyde

RM 1300/MT
RM 6827 /MT

Economic Potential Revenue Raw Material Cost

30,000

MT
RM 6827
MT
RM 1300
formaldehyde
30,000
methanol
year
MT
year
MT

= RM2048810000/year RM39000000/year
= RM2009810000/year

LEVEL 2 DECISSION: INPUT-OUTPUT STRUCTURE OF THE PROCESS


FLOWSHEET
Since a rule of thumb is required in the process design, it is desirable to recover more than
99% of all valuable materials. Thus in the second level of decision, the mole balances are
calculated for the overall system in which the limiting reactant is 100% converted (various
conversions are evaluated inside the process and would appear in the third level of decision).
Figure 3.1 shows the input-output structure of the process.

CH2O

CH3OH
O2 +
N2

Process

CO, O2, N2

H 2O

Figure 3.1: Input-Output Stream of the process


Mole Balances in Term of Extent of Reaction

Analysis of mole balance follows the extent of reaction method. The symbols 1 and 2 are
used to denote the extents of reaction for the first and second reactions (Eq. 1.1), respectively.
The mole balance of all chemical species is generally computed using the correlation as
follows:
n i =n0 + i 1

where

n i

is molar flow rate of the species i and I is the stoichiometric coefficient. Hence,

the final flow rate from Figure 3.1 can be summarised as in Table 3.1.

Species
Formaldehyde
Methanol
Water
Oxygen
Carbon Monoxide

Inlet
0
FM
0
FO2
0

Change
1 - 2
-1
1 + 2
-1/21 1/22
2

Outlet
PF
0
PH2O
PO2
PCO

Table 3.1: Mole Balance for the Second Level of Decision


In total, other than PF, there are 5 unknown variables. Information available to solve those
variables can be detailed out as follows, based on the material and energy balance textbook.
(Rousseau, 2005)
Number of unknown variables in the process

2 Independent reactions

+2

5 equation of extent of reactions

-5

ratio of O2: N2

-1

Total (variables can be calculate specifying one information available)

The remaining information is obtained from the calculation in the mole balance which
included a recycle stream. The x is being optimised based on the EP2.

10

Yield and Reaction Stoichiometry


As mentioned earlier, the yield is the fraction of methanol converted in the reactor that
corresponds to the formaldehyde flow at the reactor outlet. Moreover, this formaldehyde is all
recovered and removed (100% separation efficiency for the second level of decision) from
the process. Hence, for a production of PF, The methanol fed to the process FFM must be
F FM =

PF
Y

(3.1)
Given the composition of the fed methanol is 95% methanol and 5% water, hence
F H 2O =

0.05
F
0.95 FM

(3.2)

For the fed of oxygen


FO 2= F M
(3.3)
Where is usually equals to stoichiometry ratio of oxygen multiply by (1.2 1.5)
=

1
(1.3)
4

(3.4)
=0.325
In this level we need to consider the recycle stream of the valuable materials. In this case, it
happened to be methanol. Therefore,
FM = FFM + FM (1- x)

11

F M=

F FM
x

(3.5)
Instead of pure oxygen, air is chosen as the source for the oxygen as air is easily accessible
and cheap compare to pure oxygen. Hence, whenever air is used the composition of oxygen
in the air needed to be considered. The composition of oxygen in air is 21% while the other
79% is Nitrogen. So,
F N 2=

0.21
F
0.79 O 2

(3.6)

The product flow for water is obtained based on the probability flow chart above which
formed by combining of both equation, where x is assumed to be 1.
1
2

PH2O = FH2O +

FFMY + 3 FFM (1-Y)

(3.7)
The same method is used to determine the product flow of hydrogen, oxygen and carbon
dioxide,
PH2 =

1
2

FFMY

(3.8)
PO2= FO2 +

1
4

FFMY +

5
2

FFM (1-Y)

(3.9)
PCO2 = + 2FFM (1-Y)
(3.10)
The nitrogen is the process is inert hence

12

PN2 = FN2
(3.11)

3.3

Economic Potential 2

In this level 2, the economic potential is calculated based on the product flow from the outlet
and fed flow in the inlet. The price of the particular materials and selling price of products are
taken from Table 1. The utility cost is relatively small amount which will only cause a very
minor change; hence the utility cost is neglected at this phase. (Note: the unit used here is
kmol/yr and $/kmol)
Economic Potential 2 = Revenue Raw Material Cost Utility cost
EP 2=(P f x price of formaldehyde)(

Pf =0.2861875

Pf
x price of methanol )
Y

kmol
kg
kg 86400 s
1ton
x 32
=9.158 x
x
s
kmol
s 1 year 1000 kg
791.2512ton/ year

13

Ep2
5000000
4000000
3000000

Ep2

2000000
1000000
0
0

0.2

0.4

0.6

0.8

1.2

Figure 3.2 economic potential against conversion of methanol

The optimum conversion from this graph is around 0 to 0.2 as the economic potential is quite
high and the conversion is not low to have a food flow rate. Figure 3.2 shows the result of
economic potential for the production of formaldehyde. All range of conversion yields
positive potential and the minimum is RM426,000/ton at X almost equal to 1. The highest
profit is indicated by the Xm=0 with RM435,700/ton.
As this economic potential is the annual profit that does not have to pay anything for capital
costs and utilities costs, all the analyses are just catering the sale of products (including by
products) and the purchasing of raw materials. The next level of decisions would use the
range obtained from this level.

14

LEVEL 3
Block Flow Diagram
Methanol is being
recycled

FM

F M =F M (1 X M )

Po P N Pco

Purge
FM

Po

PN
Methanol

Pco

REACTOR

Aq.Formaldehy
de

SEPARATOR

feed,
F FM

FF

Air:

FM

Fo

FH

FN

Water,
FH

At the third level, the recycle stream is focused including the reactor.
Mole Balance (Degree of freedom)
Unknown variable (
Balance (

FM , FM , FM
0

F M + F M =F M
1

-1

FF
F
=
M
From the 2 level (
Y )

-1

nd

Specified variables (

F M =F M (1X M )
1

15

Reactor Design and Costing


Thermal Effect
Graph of X against T

X against T

4.00E-01
3.50E-01
3.00E-01
2.50E-01
2.00E-01
1.50E-01
1.00E-01
5.00E-02
0.00E+00

f(x) = 0x + 0.01
R = 1
x
Linear (x)

500 1000 1500 2000 2500 3000 3500 4000


T

The plotting above shows that the temperature is increasing due to the exothermic of the
reaction. When the temperature of the entering feed is higher, the conversion will be higher.
In this case, adiabatic condition and packed bed reactor are preferable for this reaction.
Component

3
B* 10

6
C* 10

Methanol

2.211

12.216

-3.45

Oxygen

3.639

0.506

Formaldehyde
(Formalin)
Water Vapour

2.264

7.022

3.470

1.450

0.121

Carbon
Monoxide
Nitrogen

3.376

0.557

-0.031

3.280

0.593

0.040

5
D* 10

-0.227

-1.877

16

Cp
= A+ BT +C T 2 + DT 2
R
(Retrived from Chemical Engineering Thermodynamic Book)

The heat capacity of the substances is needed to calculate the energy balance by using
Polymath. The graph of reactor temperature versus methanol conversion is obtained.
In using ODE of polymath, only one dependant variable is allowed. For the batch reactor
design algorithm, the variable involve is time. The batch reactor algorithm is used here
because the temperature is plotted against conversion and not against the reactor size variable
such as retention time, volume, or weight of the catalyst.
Levenspiel Plot

1/-rA against XA
200

f(x) = 76x + 103.13


R = 1

1/-rA 100

1/-rA
Linear (1/-rA)

0
0

0.1

0.2

0.3

0.4

XA

17

Design of the Reactor


Since the reaction occurs irreversibly in gaseous phase, packed bed reactor will be used.
From the levenspiel plot, the packed bed reactor is necessary to be used to produce high
yield. From the selectivity analysis, methanol feed must be low in order to maintain a high
selectivity. High selectivity can be sustained if the concentration of formalin is low.

M, O2,
N2

M, O2, F, CO, H2O, N2

In calculating the weight of catalyst and pressure drop,

dX
dW

and

dy
dW

will be used.

dX rM X(rM ) YX(rM )

dW
FM
FFM
PF
XYkCH 2O PM k M

PF (1 PM k M )
XYkCH 2O CM RTkM

PF (1 CM RTkM )

18

dy

T
(1 X)
dW
2y
T0

1Y 2 (1 Y )
y M [1Y 2 (1 Y)]

From Appendix C,
c=2200 kg/m3
3

Dp = 2.33 x 10

=0.5
gc=1
8
5
= ( 3.4 x 10 T +1.28 x 10
Pa.s@kg/m.s

G=FMo*MWM/Ac
o = 3.3786 0.0036T kg/m3
4
Ac=r2=3.46 10
m2

Po=1.5 atm
T= 300+273= 573K
Thus,
=

2
A c b Po

G ( 1)

150 (1)
+1.75 G
Dp
o g c D p
2

19

W against XA
14
12
10
8
W

6
4
2
0
0

0.2

0.4

0.6

0.8

1.2

XA

Cost of the Reactor,

CR

C R=index ratio of

year of reference
purchased cost (1+ installationcost percentage)
year of design

Where index ratio can be either Chemical Engineering Plant Cost Index (CEPCI: year
1990=355.4 and year 2015=2000) or Marshall & Swift Index (M&S) and the installation cost
is referred from table installation cost for equipment as a percentage of the purchased
equipment cost.
Cost of the catalyst,

CC

Price of the catalyst=

RM4000/kg

CC =4000 (weight of the catalyst used ,W )

Economic Potential
EP3(RM/year)= EP2 Cost of reactor installation Cost of catalyst Cost of separator
installation

20

Ep3 against X
4000000
3000000

f(x) = - 2609997.27x + 4747926.86


R = 0.45

Ep3 2000000

Ep3
Linear (Ep3)

1000000
0
0

0.2

0.4

0.6

0.8

1.2

From the graph, the EP3 is decreasing when the conversion approaching 1. Although the
conversion 0.1 provides us the highest profit but since the conversion is too low so 0.1 is not
an optimum conversion. At low conversion, the separation units will be very costly. The
optimum conversion from this graph is around 0.4 as the economic potential is quite high and
the conversion is not too low. At conversion of 0.4 the EP3 is around RM3, 800,000 per
annum. However in industrial it seems impossible to get a conversion of 0.4, hence the
optimum conversion lies between 0.4 and 0.5.

Conclusion
As a conclusion, we decide that the optimum conversion to be archived to produce 30000 MT
of Formaldehyde (formalin) per annum ranged between 0.4 and 0.5 with the reactor operating
8700 hours a year with 66 hours a year for maintenance and cleaning purpose. In order to
archive 0.4 to 0.5 of conversion, the reactor must be sized around 0.25 m 3 to 0.30m3 in
volume, with around 1.5kg of Fe-Mo (catalyst).

21

REFERENCE

1) Civie, P. (6 September , 2013). The Industrial Uses of Formaldehyde. Retrieved


1 June, 2015, from The Encyclopedia of Earth:
http://www.eoearth.org/view/article/153826/
2) Formaldehyde Production from Methanol. (6 December, 2010). Retrieved 5
June , 2015, from Scribd:
http://www.scribd.com/doc/55043119/Formaldehyde-Production-FromMethanol#scribd
3) Manufacture of Formaldehyde from Methanol . (May , 2005). Retrieved 1 June,
2015, from academia.edu:
22

http://www.academia.edu/6244446/iii_MANUFACTURE_OF_FORMALDEHYDE
_FROM_METHANOL_A_PROJECT_REPORT
4) Rousseau, F. &. (2005). Elementary Principles of Chemical Processes. Wiley.
5) Sanhoob, M. A., Al-sulami, A., Al-Shehri, F., & Al-rasheedi, S. (2012). Production
of Formaldehyde from Methanol. Integrated Final Report, 200.

APPENDIX

#mole balance
d(CA) / d(t) = rA
CA(0) = 87.5 #mol/L
d(CB) / d(t) = rB
CB(0) = 875 #mol/L
d(CC) / d(t) = rC
CC(0) = 0
d(CD) / d(t) = rD
CD(0) = 0
d(CE) / d(t) = rE
CE(0) = 0
d(CI)/d(t)= 0
CI(0)=3102.27
#rate law

23

r1prime=k1prime*P^0.75*yA^0.75/((1+yA^0.75)^0.5)
r2prime=k2prime*PF
rA=-r1prime
rB=-1/2*(r1prime+r2prime)
rC=r1prime-r2prime
rD=r1prime+r2prime
rE=r2prime
k1prime=0.282*exp(-36785.728/(R*T0))*exp(-36785.728/R*(1/T0-1/T))
k2prime=3.001*exp(-66412.632/(R*T0))*exp(-66412.632/R*(1/T0-1/T))
R=82.507
P=1.5
#Energy balance
d(T)/d(t)=((r1prime*V)*(difHrxn1)+(r2prime*V)*(difHrxn2))/
(NA*CpA+NB*CpB+NC*CpC+ND*CpD+NE*CpE+NI*CpI)
difHrxn1=-158800
difHrxn2=-238200
NA=CA*V
NB=CB*V
NC=CC*V
ND=CD*V
NE=CE*V
NI=CI*V
CpA=67.1608
CpB=32.6077
CpC=47.5222
CpD=36.0637
CpE=30.6431
CpI=30.1962
T(0)=573.15
V=1
T0=573.15

#Selectivity
S=(rC+0.00001)/(rE+0.00001)
Y=(rC)/(-rA)
yA0=CA0/(CT0)
yA=CA/CT
CT=CA+CB+CC+CD+CE+CI
CT0=CA0+CB0+CI0
PF=CC/CT*1.5
CA0=87.5 #mol/L
CB0=875 #mol/L
CI0=CB0*0.78/0.22
XA=1-CA/CA0
v0=1
t(0) = 0
t(f) = 3600
A=1/(-rA)

24

Calculated values of DEQ variables


Variable

Initial value

Minimal value

Maximal value

Final value

104.1505

104.1505

131.0426

131.0426

CA

87.5

56.61014

87.5

56.61014

CA0

87.5

87.5

87.5

87.5

CB

875.

853.3399

875.

853.3399

CB0

875.

875.

875.

875.

CC

18.45957

18.45957

CD

43.32014

43.32014

CE

12.43028

12.43028

CI

3102.27

3102.27

3102.27

3102.27

10 CI0

3102.273

3102.273

3102.273

3102.273

11 CpA

67.1608

67.1608

67.1608

67.1608

25

12 CpB

32.6077

32.6077

32.6077

32.6077

13 CpC

47.5222

47.5222

47.5222

47.5222

14 CpD

36.0637

36.0637

36.0637

36.0637

15 CpE

30.6431

30.6431

30.6431

30.6431

16 CpI

30.1962

30.1962

30.1962

30.1962

17 CT

4064.77

4064.77

4086.43

4086.43

18 CT0

4064.773

4064.773

4064.773

4064.773

19 difHrxn1

-1.588E+05

-1.588E+05

-1.588E+05

-1.588E+05

20 difHrxn2

-2.382E+05

-2.382E+05

-2.382E+05

-2.382E+05

21 k1prime

0.1295431

0.1295431

0.1422172

0.1422172

22 k2prime

0.7367866

0.7367866

0.8720246

0.8720246

23 NA

87.5

56.61014

87.5

56.61014

24 NB

875.

853.3399

875.

853.3399

25 NC

18.45957

18.45957

26 ND

43.32014

43.32014

27 NE

12.43028

12.43028

28 NI

3102.27

3102.27

3102.27

3102.27

29 P

1.5

1.5

1.5

1.5

30 PF

0.0067759

0.0067759

31 R

82.507

82.507

82.507

82.507

32 r1prime

0.0096015

0.0076311

0.0096015

0.0076311

33 r2prime

0.0059088

0.0059088

34 rA

-0.0096015

-0.0096015

-0.0076311

-0.0076311

35 rB

-0.0048007

-0.0067699

-0.0048007

-0.0067699

36 rC

0.0096015

0.0017223

0.0096015

0.0017223

37 rD

0.0096015

0.0096015

0.0135399

0.0135399

38 rE

0.0059088

0.0059088

39 S

961.1493

0.2926832

961.1493

0.2926832

40 T

573.15

511.744

573.15

511.744

41 t

3600.

3600.

42 T0

573.15

573.15

573.15

573.15

43 V

1.

1.

1.

1.

44 v0

1.

1.

1.

1.

45 XA

0.3530269

0.3530269

46 Y

1.

0.2256982

1.

0.2256982

47 yA

0.0215264

0.0138532

0.0215264

0.0138532

48 yA0

0.0215264

0.0215264

0.0215264

0.0215264

Differential equations
1 d(CA)/d(t) = rA

26

2
3
4
5
6

d(CB)/d(t) = rB
d(CC)/d(t) = rC
d(CD)/d(t) = rD
d(CE)/d(t) = rE
d(CI)/d(t) = 0
d(T)/d(t) = ((r1prime*V)*(difHrxn1)+(r2prime*V)*(difHrxn2))/
7
(NA*CpA+NB*CpB+NC*CpC+ND*CpD+NE*CpE+NI*CpI)
Explicit equations
1 CT = CA+CB+CC+CD+CE+CI
2 yA = CA/CT
3 T0 = 573.15
4 R = 82.507
5 k1prime = 0.282*exp(-36785.728/(R*T0))*exp(-36785.728/R*(1/T0-1/T))
6 P = 1.5
7 PF = CC/CT*1.5
8 k2prime = 3.001*exp(-66412.632/(R*T0))*exp(-66412.632/R*(1/T0-1/T))
9 r2prime = k2prime*PF
10 r1prime = k1prime*P^0.75*yA^0.75/((1+yA^0.75)^0.5)
11 rA = -r1prime
12 difHrxn1 = -158800
13 difHrxn2 = -238200
14 V = 1
15 NA = CA*V
16 NB = CB*V
17 NC = CC*V
18 ND = CD*V
19 NE = CE*V
20 CpA = 67.1608
21 CpB = 32.6077
22 CpC = 47.5222
23 CpD = 36.0637
24 CpE = 30.6431
25 CpI = 30.1962
26 NI = CI*V
27 rB = -1/2*(r1prime+r2prime)
28 rC = r1prime-r2prime
29 Y = (rC)/(-rA)
30 CB0 = 875
mol/L

31
32
33
34
35

rE = r2prime
rD = r1prime+r2prime
CI0 = CB0*0.78/0.22
S = (rC+0.00001)/(rE+0.00001)
CA0 = 87.5
mol/L

36 CT0 = CA0+CB0+CI0
37 yA0 = CA0/(CT0)

27

38 XA = 1-CA/CA0
39 v0 = 1
40 A = 1/(-rA)
General
Total number of equations

47

Number of differential equations

Number of explicit equations

40

Elapsed time

0.000 sec

Solution method

RKF_45

Step size guess. h

0.000001

Truncation error tolerance. eps

0.000001

Data file: c:\users\user\desktop\poly_cre_1.pol

#mole balance
d(FA) / d(W) = rA
FA(0) = 0.0243
d(FB) / d(W) = rB
FB(0) = 0.243
d(FC) / d(W) = rC
FC(0) = 0
d(FD) / d(W) = rD
FD(0) = 0
d(FE) / d(W) = rE
FE(0) = 0
Y=1-1.9240*XA^0.9051
FT0=FA0+FB0+FI0
FT=FA+FB+FC+FD+FE+FI0
XA=1-(FA/FA0)
FA0=0.0243
FB0=0.243
FI0=0.78*FB0/0.22
#rate law
r1prime=k1prime*P^0.75*yA^0.75/((1+yA^0.75)^0.5)
r2prime=k2prime*PF
rA=-r1prime
rB=-1/2*(r1prime+r2prime)
rC=r1prime-r2prime
rD=r1prime+r2prime
rE=r2prime
k1prime=0.282*exp(-36785.728/(R*T0))*exp(-36785.728/R*(1/T0-1/T))
k2prime=3.001*exp(-66412.632/(R*T0))*exp(-66412.632/R*(1/T0-1/T))
R=82.507
P0=1.5
yA=FA/FT

28

PF=FC/FT*P
#Energy balance
d(T) / d(W) = ((r1prime*V)*(-difHrxn1)+(r2prime*V)*(-difHrxn2))/
(FA*CpA+FB*CpB+FC*CpC+FD*CpD+FE*CpE+FI0*CpI)
difHrxn1=-158800
difHrxn2=-238200
CpA=67.1608
CpB=32.6077
CpC=47.5222
CpD=36.0637
CpE=30.6431
CpI=30.1962
T0=573
V=1
P=y*P0
#Pressure drop
d(y) / d(W) =-alpha/2/y*T/T0*FT/FT0
y(0) = 1
alpha=2*beta/(Ac*2200*(1-0.5)*(P0*101.325))
beta=G*(1-0.5)/(rho0*1*2.33e-3*0.5^3)*(150*(1-0.5)*miu/2.33e-3+1.75*G)
Ac=3.1416*(0.021/2)^2*5000
miu=3.2282e-5
G=FA0*32/Ac
rho0=1.3158
T(0)=573
W(0)=0
W(f)=12

Calculated values of DEQ variables


Variable

Initial value

Minimal value

Maximal value

Final value

Ac

1.731807

1.731807

1.731807

1.731807

alpha

0.0073848

0.0073848

0.0073848

0.0073848

beta

1069.073

1069.073

1069.073

1069.073

CpA

67.1608

67.1608

67.1608

67.1608

CpB

32.6077

32.6077

32.6077

32.6077

CpC

47.5222

47.5222

47.5222

47.5222

CpD

36.0637

36.0637

36.0637

36.0637

CpE

30.6431

30.6431

30.6431

30.6431

CpI

30.1962

30.1962

30.1962

30.1962

10 difHrxn1

-1.588E+05

-1.588E+05

-1.588E+05

-1.588E+05

11 difHrxn2

-2.382E+05

-2.382E+05

-2.382E+05

-2.382E+05

12 FA

0.0243

4.015E-08

0.0243

4.015E-08

29

13 FA0

0.0243

0.0243

0.0243

0.0243

14 FB

0.243

0.2187962

0.243

0.2187962

15 FB0

0.243

0.243

0.243

0.243

16 FC

0.0060371

0.0001923

17 FD

0.0484076

0.0484076

18 FE

0.0241076

0.0241076

19 FI0

0.8615455

0.8615455

0.8615455

0.8615455

20 FT

1.128845

1.128845

1.153049

1.153049

21 FT0

1.128845

1.128845

1.128845

1.128845

22 G

0.4490108

0.4490108

0.4490108

0.4490108

23 k1prime

0.1295167

0.1009675

0.1295167

0.1009675

24 k2prime

0.7365158

0.4698289

0.7365158

0.4698289

25 miu

3.228E-05

3.228E-05

3.228E-05

3.228E-05

26 P

1.5

1.405714

1.5

1.405714

27 P0

1.5

1.5

1.5

1.5

28 PF

0.007882

0.0002345

29 R

82.507

82.507

82.507

82.507

30 r1prime

0.0095995

3.323E-07

0.0095995

3.323E-07

31 r2prime

0.004743

0.0001102

32 rA

-0.0095995

-0.0095995

-3.323E-07

-3.323E-07

33 rB

-0.0047998

-0.0056381

-5.525E-05

-5.525E-05

34 rC

0.0095995

-0.0009761

0.0095995

-0.0001098

35 rD

0.0095995

0.0001105

0.0112763

0.0001105

36 rE

0.004743

0.0001102

37 rho0

1.3158

1.3158

1.3158

1.3158

38 T

573.

573.

842.6786

842.6786

39 T0

573.

573.

573.

573.

40 V

1.

1.

1.

1.

41 W

12.

12.

42 XA

0.9999983

0.9999983

43 Y

1.

-0.9239971

1.

-0.9239971

44 y

1.

0.9371429

1.

0.9371429

45 yA

0.0215264

3.482E-08

0.0215264

3.482E-08

Differential equations
1 d(FA)/d(W) = rA
2 d(FB)/d(W) = rB
3 d(FC)/d(W) = rC
4 d(FD)/d(W) = rD
5 d(FE)/d(W) = rE

30

d(T)/d(W) = ((r1prime*V)*(-difHrxn1)+(r2prime*V)*(-difHrxn2))/
(FA*CpA+FB*CpB+FC*CpC+FD*CpD+FE*CpE+FI0*CpI)
7 d(y)/d(W) = -alpha/2/y*T/T0*FT/FT0
6

Explicit equations
1 FA0 = 0.0243
2 FB0 = 0.243
3 FI0 = 0.78*FB0/0.22
4 XA = 1-(FA/FA0)
5 Y = 1-1.9240*XA^0.9051
6 FT0 = FA0+FB0+FI0
7 FT = FA+FB+FC+FD+FE+FI0
8 yA = FA/FT
9 P0 = 1.5
10 T0 = 573
11 R = 82.507
12 P = y*P0
13 PF = FC/FT*P
14 k1prime = 0.282*exp(-36785.728/(R*T0))*exp(-36785.728/R*(1/T0-1/T))
15 r1prime = k1prime*P^0.75*yA^0.75/((1+yA^0.75)^0.5)
16 k2prime = 3.001*exp(-66412.632/(R*T0))*exp(-66412.632/R*(1/T0-1/T))
17 rA = -r1prime
18 r2prime = k2prime*PF
19 rB = -1/2*(r1prime+r2prime)
20 rC = r1prime-r2prime
21 difHrxn1 = -158800
22 difHrxn2 = -238200
23 CpA = 67.1608
24 CpB = 32.6077
25 CpC = 47.5222
26 CpD = 36.0637
27 CpE = 30.6431
28 CpI = 30.1962
29 rD = r1prime+r2prime
30 V = 1
31 rE = r2prime
32 Ac = 3.1416*(0.021/2)^2*5000
33 rho0 = 1.3158
34 G = FA0*32/Ac
35 miu = 3.2282e-5
36 beta = G*(1-0.5)/(rho0*1*2.33e-3*0.5^3)*(150*(1-0.5)*miu/2.33e-3+1.75*G)
37 alpha = 2*beta/(Ac*2200*(1-0.5)*(P0*101.325))
General
Total number of equations

44

Number of differential equations

Number of explicit equations

37

Elapsed time

1.157 sec

31

Solution method

RKF_45

Step size guess. h

0.000001

Truncation error tolerance. eps

0.000001

Data file: c:\users\user\desktop\poly_cre_2.pol

32