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ABSTRACT

In this project we studied on manufacturing methanol. We made investigations for methanol


manufacturing process. The flow chart for the process, reactor configurations are
asked.Firstly, Using thermodynamic properties of C0,H2 and CH3OH, equilibrium line is
plotted and 100 bar is selected. Constant rate curves are obtained by using reaction rate
expression which is given at term project part.The operating lines goes through the
extremums of these curves.Adiabatic energy balance equation for each reactor gives adiabatic
line equations.These adiabatic line equations plotted until the reaching desired conversion of
0.55.This conversion is attained with 6 plug flow reactors.

Reactor Design Project


Methanol is considered as a potential source of energy and as an intermediate to produce
alternative motor vehicle fuels, fuel additives and number of petrochemicals. Conventionally,
methanol is produced from synthesis gas (gas mixtureof carbon monoxide and hydrogen
produced by reforming of natural gas) in a series of fxed bed catalytic reactors at a relatively
high pressure. It is also possible to produce synthesis gas by gasification of biomass or coal.

CO + 2H 2 CH3 OH
In this project you are asked to design the reactor(s) to be used for a methanol production
at a rate of 400 tons/day:
(A) Seach the literature for methanol production.Discuss the operating conditions of the
process and the critical points for pressure selection.
(B) Considering a feed composition of 30% CO and 70% H2 ,examine the thermodynamics of
methanol synthesis reaction in order to decide on the operating pressure. Plot equilibrium
conversion versus temperature graphs in a pressure range of 50-120 bars. In the
equilibrium calculations you should use the fugacities.
(C) Taking the pressure as 100 bars and considering a target conversion of CO as 55% decide
about the reactor configurations, operation mode (adiabatic, non adiabatic, isothermal),
reactor inlet temperature(s).
(D) Design the reactor(s) to find the catalyst volume and total reactor volume.
In methanol synthesis, a catalyst containing Cu/ZnO system, with the addition of
aluminum is generally used. You may use the rate expression given in the datapage.
DATA
For systems where the synthesis gas is composed of only CO and H2, the following rate
equation was proposed for the hydrogenation of CO over a Cu/Zno on alumina catalyst for a
temperaturen range between 450-650K and pressures 50-100 bar.
r = k(PCO P 2H 2

PCH3OH
) (mol / kgcat min)
Ke

k = 7.6 106 mol(kgcat)1 min1 atm3 at 250 C


E = 80 kJ mol 1 (activation energy)
90.13kJ.mol1
12
K e = 3.567 10 exp(
)atm2
RT
The catalytic packed bed bulk density was given as 1120 kg m 3

1.INTRODUCTION
1.1 Methyl Alcohol as an Industrial Chemical
Methanol (methyl alcohol), CH3OH, is clear, water- white liquid with a mild odor at
ambient temperatures. From its discovery in the late 1600s, methanol has grown to become
the 21st largest commodity chemical with over 12x106 metric tons annually produced in the
world. Methanol has been called wood alcohol (or wood spirit) because it was obtained
commercially from the destructive distillation of wood for over a century. However, true
wood alcohol contained more contaminants (primarily acetone, acetic acid, and ally alcohol)
than the chemical- grade methanol avaible today.
Table 1.1 Physical Properties of Methanol
Property
Freezing point oC
Boiling point oC
Critical temperature oC
Critical pressure kPa
Critical volume mL/mol
Critical compressibility factor z in PV=znRT
Heat of formation(liquid) at 25oC kj/mol
Free energy of formation(liquid) at 25oC kj/mol
Heat of fusion J/g
Heat of vaporization at boiling point J/g
Heat of combustion at 25oC J/g
Flammable limits in air
Lower, vol %
Upper, vol %
Autoignition temperature, oC
Flash point, closed cup, oC
Surface tension, mN/m (dyn/cm)
Specific heat
of vapor at 25 oC, J/(g.K)
of liquid at 25 oC, J/(g.K)
Vapor pressure at 25 oC, kPa
Solubility in water
Density at 25 oC, g/m3
refractive index, nD20
viscosity of liquid at 25 oC, mPa.s(cP)
Dielectric constant at 25 oC
Thermal conductivity at 25 oC, W/(m.K)

Value
-97,68
64,70
239,43
8096
118
0,224
-239,03
-166,81
103
1129
22662
6
36
420
12
22,6
1,370
2,533
16,96
miscible
0,78663
1,3284
0,541
32,7
0,202

For many years the largest use for methanol has been as a feedstock in the production
of formaldehyde, consuming almost half of the entire methanol produced. In the future,
3

formaldehydes importance to methanol will decrease as newer uses increase such as the
production of acetic acid and methyl tert-butyl ether (MTBE, a gasoline octane booster).
Methanols direct use as a fuel may be significant in special circumstances.
1.2 Manufacturing and Processing
Modern industrial- scale methanol production is based on exclusively on synthesis
from pressurized mixtures of hydrogen, carbon monoxide, and carbon dioxide gases in the
presence of metallic heterogeneous catalysts. The required synthesis pressure is dependent on
the activity of the particular catalyst. By convention, technology is generally distinguished by
pressure as follows; lower pressure processes, 5-10 MPa (50-100atm); medium pressure
processes, 10-25 MPa (100-250 atm); and high pressure processes, 25-35 MPa (250-350 atm).
[1]
In the late 1960a medium and low pressure methanol technology came into use with
the successful development of highly active, durable copper-zinc oxide catalysts. Copper
catalysts sensitivity to poisons required careful purification of feed streams. Low and
medium pressure technology has advantages of reduces compression power, good catalyst
life, larger capacity single- train converter designs and milder operating pressures.
Some reactions rate expressions uses for methanol production is listed on appendix
D.1
1.3 Natural Gas

Hydrocracking of heavy hydrocarbons:


CnH(2n+2) + (n-1)H2

Steam reforming of CH4:


CH4 + H2O

nCH4

CO +3H2

Water gas shift:


CO + H2O

CO2+H2

For low pressure catalysts, the excess hydrogen improves the catalyst effectiveness.
Thus, converter costs are reduced and the necessity of shifting and removing excess hydrogen
from the synthesis feed gas, as commonly practiced with high pressure technology, is
avoided. Excess hydrogen is vented during synthesis and used as fuel in the reforming step.
Thus, a high overall energy efficiency is mainted which makes the process economical. [1]

Table 1.2 Equilibrium CO, CO2 Conversion, and Exit CH3OH Concentration vs Pressure and
Temperature
Temperature
,
o
C
200
250
300
350
400

CO conversion, %
5MPa 10MPa 30MPa

CO2 conversion, %
5MPa 10MPa 30MPa

Exit CH3OH, vol %


5MPa 10MPa 30MPa

95.6
72.1
25.7
-2.3
-12.8

44.1
18.0
14.3
19.8
27.9

27.8
16.2
5.6
1.3
0.3

99.0
90.9
60.6
16.9
-7.2

99.9
98.9
92.8
73.0
38.1

82.5
46.2
24.6
23.6
30.1

99.0
91.0
71.1
52.1
44.2

37.6
26.5
14.2
4.8
1.4

42.3
39.7
32.2
21.7
11.4

1.4 Catalyst
Methanol, an important industrial chemical is produced on a large scale so called low
pressure (50-100 bar) process. The formation of methanol is catalyzed by Cu-Zn-Al or CuZn-Cr mixed oxides important design factors in modeling a methanol reactor are the values
of equilibrium constants of the following reaction. [2]
CO+2H2

CH3OH

CO2+H2

CO+H2O

Catalyst used in high pressure (25-35 MPa or 250-350atm) synthesis is zinc oxidechromium oxide. It is a more robust catalyst than the low pressure copper-based catalyst and
can tolerate higher temperature and sulfur levels. The copper- zinc oxide catalyst, However, is
more attractive and can be operated at lower pressure (5-25 MPa or 50-250 atm) and
temperature (200-300 C). [1]
1.5 Low Pressure Processes
A more active catalyst than the above can be made from a combination of copper and
zinc together with a textural promoter such as chromia or alumina. These permit the use of a
lower pressure in the range of about 5 to 10 MPa, and a temperature of about 240 to 260
centigrade degrees. Recent laboratory studies indicate that the active phase is a solution of Cu
in ZnO and that methanol yield are increased by the presence of CO2, H2O or O2 in the
synthesis gas. If none of these is present, the catalyst gradually loses activity, since the CuZnO phase apparently may be gradually reduced to inactive copper metal. This process is
irreversible once the crystallites of copper metal have grown. The fact that the copper
produces a chemical effect rather than a physical effect is also shown by the fact that this
catalyst exhibits considerably lower apparent activation energy than the Zno-Cr2O3 catalyst.
Low pressure process utilizes a single bed of catalyst and quench cooling, obtained by
5

lozenge distributors especially designed to obtain good gas distribution and gas mixing and to
permit rapid loading and unloading of catalyst. A low pressure methanol synthesis process is
advantageously combined with production of synthesis pressure, thus avoiding the necessity
of intermediate gas compression. These low pressure processes are usually the process of
choice in new installations.
To produce relatively pure methanol product directly requires care in catalyst
manufacture , and requires procedures to avoid catalyst contamination. [3].
1.5.1 Catalyst Characteristic
Zinc oxide serves several important functions that enhance the stability and life of
the catalysts.
Its credited with an important role in the proprietary manufacturing produce that
creates a high- surface area of copper
Along with alumina, it prevents copper agglomeration
ZnO reacts readily with copper, poisons such as sulfur and chlorine compounds. [4]
1.5.2 Side Reactions
Prior to commercialization of the low-to-medium pressure process using copper
catalysts, the most troublesome side reaction was the reverse of thee steam reforming
reaction. Occurs in high pressure plants above 450 C and causes exit bed temperatures to
exceed 600 C. Such runaway temperatures usually require reactor shutdown to prevent
catalyst and equipment damage. The low pressure copper-based catalysts operate in a lower
temperature range, ie, 200-300 C , where the methanation reaction is unimportant.
Alcohols other than methanol are produced in small quantities with ethanol the chief
impurity. Formation of the higher alcohols can be suppressed by keeping the reaction
temperature as low as possible for the methanol production rate desired. High hydrogen
concentration also suppresses the formation of higher alcohols and the other by products.
Other by products produced is small amounts are aldehydes, ketones, ethers and esters. [1]

2.THERMODYNAMIC DATA

Table 2.1 Thermodynamics properties of methanol,carbon monoxide and hydrogen gaseous


Components

H 298 (kj/mol)

G 298 (kj/mol)

CH3OH (Methanol)

-201,2

-162

H2

CO

-110,52

-137,2

( Referrence : Sandler , S.I, Chemical and Engineerig Thermodynamics, Third edition, John Wiley &
Sons Inc. , 1999 , page 759)

C P,CO (T, K) = 27,113 + 0,655 X 102 T 0,1 X 105 T 2 [j /mol.K]


C P,H 2 (T, K) = 26,113 + 0,435 X 102 T 0,033 X 105 T 2 [j /mol.K]
C P,CH3OH (T, K) = 19,038 + 9,146 X 102 T 1,218 X 105 T 2 - 8,034 X 109 T 3 [j /mol.K]
( Referrence : Sandler , S.I, Chemical and Engineerig Thermodynamics, Third edition, John Wiley &
Sons Inc. , 1999 , page 745-747)

Table 2.2 Critical tempertaure and pressure of substances

CO

H2

513.2 K
133 K
33.3 K

79.54 bar
34.96 bar
12.97 bar

3.CALCULATIONS
3.1. Obtaining equilibrium constant as a function of temperature, Kf (T) :
+ H 298 and G298 values are given at thermodynamics data part.

r o d

c t s

t a n

r e a

Hc

t s

H 298 = (-201,2)-(-110,52)

= -90,68 kj/mol = -90680 j/mol

r o

c t s

t a n

r e a

t s

G 298 = (-162,0)-(-137,2)

= -24,8 kj/mol = -24800j/mol


G = RT ln K 298 = 8,314

J
298K ln K298 =-24800 j/mol
mol K

ln K 298 = 10,0097 K 298 = 22243,38

dInK f H
=
dT
R T2

H
dT
2
T 0 RT

.... Van't Hoff Equation ( InKf )T = InK +

C P = CP,CHOH 2CP,H 2 CP,CO

TR

TR

dH = cpdT

+ Cp values of substances are given at thermodynami properties part.


C P = -60,301 + 7,621X 102 T 1,052 X 105 T 2 - 8,034 X 109 T 3 (J/mol.K)

H = H298 +

Cp

dT

298

H = - 75985,54 + (60,301 T) + (0, 0381 T 2 ) (3,5067 106 T3 ) (2, 0085 109 T4 )

d ln K f =

298

1 T H(T)dT
R 298
T2

R=8,3145 J/mol.K;
ln K 298 = 10,0097

(InKf)= InK 298 +


(9,32935 +

9139, 46
7, 2529 ln(T) + 4,5826 103 T 4, 2178 107 T2 2, 415 1010 T3 )
T

K f = exp(19,33905 +

9139, 46
7, 2529 ln(T) + 4,5826 103 T 4, 2178 107 T2 2, 415 1010 T3 )
T

Table 3.1 Equilibrium constant versus temperature data


T
400
420
440
460
480
500
520
540
560
580
600

Kf
1,619805
0,415906
0,119779
0,03814
0,013267
0,00499
0,002012
0,000863
0,000392
0,000187
9,33E-05

3.2 Plotting equilibrium conversion versus temperature graphs in a pressure range of


50-120 bars
K T = K K y P n

= f / P ( fugacity coefficient)

Basis: 100 moles/s Feed composition enter the reactor


CO + 2 H 2 CH 3OH

H2 B ,

CO A ,

CH3OH C

A + 2B C
30 70
-a -2a a
---- ---- ---30-a 70-2a a
nT = 30 a + 70 2a + a = 100 2a
a=CA0 . XAe

Ky =
K =

CA0 = 30 (due to basis 100 moles reactant)

a = 30 XAe

yc
y A .yB

ic
( ia .ib 2 )

n = (1 1 2) = 2

+ With changing the operating pressure, reduced pressure (Pr) and temperature (Tr) values be
changed . So, fugacities of substances might be changed. According to this change, obtained
different equilibrium conversion( X Ae ) versus temperature functions by pressures.
Tr = T / TC
Pr = P / PC
Reduced temperature and pressure values of substances are shown on Appendix A.1
+ At P = 50 bar, temperature range of 400-600 K ;
Table 3.2 Reduced Pressures at P=50 bar
Pr(metanol) Pr(CO)
0,628614534 1,43020595

Pr(H2)
3,855050116

10

Fugacity coefficient of substances are read on a graph by parameters Tr,Pr, shown on


Appendix A.1
Table 3.3 Equilibrium constant and Xae values for temperature range of 400-600K, P=50bar
T
400
420
440
460
480
500
520
540
560
580
600

Kf
1,619805
0,415906
0,119779
0,03814
0,013267
0,00499
0,002012
0,000863
0,000392
0,000187
9,33E-05

K(fugacity coefficient)
0,15049
0,23764
0,35310
0,49655
0,70088
0,74634
0,78482
0,81485
0,84074
0,86378
0,88197

Ky
26909,64
4375,284
848,0635
192,0247
47,32129
16,71539
6,409849
2,649156
1,164987
0,541032
0,264582

Sample calculation : At T=400K (P=50bar)

Kf =

30X Ae
100-60X Ae
30-30X Ae
100 60X Ae

1, 619805 =

26909,64 =

70 60XAe

100 60XAe

ic
502
2
( ia .ib )

30X Ae
100-60X Ae
30-30X Ae 70 60XAe

100 60X Ae 100 60XAe

0,1538
502
(1, 017) 2 1, 012

30X Ae
100-60X Ae
30-30X Ae 70 60XAe

100 60X Ae 100 60XAe

An equation Ky = f( X Ae ) such as:

Ky =

30X Ae
100-60X Ae
30-30X Ae 70 60XAe

100 60X Ae 100 60XAe

We calculate Xae value using a matlab function (See Appendix A.2)


11

Xae
0,99940
0,99650
0,98380
0,95751
0,86850
0,76720
0,63150
0,47240
0,31600
0,19120
0,10870

By using other Ky values on this matlab function, we get the Xae values on Table 3.3
+ At P = 75 bar, temperature range of 400-600 K ;
Table 3.4 Reduced Pressures at P=75 bar
Pr(metanol) Pr(CO)
0,9429218 2,145308924

Pr(H2)
5,782575173

Fugacity coefficient of substances are read on a graph by parameters Tr,Pr, shown on


Appendix A.1
Table 3.5 Equilibrium constant and Xae values for temperature range of 400-600K, P=75bar
T
400
420
440
460
480
500
520
540
560
580
600

K(fugacity
coefficient)
0,092810483
0,156250745
0,231447055
0,325141594
0,434626865
0,557073141
0,642367583
0,685524544
0,722445487
0,752806781
0,778071256

Kf
1,619805
0,415906
0,119779
0,03814
0,013267
0,00499
0,002012
0,000863
0,000392
0,000187
9,33E-05

Sample calculation : At T=400K (P=75bar)

Kf =

30X Ae
100-60X Ae
30-30X Ae
100 60X Ae

1,619805 =

98172,15 =

70 60XAe

100 60XAe

ic
752
2
( ia .ib )

30X Ae
100-60X Ae
30-30X Ae
100 60X Ae

70 60XAe

100 60XAe

0, 09281 752

30X Ae
100-60X Ae
30-30X Ae 70 60XAe

100 60X Ae 100 60XAe

An equation Ky = f( X Ae ) such as:

12

Ky
98172,15
14972,54
2911,074
659,8286
171,6992
50,38741
17,62038
7,085048
3,050439
1,396763
0,6748

Xae
0,9998
0,9989
0,9948
0,9845
0,9427
0,8733
0,7735
0,6476
0,4993
0,3496
0,2237

Ky =

30X Ae
100-60X Ae
30-30X Ae 70 60XAe

100 60X Ae 100 60XAe

We calculate Xae value using a matlab function (See Appendix A.2)


By using other Ky values on this matlab function, we get the Xae values on Table 3.5
+ At P = 120 bar, temperature range of 400-600 K ;
Table 3.6 Reduced Pressures at P=120 bar
Pr(metanol) Pr(CO)
1,508674881 3,432494279

Pr(H2)
9,252120278

Table 3.7 Equilibrium constant and Xae values for temperature range of 400-600K, P=120bar
T
400
420
440
460
480
500
520
540
560
580
600

K(fugacity
coefficient)
0,063209575
0,099519313
0,14732625
0,207338687
0,278338222
0,359381778
0,44432146
0,523088292
0,581157042
0,627223183
0,665798469

Kf
1,619805
0,415906
0,119779
0,03814
0,013267
0,00499
0,002012
0,000863
0,000392
0,000187
9,33E-05

Ky
369013,7
60179,7
11707,52
2648,886
686,3599
199,9485
65,21412
23,77009
9,707646
4,291649
2,018792

Sample calculation : At T=400K (P=120bar)

Kf =

30X Ae
100-60X Ae
30-30X Ae 70 60XAe

100 60X Ae 100 60XAe

1,619805 =

ic
1202
2
( ia .ib )

30X Ae
100-60X Ae
30-30X Ae
100 60X Ae

70 60XAe

100 60XAe

0,063209575 752

13

Xae
0,99999
0,9997
0,9987
0,9943
0,9806
0,9486
0,8915
0,8065
0,6956
0,5624
0,42

369013,7 =

30X Ae
100-60X Ae
30-30X Ae 70 60XAe

100 60X Ae 100 60XAe

An equation Ky = f( X Ae ) such as:

Ky =

30X Ae
100-60X Ae
30-30X Ae 70 60XAe

100 60X Ae 100 60XAe

We calculate Xae value using a matlab function (See Appendix A.2)


By using other Ky values on this matlab function, we get the Xae values on Table 3.7
Finaly, Xae T graph plotted on graph 3.1 at selected pressure of 50,75 and 120 bar.

Figure 3.1 Xae versus Temperature(K) graph for methanol production at given conditions

14

3.3 Drawing constant rate curves to get operating line


The rate expression which will be used for obtaining kinetic data is given in the
reactor desing project part as :
r = k(PCO P 2H 2

PCH3OH
);
Ke

Daltons law presents an expression about relation between ya (molar fraction) and
pressure as PA = PT ya . Total amount of A in the total mixture (ya = FA / FT ) can also be
defined.
yA =

FA PA
=
FT PT

PA =

FA
PT (3.1);
FT

A + 2B C
Fa0

Fb0

-Fa0Xa -2Fa0Xa

Fa0Xa

------------------------------------

FA = FA0 FA0 XA
FB = FB0 2FA0 XA
FC = FA0 X A
FT = FA0 (1 2XA ) + FB0
Using formula 3.1 and expressions above, these are derived :
r=

ra
; r=-ra ; FA = CA V0 ;
1

FA =

CA0 (1 X A )
V0 ;
1+ X A

FB =

(C B0 2CA0 XA )
V0 ;
1+ X A

FC =

C A0 X A
V0 ;
1+ X A

FT = FA + FB + FC

FT =

CA 0 + CB0 2CA0 XA
V0 ;
1+ X A

15

CA 0 (1 X A )
V0
1+ X A
(1 XA )
PA =
100 =
100 (Carbon Monoxide)
CA 0 + CB0 2CA0 XA
7
(1 2X A ) +
V0
3
1+ X A
(CB0 2CA0 XA )
7
V0
2X A
1+ X A
PB =
100 = 3
100 (Hydrogen gas)
C A0 + CB0 2CA0 XA
7
(1 2X A ) +
V0
3
1+ X A
CA0 X A
V0
1+ X A
XA
PC =
100 =
100 (Methanol)
C A0 + CB0 2CA0 XA
7
(1 2X A ) +
V0
3
1+ X A
All of the partial pressure expressions numerators and denominators are divided by C A0 ,
(C B0 / CA0 = 70 / 30) The rate expression is obtained as a function of temperatures(T) and
molar fractions (Xa).
XA

100)
7
(1 2XA ) +
(1 X A )
3
ra = (k) ((
100) (
100)2
)
7
7
3,567E

12

exp(90130
/
8,314

T)
(1 2X A ) +
(1 2XA ) +
3
3
(

7
2X A
3

k = 743,198 exp(-80000 / (8,3145 T))


The constant rate curves are drawen by cooperation with an C#.NET program and
Excel . (See Appendix B.1 for C# program)
Constant rate curves are drawen for the vaules of r; 0; 0,05, 0,1, 0,35, 0,5, 1, 2, 5 and 8
Kinetics and thermodynamics equilibrium lines (r=0) are shown on figure 3.2

16

Figure 3.2 Equilibrium lines from kinetics and thermodynamics


Table 3.1 Constant rates T,Xa data
r=0,1
T
462
463
465
466
467
475
476
478
479
481
482
502
504
553
554
555
559
561
567
569
613
667

Xa
0
0,03
0,12
0,15
0,18
0,38
0,4
0,43
0,45
0,48
0,49
0,66
0,67
0,64
0,64
0,63
0,62
0,61
0,58
0,57
0,35
0,14

r=0,35
T
492
494
498
505
507
509
512
513
514
522
530
539
548
559
583
598
600
602
604
606

Xa
0,01
0,08
0,2
0,35
0,38
0,41
0,45
0,46
0,47
0,54
0,58
0,6
0,6
0,58
0,49
0,42
0,41
0,4
0,39
0,38

r=0,5
T
502
506
507
515
517
523
524
525
536
539
543
558
567
581
586
588
597
599
618
627
663

Other constant rate datas given at appendix B.2.


17

Xa
0,04
0,16
0,19
0,35
0,38
0,45
0,46
0,47
0,54
0,55
0,56
0,56
0,54
0,49
0,47
0,46
0,42
0,41
0,32
0,28
0,15

r=0
T
400
401
408
409
410
411
434
435
436
437
504
505
506
508
533
538
548
598
600
660
696

Xa
0,98
0,98
0,97
0,97
0,97
0,97
0,95
0,95
0,95
0,95
0,83
0,83
0,83
0,82
0,74
0,72
0,68
0,43
0,42
0,16
0,08

Figure 3.3 Constant rate curves at 100 bar


3.4 Energy Balance
Inlet stream : FCO, F H 2
Outlet stream : F CH 3OH , FCO, F H 2
General Energy Balance equation :
TR

T0

Tf

FC
i Pi dT +

i(inlet )

TR

FC
i Pi dT QRemovedbythewalls = ( HR )FA0 XA

i(outlet )

Flow reactors are used for methanol production.At PFR reactors adiabatic operations
are easier to control than isothermal operations. So, heat lost by the system is neglected.
Cp(T) functions listed on thermodynamics data chapter and H R |298 is calculated in
calculations 3.1.

18

3.4.1 Adiabatic lines to calculate number of reactors to achieve 0.55 conversion of A


Taken basis 100 mol/s feed composition
FT0 = 100mol / s = 70molH2

2g
28g
+ 30molCO
= 980g / s ;
molH 2
molCO

FA0 = 30mol / s ;
M methanol = 32g / mol
F(CH3OH ) = F(CH3OH)0 + F(CO)0 XCO = 0 + 30 0,55 = 16,5mol / s methanol = 528 g/s methanol
Daily production =

528g (60 60 24)s 1ton

6 = 45,61 ton/day methanol


s
1day
10 g

Figure 3.4.1 Adiabatic lines and number of reactors


According to figure 3.4 six plug flow reactor must be used to achive 0,55 conversion
at the exit.

Figure 3.4.2 6 PFR Reactors

19

3.5 Reactor Volumes Calculation


3.5.1 Reactor 1
Energy balance for reactor 1:
TR

Q R byflows =

Tf

(FA0C PA + FB0C PB)dT +

T0
TR

Q R byflows =

(F C
A

PA

+ F BC PB + F BC PB)dT

TR
Tf

(FA0C PA + FB0C PB)dT +

T0

(F

C PA F A 0X A1C PA + F B0C PB 2F A 0X A1C PB + F A0X A1C PC)dT

A0

TR

Tf

(F

A0

X A1 =

CPA + FB0 CPB )dT

T0
Tf

(F

A0

CPA + 2FA0 CPB FA 0 CPC )dT + (HR )FA0

TR

Tf

Tf

F
T0 (CPA + FA0B0 CPB )dT

X A1 =

(C

= T0

Tf

(C

PA

FB0
CPB )dT
FA0
(H R |T )

PA

+ 2CPB CPC )dT + (HR )

TR

X A1 =

88, 0433(Tf T0 ) + 0, 0167(Tf 2 T0 2 ) 1, 77 10 6 (Tf 3 T0 3)


90680 + (60,301(298 T0 ) 0, 038105(298 2 T0 2) + 3,507 10 6( 2983 T0 3 ) 2, 0085 109 (2984 T0 4 ))

.. 3.5.1

V1
=
FAo

0,1593

dX A
3.5.2
RA

3.5.1 and 3.5.2 solved simultaneously.


XA

100)
7
(1 2XA ) +
(1 X A )
3
ra = (k) ((
100) (
100)2
)
7
7
3,567E

12

exp(90130
/
8,
314

T)
(1 2X A ) +
(1 2XA ) +
3
3
(

7
2X A
3

k = 743,198 exp(-80000 / (8,3145 T))

20

From adiabatic line equation and ra equation, data on table 3.5.1 obtained
Table 3.5.1 Reactor-1 data
To

Tf

Xa

Pco

Ph2

Pch3oh

Ke

(-ra)

1/-ra

490

490

2,20397E-06

30

70

0,014456

0,323983

3,086582

490

500

0,009866

3,2641E-06

29,8809

69,82135

0,297754

0,009287

0,475376

2,103597

490

510

0,019696

4,76028E-06

29,76082

69,64123

0,597958

0,006071

0,686615

1,456419

490

520

0,029492

6,84225E-06

29,63972

69,45958

0,900698

0,004034

0,97692

1,023625

490

530

0,039255

9,70108E-06

29,51757

69,27636

1,206064

0,002722

1,369968

0,729944

490

540

0,048988

1,35777E-05

29,39434

69,09151

1,514147

0,001864

1,894161

0,527938

490

550

0,058692

1,87725E-05

29,26998

68,90498

1,825039

0,001294

2,582348

0,387244

490

560

0,06837

2,56562E-05

29,14447

68,7167

2,138834

0,00091

3,470503

0,288143

490

570

0,078022

3,46819E-05

29,01775

68,52662

2,45563

0,000648

4,594486

0,217652

490

580

0,087652

4,6398E-05

28,88979

68,33469

2,775525

0,000467

5,983472

0,167127

490

590

0,09726

6,14627E-05

28,76055

68,14083

3,098619

0,00034

7,647774

0,130757

490

600

0,106848

8,06591E-05

28,62999

67,94499

3,425015

0,00025

9,557504

0,10463

490

610

0,116418

0,000104912

28,49807

67,74711

3,754818

0,000186

11,60663

0,086158

490

620

0,125971

0,000135305

28,36475

67,54712

4,088137

0,00014

13,55422

0,073778

490

630

0,13551

0,000173099

28,22997

67,34495

4,42508

0,000106

14,93089

0,066975

490

640

0,145035

0,000219751

28,0937

67,14054

4,765762

8,1E-05

14,89287

0,067146

490

650

0,154548

0,000276936

27,95588

66,93382

5,110296

6,24E-05

11,99905

0,08334

490

655

0,1593

0,000310066

27,88638

66,82957

5,284045

5,49E-05

8,788086

0,11379

By -1/ra vs Xa data on table 3.5.1 excel regression gives this equation


-1/ra=y(Xa)= (-157200*x^5) + (85543*x^4) - (18291*x^3) + (1979.3*x^2) - (114.38*x) +
(3.0754);
Using simpsons integration rule the equation above is integrated by simpson matlab
function (See Appendix C.1 for simpson fuction and reactor volume functions)
Simpson('reactorvolume1',0,0.1593,1000) gives
V1/Fa0 = 0.0879
V1 = 30*0,0879 = 2,637
3.5.1 Reactor 2
0,2863

V2
dX A
=
FA 20 0,1593 R A
Inlet

outlet

A : FA1=FA0-FA0*XA1

A : FA2 = FA0 FA0XA2

B: FB1=FB0-2*FA0*XA1

B : FB2 = FB0 2*FA0*XA2

C: FC1=FA0*XA1

C : FC2 = FA0*XA2

21

TR

Tf

FC
i Pi dT +

i(inlet)

T0

TR

TR

FC
i Pi dT QRe movedbythewalls = (HR )FA0 XA

i(outlet)

TR

FA0C PA dT

T0

FA0 XA1CPA dT +

T0

TF

FA0 X A 2 CPA dT +
TR

Tf

XA2 =

(CPA +

T0

TR

TR

TR

FB0 CPB dT 2 FA0 XA1 CPB dT +

T0

T0

TF

FB0 CPB dT 2 FA0 XA2 CPB dT +


TR

TR

TR

FA0 XA1 CPC dT +

T0

Tf

A0

CPA dT

TR

TF

A0

XA 2 CPC dT = (HR )FA0 XA2

TR

TR

TR

FB0
CPB )dT XA1 ( 2CPB dT CPC dT + CPA )
FA0
T0
T0
T0
(H R |T )

A = ( 2CPB dT
T0

TF

TR

TR

TR

CPC dT +

T0

PA

T0

A = (60,301(298 T0 ) 0, 038105(2982 T02 ) + 3,507 10 6 (2983 T03) 2, 0085 10 9(298 4 T 04))

X A2 =

88, 0433(Tf T0) + 0, 0167(T f 2 T 0 2) 1,77 10 6(T f 3 T 0 3) + X A1 A


90680 + (60,301(298 T 0) 0,038105(298 2 T 0 2) + 3,507 10 6( 2983 T0 3) 2, 0085
10 9 (2984 T0 4))

Table 3.5.2 Reactor-2 data


To

Tf

497

497

497

507

497

517

497

527

497

537

497

547

497

557

497

567

497

577

497

587

497

597

497
497

607
617

Xa
0,1833
2
0,1946
59
0,2060
16
0,2173
9
0,2287
81
0,2401
9
0,2516
17
0,2630
61
0,2745
22
0,2860
01
0,2974
96
0,3090
1
0,3205

k
2,90614E06
4,25746E06
6,14567E06
8,74859E06
1,22912E05

Pco
27,528
28
27,355
19
27,179
12
27,000
02
26,817
81
26,632
1,7055E-05 39
2,33885E- 26,443
05
7
3,17187E- 26,251
05
64
4,25638E- 26,056
05
13
5,65477E- 25,857
05
06
7,44142E- 25,654
05
35
9,70439E- 25,447
05
9
0,0001254 25,237

22

Ph2
66,292
43
66,032
78
65,768
68
65,500
03
65,226
71
64,948
59
64,665
55
64,377
46
64,084
19
63,785
59
63,481
53
63,171
85
62,856

Pch3oh
6,1792
89
6,6120
37
7,0521
93
7,4999
43
7,9554
83
8,4190
14
8,8907
46
9,3708
94
9,8596
83
10,357
34
10,864
12
11,380
25
11,906

Ke
0,0105
86
0,0068
85
0,0045
53
0,0030
58
0,0020
85
0,0014
42
0,0010
1
0,0007
17
0,0005
15
0,0003
74
0,0002
74
0,0002
03
0,0001

(-ra)
0,3498
83
0,5037
3
0,7129
89
0,9919
56
1,3554
96
1,8164
35
2,3803
87
3,0361
86
3,7389
6
4,3812
23
4,7448
36
4,4230
31
2,6964

1/-ra
2,8581
1,9851
89
1,4025
46
1,0081
09
0,7377
37
0,5505
29
0,4201
0,3293
61
0,2674
54
0,2282
47
0,2107
55
0,2260
89
0,3708

71

52

41

59

By -1/ra vs Xa data on table 3.5.2 excel regression gives this equation


-1/ra=y(Xa)= (38246*x^4) - (36734*x^3) + (13296*x^2) - (2154.8*x) + (132.5);
Simpson('reactorvolume2',0.1593,0.2863,1000)
V2/Fa20 = 0,0889
FA 20 = FA0 (1 XA1 ) =30*(1-0,1593) = 25,221 mol/s
V2 = 25,221 * 0,0889 = 2,242
Other Reactors volume calculation shown on Appendix C.3
v1,v2,v3,v4,v5 and v6 values are not in unit of volume.
r = k(PCO P 2H 2

PCH3OH
) (mol / kgcat min)
Ke

k = 7.6 106 mol(kgcat)1 min1 atm3

at 250 C

V1
dX A
=
FA0 [mol / s]
ra[mol / kgcat min]
After making unit correction (seconds convert to minute), kgcat unit is obtained.
Table 3.5.3 Catalyst uses
Reactors

Calculated

Catalyst mass(kg)

Reactor 1

2,637

158,22

Reactor 2

2,242

134,52

Reactor 3

1,394

83,64

Reactor 4

1,6075

96,45

Reactor 5

1,267

76,02

Reactor 6

0,501

30,06

Total catalyst mass

662.43

23

662, 43kgcat 1m3 catalyst


1m3 reactor

=1,4786 m
1
1120kgcat (1 0.6)m3 catalyst

Table 3.5.4 Reactor volumes


Reactors

Volume(lt)

Reactor 1

353,16

Reactor 2

300,26

Reactor 3

186,69

Reactor 4

215.29

Reactor 5

169,68

Reactor 6

67

Total volume

1478,6 lt

24

4.RESULTS & DISCUSSIONS


Firstly, thermodynamics equilibrium line is drawn by using vant hoff equation for
different pressures (figure 3.1). Plot shows that methanol production is rising by pressure
increasing. But, at very high pressures catalyst lifetime is decreasing and also reactor material
may not resist the high pressures. So, Achieving 0.55 converion of methanol, pressure of 100
bar is selected.
Constant rate curves drawn as figure 4.1 by using ra=f(Xa,T) formula. The line goes
through the maximum points of these curves is operating line.To close to operating line, first
reactor inlet temperature is selected 490. If more less T0 value is selected, the number of
reactors should be decreased. But, according to the rate equation(the function of temperature
and conversion); reaction rate is decreasing with temperature decreasing. If,T0 value is very
high, the reactor number will increase. So, optimum tempretature should be selected.

Figure 4.1 Adiabatic lines and number of reactors (Xa(y-axis) vs T(x-axis))


Xa=f(T) function is obtained by using adiabatic energy balance. Using these lineer
functions, adiabatic lines for each reactor are drawn(figure 4.1).
ra=f(T,xa) is also function of temperature.adiabatic line and rate equations are solved
simultaneously and Xa vs -1/ra data are obtained.These data plotted on figure 4.2.Each reactor

25

functions is monitorized with excel.And using these functions in a simpsons integration rule
matlab function, areas under the curves are calculated.These results equals to Vi/Fa0(i)
Fa0 unit is selected as [mol/s]. It is converted to mol/min. ra unit is [mol/kgcat*min].
After doing these unit conversions, areas under the curves(at figure 4.2) gives the result
[kgcat]. The reactor volume results are obtained by dividing the kgcat results by catalyst
density and a volume conversion factor (volume of catalyst to volume of reactor).(catalyst
void volume is selected 0,6).

Figure 4.2 -1/ra(y axis) vs Xa(x axis)

26

Appendix - A.1
Table App.A.1.1 Reduced temperatures of substances
T,K
400
420
440
460
480
500
520
540
560
580
600

Tr(metanol)
0,77942323
0,81839439
0,85736555
0,89633671
0,93530787
0,97427903
1,01325019
1,05222136
1,09119252
1,13016368
1,16913484

Tr(CO)
3,007518797
3,157894737
3,308270677
3,458646617
3,609022556
3,759398496
3,909774436
4,060150376
4,210526316
4,360902256
4,511278195

Tr(H2)
12,01201201
12,61261261
13,21321321
13,81381381
14,41441441
15,01501502
15,61561562
16,21621622
16,81681682
17,41741742
18,01801802

Table App.A.1.2 Fugacity coefficients of substances at P = 50 bar


T,K
400
420
440
460
480
500
520
540
560
580
600

(CO)

(methanol)

1,012
1,014
1,015
1,017
1,018
1,018
1,019
1,019
1,02
1,02
1,02

0,1538
0,2424
0,3591
0,504
0,7093
0,7553
0,7919
0,8222
0,8475
0,869
0,8873

(H2)
1,017
1,017
1,016
1,016
1,015
1,015
1,014
1,014
1,014
1,013
1,013

Table App.A.1.3 Fugacity coefficients of substances at P = 75 bar


T
400
420
440
460
480
500

(CO)

(methanol)

(H2)

1,0900
1,0220
1,0240
1,0260
1,0280
1,0290

0,1067
0,1681
0,2490
0,3498
0,4685
0,5999

1,0270
1,0260
1,0250
1,0240
1,0240
1,0230

27

520
540
560
580
600

1,0290
1,0300
1,0300
1,0310
1,0310

0,6904
0,7375
0,7757
0,8075
0,8346

1,0220
1,0220
1,0210
1,0200
1,0200

Table App.A.1.4 Fugacity coefficients of substances at P = 120 bar


T
400
420
440
460
480
500
520
540
560
580
600

(CO)
1,03400
1,03900
1,04200
1,04500
1,04700
1,04800
1,05000
1,05000
1,05100
1,05100
1,05100

(methanol)
0,07151
0,11270
0,16700
0,23480
0,31520
0,40580
0,50170
0,58950
0,65430
0,70480
0,74670

(H2)
1,04600
1,04400
1,04300
1,04100
1,04000
1,03800
1,03700
1,03600
1,03500
1,03400
1,03300

Appendix A.2
Ky =

30X Ae
100-60X Ae
30-30X Ae 70 60XAe

100 60X Ae 100 60XAe

By expanding this equation ;


X Ae3 (36 36 Ky ) + XAe 2 (120 + 84 Ky + 36 Ky ) + XAe ( 100 49 Ky 84 Ky ) + 49 Ky = 0

For Solving this equation on MATLAB R2007a, we defined these parameters:


a = (36 36 K y )
b = (120 + 84 K y + 36 K y )
c = (100 49 K y 84 K y )
d = 49 K y
a,b,c,d are polynomial coefficients and there is a function on matlab to find roots of high order
functions by using these polynomial coefficients.
M.File of Matlab is ;
function a=c(A)
a = -36 - (36 * A);

28

b = 120 + (84 * A) + (36 * A);


c = -100 - (49 * A) - (84 * A);
d = 49*A;
p=[a b c d];
a = roots(p);

and we call the function on command window like c(Ky)


Example :
c (31217.42) gives the result below
ans =
1.1669 + 0.0075i
1.1669 - 0.0075i
0.9995
Our Xae value is 0,995. Other roots are imaginer and not validating Xae.(Xae must be
0<Xae<1 and real )
By using other Ky values on this matlab function, we get the Xae values on Table 3.3, 3.5,
3.7.

29

Appendix B.1
The rate expression is derived as a function of T and Xa.
XA

100)
7
(1 X A )
3
r = (k) ((
100) (
100) 2
)
7
7
3,567E

12

exp(90130
/ 8,314 T)
(1 2X A ) +
(1 2X A ) +
3
3
(

7
2X A
3

(1 2X A ) +

The execution of program is based on scanning T and Xa values at the range of


(400<T<650 T+=0.1) and (0<Xa<1 Xa+=0.01). In the program constant r value is given from
textbox and the program calculate and r value from T and Xa values. If r(given from textbox)
r(calculated from equation) = 0 (almost 0, its sensivity differs by T and r to obtain more
data).
The variables are defined as;
k = 743.198 * (Math.Exp(-80000 / (8.3145 * T)));
Pco = ((1 - Xa)/((10/3)-(2*Xa)))*100;
Ph2 = (((7/3)-(2*Xa))/((10/3)-(2*Xa)))*100;
Pch3oh = ((Xa)/((10/3)-(2*Xa)))*100;
Ke = (0.000000000003567) * ((Math.Exp((90130) / (8.3145 * T))));
ra = (k * ro * ((Pco * (Ph2 * Ph2)) - (Pch3oh / Ke)));

Main code block of this program is :


for (T = 400; T < 700; T += 1)
{
for (Xa = 0; Xa < 1; Xa += 0.01)
{
k = 743.198 * (Math.Exp(-80000 / (8.3145 * T)));
Pco = ((1 - Xa)/((10/3)-(2*Xa)))*100;
Ph2 = (((7/3)-(2*Xa))/((10/3)-(2*Xa)))*100;
Pch3oh = ((Xa)/((10/3)-(2*Xa)))*100;
Ke = (0.000000000003567) * ((Math.Exp((90130) / (8.3145 * T))));
ra = (k * ((Pco * (Ph2 * Ph2)) - (Pch3oh / Ke)));
if (r <= 0.03 && (ra - r) < 0.000015&& (ra - r) > -0.000015)
{
listBox1.Items.Add(T.ToString() + " " + Xa.ToString() + " " + ra.ToString());
listBox2.Items.Add(T.ToString());
listBox3.Items.Add(Xa.ToString());
}
if (T < 470 && r > 0.03 && r <= 0.15 && (ra - r) < 0.00015 && (ra - r) > -0.00015)
{
listBox1.Items.Add(T.ToString() + " " + Xa.ToString() + " " + ra.ToString());
listBox2.Items.Add(T.ToString());

30

listBox3.Items.Add(Xa.ToString());
}
if (T<550 && T > 470 && r > 0.03 && r <= 0.15 && (ra - r) < 0.001 && (ra - r) > -0.001)
{
listBox1.Items.Add(T.ToString() + " " + Xa.ToString() + " " + ra.ToString());
listBox2.Items.Add(T.ToString());
listBox3.Items.Add(Xa.ToString());
}
if (T > 550 && r > 0.03 && r <= 0.15 && (ra - r) < 0.03 && (ra - r) > -0.03)
{
listBox1.Items.Add(T.ToString() + " " + Xa.ToString() + " " + ra.ToString());
listBox2.Items.Add(T.ToString());
listBox3.Items.Add(Xa.ToString());
}
...

//(other if else loops exist here for other range of T for varying (r-ra) sensibilities.These code
block written to get uniform distributed data at temperature range 400 700 K)
else
{
continue;
}

All code block and .exe file of this program is given at CD-ROM (attached to report).

Figure A.3 A screenshot from constant rate program

31

Appendix B.2
Table B.2 constant rate data
r=1
T
520
523
524
532
534
538
539
540
541
541
542
546
553
553
556
573
577
581
590
605
621
659
679

Xa
0,01
0,1
0,13
0,29
0,32
0,37
0,38
0,39
0,4
0,4
0,41
0,44
0,47
0,47
0,48
0,48
0,47
0,46
0,43
0,37
0,3
0,16
0,11

r=2
T
541
542
542
543
543
544
545
545
546
546
547
547
548
549
550
550
552
553
560
561
561
564
566
569
569
572
573
588
588
593
597
597
615

Xa
0,03
0,06
0,06
0,08
0,09
0,11
0,13
0,13
0,15
0,15
0,17
0,17
0,19
0,2
0,22
0,22
0,25
0,26
0,33
0,34
0,34
0,36
0,37
0,38
0,38
0,39
0,39
0,39
0,39
0,38
0,37
0,37
0,31

r=5
T
569
570
571
572
579
580
581
582
586
596
614
624
632
643

Xa
0
0,02
0,04
0,06
0,16
0,17
0,18
0,19
0,22
0,26
0,26
0,24
0,22
0,19

r=8
T
590
597
600
604
607
627

Xa
0,07
0,14
0,16
0,18
0,19
0,2

For more little scattered constant rate data by different values of r are available in the
Excel file (constant rate curces at 100 bar.xls) on CD-ROM.

32

Appendix C.1
Simpsons integration M.File on matlab:
function I=Simpson(f,a,b,n)
%f nin integrali simpson kural
% n ift say olacak
h=(b-a)/n;
S= feval(f,a);
for i=1:2:n-1
x(i)=a+h*i;
S=S+4*feval(f,x(i));
end
for i=2:2:n-2
x(i)=a+h*i;
S=S+2*feval(f,x(i));
end
S=S+feval(f,b);
I=h*S/3;

The function is called from command window like:


V1/Fa01=Simpson(reactorvolume1,0,0.1563,1000)
reactorvolume1 = is another m.file which includes function of -1/ra by Xa;
0 = Xa0;
0.1563 = Xa1;
1000 = Diveding factor (if it is larger, result of the numerical result approaches analytical
result )

Appendix C.2
M.Files of reactor volume equations (-1/ra function by Xa) :
Reactor 1:
function y1=reactorvolume1(x)
y1=(-157200*x^5) + (85543*x^4) - (18291*x^3) + (1979.3*x^2) - (114.38*x) + (3.0754);

Reactor 2:
function y2=reactorvolume2(x)
y2=(38246*x^4) - (36734*x^3) + (13296*x^2) - (2154.8*x) + (132.5);

Reactor 3:
function y3=reactorvolume3(x)
y3=(65582*x^4) - (91531*x^3) + (48084*x^2) - (11278*x) + (997.57);

Reactor 4:
function y4=reactorvolume4(x)
y4=(119805*x^4) - (207253*x^3) + (134786*x^2) - (39071*x) + (4261.7);

Reactor 5:
33

function y5=reactorvolume5(x)
y5=(177966*x^4) - (355243*x^3) + (266463*x^2) - (89032*x) + (11184);

Reactor6:
function y6=reactorvolume6(x)
y6=(366299*x^4) - (785097*x^3) + (631702*x^2) - (226167*x) + (30405);

Appendix C.3
C.3.1 Reactor 3
0,3863

V3
dX A
=
FA30 0,2863 R A
Inlet

outlet

A : FA2=FA0-FA0*XA2

A : FA3 = FA0 FA0XA3

B: FB2=FB0-2*FA0*XA2

B : FB3 = FB0 2*FA0*XA3

C: FC2=FA0*XA2

C : FC3 = FA0*XA3

TR

T0

Tf

FC
i Pi dT +

i(inlet)

TR

TR

FC
i Pi dT QRe movedbythewalls = (HR )FA0 XA

i(outlet)

TR

FA0 C PA dT

T0

FA0X A 2C PAdT +

T0

TF

TF

TR

TR

FA0 X A3CPA dT +

TR

TR

TR

Tf

T0

T0

T0

TR

FB0C PBdT 2 FA0X A 2C PBdT +


TF

TF

TR

TR

FB0 CPB dT 2 FA0 XA3 CPB dT +

Tf

X A3

TR

TR

A0

FA0X A 2C PCdT +

C PAdT

A0

XA3 CPC dT = (HR )FA0 XA3


TR

F
T0 (CPA + FA0B0 CPB )dT XA 2 (T0 2CPB dT T0 CPC dT + T0 CPA )
=
( H R |T )
TR

A = ( 2CPB dT
T0

TR

T0

TR

CPC dT +

PA

T0

A = (60,301(298 T0 ) 0, 038105(298 2 T0 2) + 3,507 10 6(298 3 T0 3 ) 2, 0085 109 (2984 T0 4 ))

X A3 =

88, 0433(Tf T0 ) + 0, 0167(Tf 2 T0 2 ) 1, 77 10 6 (Tf 3 T0 3 ) X A 2 A


90680 + (60,301(298 T0 ) 0, 038105(298 2 T0 2 ) + 3,507 10 6 ( 2983 T0 3 ) 2, 0085 109 (2984 T0 4 ))

34

Table C.3.1 Reactor-3 data


To

Tf

Xa

Pco

Ph2

Pch3oh

Ke

(-ra)

1/-ra

502

502

0,2863

3,52419E-06

25,85183

63,77774

10,37043

0,008519

0,366295

2,730037

502

512

0,2963

5,12434E-06

25,67561

63,51341

10,81098

0,005587

0,520835

1,919994

502

522

0,3063

7,34494E-06

25,4968

63,2452

11,25799

0,003724

0,72688

1,375743

502

532

0,3163

1,03863E-05

25,31535

62,97302

11,71163

0,002521

0,994431

1,005601

502

542

0,3263

1,45004E-05

25,13118

62,69677

12,17204

0,001731

1,330492

0,751602

502

552

0,3363

2,00009E-05

24,94425

62,41638

12,63937

0,001205

1,733817

0,576762

502

562

0,3463

2,72739E-05

24,75449

62,13173

13,11378

0,000849

2,185292

0,457605

502

572

0,3563

3,67905E-05

24,56183

61,84274

13,59543

0,000606

2,631077

0,380073

502

582

0,3663

4,91199E-05

24,3662

61,54931

14,08449

0,000438

2,95395

0,33853

502

592

0,3763

6,4944E-05

24,16755

61,25132

14,58113

0,00032

2,925888

0,341777

502

602

0,3863

8,50728E-05

23,96579

60,94869

15,08552

0,000236

2,131355

0,469185

By -1/ra vs Xa data on table C.3.1 excel regression gives this equation


-1/ra=y(Xa)= (65582*x^4) - (91531*x^3) + (48084*x^2) - (11278*x) + (997.57);
Simpson('reactorvolume3',0.2863,0.3863,1000)gives
V3/Fa30 = 0.0757
FA30 = FA0 (1 XA3 ) =30*(1-0,3863) = 18,411 mol/s
V3 = 18,411 * 0.0757= 1,394
Reactor 4
0,4663

V4
dXA
=
FA40 0,3863 R A
Tf

XA4

TR

TR

TR

F
T0 (CPA + FA0B0 CPB )dT XA3 (T0 2CPB dT T0 CPC dT + T0 CPA )
=
(H R |T )
TR

A = ( 2CPB dT
T0

TR

T0

TR

CPC dT +

PA

T0

A = (60,301(298 T0 ) 0, 038105(2982 T02 ) + 3,507 10 6 (2983 T03) 2, 0085 10 9(298 4 T 04))


XA4 =

(88, 0433(Tf T0 ) + 0, 0167(Tf 2 T0 2 ) 1, 77 10 6 (Tf 3 T0 3 )) X A3 A


90680 + (60,301(298 T0 ) 0, 038105(298 2 T0 2 ) + 3,507 10 6 (2983 T0 3 ) 2, 0085 10 9 (2984 T0 4 ))

35

Table C.3.2 Reactor-4 data


To

Tf

Xa

Pco

Ph2

Pch3oh

Ke

(-ra)

1/-ra

507

507

0,3863

4,25746E-06

23,96579

60,94869

15,08552

0,006885

0,369699

2,704904

507

517

0,3963

6,14567E-06

23,76086

60,64128

15,59786

0,004553

0,515938

1,938218

507

527

0,4063

8,74859E-06

23,55267

60,329

16,11833

0,003058

0,703841

1,420776

507

537

0,4163

1,22912E-05

23,34115

60,01173

16,64712

0,002085

0,935085

1,069422

507

547

0,4263

1,7055E-05

23,12623

59,68934

17,18443

0,001442

1,201953

0,831979

507

557

0,4363

2,33885E-05

22,90781

59,36171

17,73049

0,00101

1,477438

0,676848

507

567

0,4463

3,17187E-05

22,6858

59,02871

18,28549

0,000717

1,697902

0,588962

507

577

0,4563

4,25638E-05

22,46014

58,6902

18,84966

0,000515

1,733567

0,576845

507

587

0,4663

5,65477E-05

22,23071

58,34606

19,42323

0,000374

1,339535

0,746528

507

587

0,4663

5,65477E-05

22,23071

58,34606

19,42323

0,000374

1,339535

0,746528

By -1/ra vs Xa data on table C.3.2 excel regression gives this equation


-1/ra=y(Xa)= (119805*x^4) - (207253*x^3) + (134786*x^2) - (39071*x) + (4261.7);
Simpson('reactorvolume4',0.3863,0.4663,1000)gives
V4/Fa40 = 0.1004
FA 40 = FA0 (1 XA4 ) =30*(1-0,4663) =16,011 mol/s
V4 = 16,011 * 0,1004= 1,6075
Reactor 5
0,5243

V5
dX A
=
C.5.1
FA50 0,4663 R A
2
2
3
(88, 0433(T
T ) 1, 77 6 103 (T
X4
A
f
0T )+ 0, 0167(T
f
0
f
0 T )) A
XA 5 =
2
2

6
3
3
90680+ (60, 301(2980 T ) 0,038105(298 0 T ) 3, 298
507 + 10T )( 2,
00085 10 (298
9

C.5.2

T ))
4

Solving simultaneously equation C.5.1 and C.5.2


Table C.3.3 Reactor-5 data

To

Tf

Xa

Pco

Ph2

Pch3oh

Ke

(-ra)

1/-ra

514

514

0,4663

5,51309E-06

22,23071

58,34606

19,42323

0,005146

0,396415

2,522606

514

519

0,4713

6,60261E-06

22,11455

58,17183

19,71362

0,0042

0,463111

2,159311

514

524

0,4763

7,88028E-06

21,99742

57,99614

20,00644

0,003441

0,537237

1,861376

514

529

0,4813

9,3738E-06

21,87931

57,81896

20,30174

0,00283

0,618375

1,61714

514

534

0,4863

1,11142E-05

21,76019

57,64028

20,59953

0,002336

0,705488

1,417458

514

539

0,4913

1,31362E-05

21,64006

57,46008

20,89986

0,001935

0,79665

1,255256

514

544

0,4963

1,54783E-05

21,5189

57,27835

21,20276

0,001608

0,888692

1,12525

36

4
0

514

549

0,5013

1,81837E-05

21,3967

57,09505

21,50825

0,001341

0,976726

1,023828

514

554

0,5063

2,12999E-05

21,27345

56,91017

21,81638

0,001122

1,053527

0,949192

514

559

0,5113

2,48796E-05

21,14913

56,7237

22,12717

0,000942

1,108712

0,901947

514

564

0,5163

2,8981E-05

21,02373

56,5356

22,44067

0,000793

1,127685

0,886772

514

572

0,5243

3,67905E-05

20,82081

56,23122

22,94797

0,000606

1,029673

0,971182

By -1/ra vs Xa data on table C.3.3 excel regression gives this equation


-1/ra=y(Xa)= (177966*x^4) - (355243*x^3) + (266463*x^2) - (89032*x) + (11184);
Simpson('reactorvolume5',0.4663,0.5243,1000) gives
V5/Fa50 = 0.0888
FA50 = FA0 (1 XA5 ) =30*(1-0,5243) = 14,271 mol/s
V5 = 14,271 * 0,0888 = 1,267
Reactor 6
0,5533

V6
dX A
=
.C.6.1
FA60 0,5243 R A
X A5 =

(88, 0433(Tf T0 ) + 0, 0167(Tf 2 T02 ) 1, 77 10 6 (Tf 3 T03 )) XA4 A


90680 + (60,301(298 T0 ) 0, 038105(2982 T02 ) + 3,507 10 6 (298 3 T03 ) 2, 0085 10 9 (2984 T04 ))

C.6.2
Solving simultaneously equation C.6.1 and C.6.2
Table C.3.4 Reactor-6 data
To

Tf

Xa

Pco

Ph2

Pch3oh

Ke

(-ra)

1/-ra

533

533

0,5243

1,07448E-05

20,82081

56,23122

22,94797

0,002426

0,605749

1,650848

533

537

0,5283

1,22912E-05

20,71828

56,07742

23,2043

0,002085

0,664023

1,505973

533

542

0,5333

1,45004E-05

20,5891

55,88365

23,52725

0,001731

0,73527

1,360045

533

547

0,5383

1,7055E-05

20,45878

55,68816

23,85306

0,001442

0,7999

1,250157

533

552

0,5433

2,00009E-05

20,32729

55,49093

24,18178

0,001205

0,850469

1,175822

533

557

0,5483

2,33885E-05

20,19463

55,29194

24,51343

0,00101

0,876376

1,141063

533

562

0,5533

2,72739E-05

20,06078

55,09116

24,84806

0,000849

0,862807

1,159007

By -1/ra vs Xa data on table C.3.4 excel regretion gives this equation


-1/ra=y(Xa)= (366299*x^4) - (785097*x^3) + (631702*x^2) - (226167*x) + (30405)
Simpson('reactorvolume6',0.5243,0.5533,1000) gives
V6/Fa60 = 0.0374
FA60 = FA0 (1 XA6 ) =30 *(1-0,5533) = 13,401 mol/s

37

V6 = 13,401 * 0,0374 = 0,501

Appendix D.1
Rate equation uses for methanol productions[7]

38

References
1- Wade L.E. Gengelbach, R.B. Taumbley, J.L. Hallhover W.L. Krk-Other Encyclopedia of
Chemical Technology, 3rd. Edition, Wiley New York 1981 Vol 15 page 398-415
2- G.H. Graaf, Sytsema P.J.J., Stamhus E.J., Joosten G.E.H. Chem. Eng.Sci. Vol 41, 11,
page 2883 (1986)
3- Satterfield N.D., Heterogeneous Catalysis in Practice, McGraw Hill, 1980
4- Howard F. Rase, Handbook of Commercial Catalysts, Crc Pres,2000, page 429-430
5- Sandler , S.I, Chemical and Engineerig Thermodynamics, Third edition, John Wiley &
Sons Inc. , 1999 , page 759
6- Smith, J.M., VanNess, H.C., Introduction to Chemical Engineering Thermodynamics, 3rd
Ed., McGrow Hill, Newyork, 1996.
7- http://www.rajwantbedi.com/dg1_final.pdf

39

SYMBOLS
Cpi

: Heat capasity

: Fugacity coefficient

J/mol.K

G 298 : Standart Gibbs energies of formation ,


H 298 : Standart Enthalpies

J/mol

J/mol

Kf

: Equilibrium constant

Ky

: Equilibrium constant (molar fractions)

: Equilibrium constant(fugacity coefficients)

Tr

: Reduced Temperature

Pr

: Reduced Pressure

: Pressure

bar

: Ideal gas law constant

8,314 J/mol.K

: Temperature

XA

: Fractional conversion of Carbon monoxide

X Ae

: Equilibrium conversion of Carbon monoxide

40

41