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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,H 2 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
mixture of 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 CH 3 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) Search 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% H 2, 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, nonadiabatic, 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 data page.

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 temperature range between 450-650K and
pressures 50-100 bar.

at
250C

The catalytic packed bed bulk density was given as

INTRODUCTION
Methyl Alcohol as an Industrial Chemical
Methanol (methyl alcohol), CH 3OH, 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 12x10 6 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 available 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 (100250 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

nCH4

Steam reforming of CH4:


CH4 + H2O

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, %
CO2 conversion, %
Exit CH3OH, vol %
5MPa 10MPa 30MPa 5MPa 10MPa 30MPa 5MPa 10MPa 30MPa
95.6
72.1
25.7
-2.3
-12.8

99.0
90.9
60.6
16.9
-7.2

99.9
98.9
92.8
73.0
38.1

44.1
18.0
14.3
19.8
27.9

82.5
46.2
24.6
23.6
30.1

99.0
91.0
71.1
52.1
44.2

27.8
16.2
5.6
1.3
0.3

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 Cu-Zn-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


oxide-chromium oxide. It is a more robust catalyst than the low pressure copperbased catalyst and can tolerate higher temperature and sulfur levels. The copperzinc 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 CO 2, H2O or O2 in the synthesis
gas. If none of these is present, the catalyst gradually loses activity, since the Cu-ZnO 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]

1.5.2Side 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)

G298 (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)

P,CO

(T,K) 27,113 + 0,655 X102 T 0,1 X105 T2 [j /mol.K]

P,H2

(T,K) = 26,113 + 0,435 X102 T 0,033 X105 T2 [j /mol.K]

CP,CH3OH (T,K) = 19,038 + 9,146 X102 T 1,218 X105 T2 - 8,034 X 109 T3 [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, K f
(T) : + H 298 and G298 values are given at thermodynamics data part.

H 298

p r

ta

d u c ts

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

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

p r

G
o d u c ts

ta

G298 = (-162,0)-(-137,2)

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


G RT ln K298

J
8,314 mol K 298K ln K298 =-24800 j/mol

ln K298 = 10,0097 K298 = 22243,38

dInKf H .... Van't Hoff Equation


dT R 2
T
C C
P

P,CHOH

P,H2

T 0

dT

RT

P,CO

dH cpdTT

TR

2C

(InKf )T InK

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


CP = -60,301 + 7,621X102 T 1,052 X105 T2 - 8,034 X 109 T3 (J/mol.K)

H = H298 + Cp dT
298

H = - 75985,54 + (60,301 T) (0,0381 T2 ) (3,5067 106 T3 ) (2,0085 109 T4 )

d ln Kf
298

1
R

298

H(T)dT
T

R=8,3145 J/mol.K;
ln K298 = 10,0097

(InKf)= InK298 +
9139,46
(9,32935

7,2529ln(T) 4,5826 103 T 4,2178 107 T2 2,4151010 T3 )

Kf exp(19,33905

9139,46

7,2529ln(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 Pn f / P ( fugacity coefficient)
Basis: 100 moles/s Feed composition enter the reactor

CO 2H 2 CH 3OH

CO A ,

H2 B ,

CH3OH C

A 2B C
30 70
-a -2a a
---- ---- ---30-a 70-2a a
nT = 30 a + 70 2a + a = 100 2a CA0 = 30 (due to basis 100 moles reactant)
a=CA0 . XAe a = 30 XAe
yc
Ky yA .yB

ic

K 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( XAe ) 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

10

Pr(H2)
3,855050116

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

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

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

30XAe
100-60XAe
Kf 30-30XAe
100 60XAe

70 60XAe

ia .ib 2

50 2

100 60XAe
30XAe

100-60XAe
1,619805

ic

30-30X

Ae

70 60X Ae

50
0,1538
2
(1,017) 1,012

100 60XAe 100 60XAe


30XAe
100-60XAe
26909,64 = 30-30X Ae 70 60XAe 2

100 60XAe

100 60XAe

An equation Ky = f( XAe ) such as:


30XAe
Ky

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

100 60XAe 100 60XAe


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

11

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

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)
0,092810483
0,156250745
0,231447055
0,325141594
0,434626865
0,557073141
0,642367583
0,685524544
0,722445487
0,752806781
0,778071256

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

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


30XAe
100-60XAe
Kf 30-30XAe
100 60XAe

1,619805

70 60XAe

60X

ia .ib

Ae
100
30XAe
100-60XAe

30-30X

Ae

70 60X Ae

0,09281 75
2

100 60XAe 100 60XAe


30XAe
100-60XAe
98172,15 = 30-30X Ae 70 60XAe

75 2

ic

100 60XAe 100 60XAe


An equation Ky = f( XAe ) such as:

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

12

30XAe
Ky

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

100 60XAe 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)


30XAe
100-60XAe

Kf 30-30XAe 70 60XAe

100 60XAe

60X

1202

ic

ia .ib

Ae
100
30XAe
100-60XAe
0,063209575 752
1,619805
70 60X 2
30-30X Ae
Ae

100 60XAe 100 60XAe

13

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

30XAe
100-60XAe
369013,7 = 30-30X Ae 70 60X Ae

100 60XAe 100 60XAe


An equation Ky = f( XAe ) such as:
30XAe
Ky

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

100 60XAe 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 :
PCH3OH

r k(PCO P2H2

) ; 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

F
A

PA

PA

FT PT
A 2B C
Fa0

FA

PT (3.1);

FT

Fb0

-Fa0Xa -2Fa0Xa Fa0Xa


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

F F F X
A

A0

A0

FB FB0 2FA0 XA

F F X
C

A0

FT FA0 (1 2XA ) FB0


Using formula 3.1 and expressions above, these are derived :
r ra ; r=-ra ; FA CA V0 ;
1
FA

C (1 X )
A0

V0 ;

1 XA

F
B

(C 2C X )
B0

A0

V0 ;

1 XA

FC

C X
A0

V0 ;

1 XA
FT FA FB FC

FT

C C 2C X
A0

B0

1 XA

15

A0

V0 ;

C (1 X )
A0

PA C

A0

1 X A
C 2C X
B0

A0

100
0

(1 XA )
(1 2X A ) 7

1 XA

(C 2C X )
B0

PB C

A0

A0

3
V

1 XA
C 2C X
B0

A0

7 2X
A
3
100
100 (Hydrogen gas)
(1 2X A ) 7

1 XA
C X
A0

PC C

A0

1 XA
C 2C X
B0

100 (Carbon Monoxide)

A0

100
0

(1 2X A ) 7

1 XA

100 (Methanol)

All of the partial pressure expressions numerators and denominators are divided
by CA0 , (CB0 / CA0 70 / 30) The rate expression is obtained as a function of
temperatures(T) and molar fractions (Xa).
XA

7 100)
3
2
ra (k) ((
7 100) (
7 100) 3,567E 12 exp(90130 / 8,314 T) )
(1 2XA )
(1 2XA )
3
3
(1 XA )

7
2XA
3

(1 2XA )

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

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

Other constant rate datas given at appendix B.2.


17

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 H2
Outlet stream : F CH 3 OH , FCO,
F H2 General Energy Balance equation :
TR

T0

FC dT
i(inlet)

i Pi

Tf

FC dT Q

i(outlet)

i Pi

Removedbythewalls

( H )F X
R A0 A

TR

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 HR |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 molCO 980g / s ;

molH2
FA0 30mol / s ;
Mmethanol 32g / mol
F
F
F
(CH3OH)

(CH3OH)0

(CO)0

0 30 0,55 16,5mol / s methanol = 528 g/s methanol

CO

Daily production = 528g (60 60 24)s 1ton6 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

R byflows

T0
TR

R byflows

Tf

(FA0C PA FB0C PB)dT (F AC PA F BC PB F BC PB)dT


(F

A0

PA

FC
B0

TR
Tf

PB

)dT (F C
A0

T0

PA

F X C
A0

A1

PA

F C PB 2F X C F X C PC )dT
B0

A0

A1 PB

A0

A1

TR

Tf

XA1

T0
Tf

(F C F C )dT
A0

PA

B0

PB

(FA0C PA 2FA0 CPB FA0 CPC )dT ( HR )FA0

TR

Tf

(C PA
T0

XA1

F
B0 Tf

CPB )dT

B0

(C

PA

Tf

CPB )dT

A0

T0

A0

( H R |T )

(C PA 2C PB C PC )dT ( HR )

TR

X
A1

88,0433(T T ) 0,0167(T 2 T 2 ) 1,77 10 6 (T 3 T 3)


f

90680 (60,301(298 T ) 0,038105(298 T ) 3,507 10


0

3
( 298

) 2,0085
10

))

(298 T

.. 3.5.1

V
F
Ao

0,1593

dX
R

3.5.2

3.5.1 and 3.5.2 solved simultaneously.


XA

7
(1 XA )

2XA

ra (k) (( (1 2XA ) 7 100) ( (1 2XA ) 7


3
3

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

100)

7
( (1 2XA ) 3

100)

)
3,567E 12 exp(90130 / 8,314 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

490

490

2,20397E-06 30

490

500

0,009866 3,2641E-06

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

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

490

570

0,078022 3,46819E-05 29,01775 68,52662 2,45563

490

580

0,087652 4,6398E-05

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

490

630

0,13551

490

640

0,145035 0,000219751 28,0937

490

650

0,154548 0,000276936 27,95588 66,93382 5,110296 6,24E-05 11,99905 0,08334

490

655

0,1593

29,8809

Ph2

Pch3oh

Ke

(-ra)

1/-ra

70

0,014456 0,323983 3,086582

69,82135 0,297754 0,009287 0,475376 2,103597

2,56562E-05 29,14447 68,7167

2,138834 0,00091

1,023625

3,470503 0,288143

0,000648 4,594486 0,217652

28,88979 68,33469 2,775525 0,000467 5,983472 0,167127

0,000173099 28,22997 67,34495 4,42508

13,55422 0,073778

0,000106 14,93089 0,066975

67,14054 4,765762 8,1E-05

14,89287 0,067146

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

V
F
A20

0,2863
2

dX A

0,1593

Inlet

outlet

A : FA1=FA0-FA0*XA1

A : FA2 = FA0 FA0XA2

B: FB1=FB0-2*FA0*XA1

B : FB2 = FB0 2*FA0*XA2 C : FC2 =

C: FC1=FA0*XA1

FA0*XA2

21
TR

Tf

FC dT

i(inlet)

Pi

T0

TR

FC dT Q

i(outlet)

Pi

Removedbythewalls

( H )F X
R

A0

TR

F C dT
A0

TR

PA

T0

TR

A0

A1

PA

T0

TF

F X

A0

A2

PA

B0

B0

(C PA

T0

PB

A0

Tf

A1

PB

F X C dT
A0

A0

TF

A1

PC

F C dT
A0

PA

TR

F X C dT ( H )F X
A0

A2 PB

A2

PC

A0

A2

TR

TR

F CPB )dT X A1 (

A0

T0

TR

TR

2CPB dT

T0

TR

C dT C )
PC

T0

PA

T0

( H R |T )

A2

TR

A= (

TF

PB

TR

F
Tf

TR

T0

dT F C dT 2

TR

B0

T0
TF

TR

F X C dT F C dT 2 F X C dT F X C dT

TR

2C dT
PB

T0

T0

TR
PC

dT CPA )
T0

A (60,301(298 T ) 0,038105(2982 T 2 ) 3,507 10 6 (2983 T 3) 2,0085 10 9(298 4 T 4))


0

X
A2

88,0433(T T ) 0,0167(T f 2 T 2) 1,77 10 6(T


f

2
0

90680 (60,301(298 T ) 0,038105(298 T

2
)

3
f

T 3) X A
0

3
T )

3,507 10 ( 298

A1

2,0085

9
10

4
(298

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

22

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

607

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

617

0,3205

4
T ))

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

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

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

(-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

1/-ra

1,7055E-05
2,33885E05
3,17187E05
4,25638E05
5,65477E05
7,44142E05
9,70439E05

Pco
27,528
28
27,355
19
27,179
12
27,000
02
26,817
81
26,632
39
26,443
7
26,251
64
26,056
13
25,857
06
25,654
35
25,447
9

0,0001254

25,237

62,856

11,906

0,0001

2,6964

0,3708

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

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
FA20 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(PCOP2H2

PCH3OH

(mol / kgcat min)

Ke
6

k 7.610 mol(kgcat) 1 min1 atm3


V1
F [mol / s]
A0

at 250 C

dX A
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

23

662.43

662,43kgcat 1m3 catalyst


1

1120kgcat

1m3 reactor

=1,4786 m

(1 0.6)m catalyst

Table 3.5.4 Reactor volumes

24

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

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

(methanol)
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
27

(CO)
1,0900
1,0220
1,0240
1,0260
1,0280
1,0290

(methanol)
0,1067
0,1681
0,2490
0,3498
0,4685
0,5999

(H2)
1,0270
1,0260
1,0250
1,0240
1,0240
1,0230

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)

(methanol) (H2)

1,03400
1,03900
1,04200
1,04500
1,04700
1,04800
1,05000
1,05000
1,05100
1,05100
1,05100

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

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
30XAe
Ky

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

100 60XAe 100 60XAe


By expanding this equation ;
3

( 36 36 K ) X

Ae

(120 84 K 36 K ) X ( 100 49 K 84 K ) 49 K 0

Ae

yAe

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


a = ( 36 36 Ky )
b = (120 84 Ky 36 Ky )
c = ( 100 49 Ky 84 Ky )
d = 49 Ky
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.
X
A

7
3 2XA

(1 XA )
r (k) ((

7 100)
((1 2XA ) 3

7 100) (
7 100) 3,567E 12 exp(90130 /8,314 T)
(1 2XA )
(1 2XA )
3
3

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:n1
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

V3 0,3863 dXA

F
A30

R
0,2863

Inlet

outlet

A : FA2=FA0-FA0*XA2

A : FA3 = FA0 FA0XA3

B: FB2=FB0-2*FA0*XA2

B : FB3 = FB0

C: FC2=FA0*XA2

2*FA0*XA3 C : FC3 =
FA0*XA3

TR

FC dT

i(inlet)

Pi

T0

FC dT Q

i(outlet)

Pi

( H )F X

Removedbythewalls

A0

TR

TR

Tf

F C dT
A0

TR

PA

T0

TR

A0

A2

PA

T0

TF

F X C

A3

A0

PA

TR

dT

T0

TF
B0

F C dT 2

PA

B0

TR

TR

PB

A2

PB

TF

F X C dT
A0

A3

A0

A2

PC

T0
TF

Tf

A0

PA

TR

F X C dT (H )F X

A0

PB

TR

A3 PC

R A0

A3

TR

TR

TR

F CPB )dT XA2 ( 2CPB dT


A0

A0

T0

PB

B0

(C

T0

F
Tf

TR

F X C dT F C dT 2 F X C dT F X C dT F C dT

T0

T0

TR

CPC dT

C )
PA

T0

( HR |T )

A3

TR

TR

TR

T0

T0

T0

A = ( 2CPBdT CPC dT CPA )


A (60,301(298 T ) 0,038105(298 2 T 2 ) 3,507 10 6 (2983 T 3 ) 2,0085 109 (2984 T4 ))
0

A3

88,0433(T T ) 0,0167(T
f

T 2 ) 1,77 106 (T 3 T 3) X A2 A
0

90680 (60,301(298 T ) 0,038105(298 2 T 2 ) 3,507 10 6( 298 T 3


0

3
0

) 2,0085 10 9

(298

T 4 ))
0

Table C.3.1 Reactor-3 data


To

Tf

Xa

Pco

Ph2

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

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

502

592

0,3763

6,4944E-05

24,16755 61,25132 14,58113 0,00032

502

602

0,3863

8,50728E-05 23,96579 60,94869 15,08552 0,000236 2,131355 0,469185

63,2452

Pch3oh

Ke

(-ra)

11,25799 0,003724 0,72688

61,54931 14,08449 0,000438 2,95395

1/-ra

1,375743

0,33853

2,925888 0,341777

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
V
F
A40

0,4663
4

dX
R

0,3863
Tf

XA4

(C

T0

PA

A
A

B0
A0

TR

TR

TR

CPB )dT XA3 ( 2CPB dT CPC dT CPA )


T0

T0

T0

( HR |T )

TR

TR

T0

T0

A = ( 2CPBdT

TR

CPC dT CPA )
T0

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

A4

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


f0

35

90680 (60,301(298 T ) 0,038105(298 2 T2 ) 3,507 10 6


0

(298

T 3 ) 2,0085 10 9 (298 4 T 4 ))
0

Table C.3.2 Reactor-4 data


To

Tf

Xa

Pco

507

507

0,3863

4,25746E-06

23,96579 60,94869 15,08552 0,006885 0,369699 2,704904

Ph2

Pch3oh

Ke

(-ra)

1/-ra

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

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

507

567

0,4463

3,17187E-05

22,6858

507

577

0,4563

4,25638E-05

22,46014 58,6902

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

0,003058 0,703841 1,420776

1,477438 0,676848

59,02871 18,28549 0,000717 1,697902 0,588962


18,84966 0,000515 1,733567 0,576845

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
FA40 FA0 (1 XA4 ) =30*(1-0,4663) =16,011
mol/s V4 = 16,011 * 0,1004= 1,6075
Reactor 5
V
F

0,5243
5

A50

dX

R
0,4663

C.5.1

(88, 0433(T T )
f

A5

0, 0167(T

2
f

1,77

10 (T

T )) X

A4

90680 (60, 301(2980 T ) 0, 038105(298 0 T ) 3, 298507 10T )( 2, 00085 10 (298


C.5.2 Solving simultaneously equation C.5.1 and C.5.2
Table C.3.3 Reactor-5 data

36

To

Tf

514

514

514

Xa

Pco

Ph2

Pch3oh

Ke

(-ra)

1/-ra

0,4663

5,51309E-06

22,23071

58,34606

19,42323

0,005146

0,396415

2,522606

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

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

514

559

0,5113

2,48796E-05

21,14913

56,7237

21,81638

0,001122

1,053527 0,949192

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
6

A60

dX

0,5243

.C.6.1

6
(88,0433(T T ) 0,0167(T 2 T 2 ) 1,77 10 (T3 T3 )) X A
A5
2
2
6
3
9
4
90680 (60,301(298 T )
)
T 3 )
T 4 ))
0,038105(298 T
3,507 10 (298
2,0085 10 (298

A4

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

533

542

0,5333

1,45004E-05 20,5891

533

547

0,5383

1,7055E-05

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

533

562

0,5533

2,72739E-05 20,06078 55,09116 24,84806 0,000849 0,862807 1,159007

0,002085 0,664023 1,505973

55,88365 23,52725 0,001731 0,73527

20,45878 55,68816 23,85306 0,001442 0,7999

1,360045
1,250157

0,876376 1,141063

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

J/mol.K

: Fugacity coefficient
G298 : Standart Gibbs energies of formation , J/mol

H 298 : Standart Enthalpies

J/mol

Kf

: Equilibrium constant

Ky

: Equilibrium constant (molar fractions)

Tr

: Equilibrium constant(fugacity coefficients)


: Reduced Temperature

: Reduced Pressure
: Pressure

bar

: Ideal gas law constant

8,314 J/mol.K

: Temperature

XA

: Fractional conversion of Carbon monoxide

X
Ae

40

: Equilibrium conversion of Carbon monoxide

41