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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
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.
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
nCH4
CO +3H2
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
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].
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
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
P,H2
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)
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)
p r
G
o d u c ts
ta
G298 = (-162,0)-(-137,2)
J
8,314 mol K 298K ln K298 =-24800 j/mol
P,CHOH
P,H2
T 0
dT
RT
P,CO
dH cpdTT
TR
2C
(InKf )T InK
H = H298 + Cp dT
298
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
Kf exp(19,33905
9139,46
Kf
1,619805
0,415906
0,119779
0,03814
0,013267
0,00499
0,002012
0,000863
0,000392
0,000187
9,33E-05
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
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
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
100-60XAe
30-30X Ae 70 60X Ae
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
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
1,619805
70 60XAe
60X
ia .ib
Ae
100
30XAe
100-60XAe
30-30X
Ae
70 60X Ae
0,09281 75
2
75 2
ic
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
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
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
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
30-30X Ae 70 60X Ae
Figure 3.1 Xae versus Temperature(K) graph for methanol production at given conditions
14
r k(PCO P2H2
) ; Ke
F
A
PA
PA
FT PT
A 2B C
Fa0
FA
PT (3.1);
FT
Fb0
F F F X
A
A0
A0
FB FB0 2FA0 XA
F F X
C
A0
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
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 )
16
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
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
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.
18
2g
28g
30molCO molCO 980g / s ;
molH2
FA0 30mol / s ;
Mmethanol 32g / mol
F
F
F
(CH3OH)
(CH3OH)0
(CO)0
CO
19
R byflows
T0
TR
R byflows
Tf
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
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
3
( 298
) 2,0085
10
))
(298 T
.. 3.5.1
V
F
Ao
0,1593
dX
R
3.5.2
7
(1 XA )
2XA
100)
7
( (1 2XA ) 3
100)
)
3,567E 12 exp(90130 / 8,314 T)
20
Tf
Xa
Pco
490
490
2,20397E-06 30
490
500
0,009866 3,2641E-06
490
510
490
520
490
530
490
540
490
550
490
560
0,06837
490
570
490
580
0,087652 4,6398E-05
490
590
0,09726
7,647774 0,130757
490
600
9,557504 0,10463
490
610
490
620
490
630
0,13551
490
640
490
650
490
655
0,1593
29,8809
Ph2
Pch3oh
Ke
(-ra)
1/-ra
70
2,138834 0,00091
1,023625
3,470503 0,288143
13,55422 0,073778
14,89287 0,067146
V
F
A20
0,2863
2
dX A
0,1593
Inlet
outlet
A : FA1=FA0-FA0*XA1
B: FB1=FB0-2*FA0*XA1
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
X
A2
2
0
2
)
3
f
T 3) X A
0
3
T )
3,507 10 ( 298
A1
2,0085
9
10
4
(298
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
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
PCH3OH
Ke
6
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
23
662.43
1120kgcat
1m3 reactor
=1,4786 m
(1 0.6)m catalyst
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
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)
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
(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
(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
(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
( 36 36 K ) X
Ae
(120 84 K 36 K ) X ( 100 49 K 84 K ) 49 K 0
Ae
yAe
28
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
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).
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;
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)
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
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
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
A3
88,0433(T T ) 0,0167(T
f
T 2 ) 1,77 106 (T 3 T 3) X A2 A
0
3
0
) 2,0085 10 9
(298
T 4 ))
0
Tf
Xa
Pco
Ph2
502
502
0,2863
502
512
0,2963
502
522
0,3063
7,34494E-06 25,4968
502
532
0,3163
502
542
0,3263
502
552
0,3363
502
562
0,3463
502
572
0,3563
502
582
0,3663
4,91199E-05
24,3662
502
592
0,3763
6,4944E-05
502
602
0,3863
63,2452
Pch3oh
Ke
(-ra)
1/-ra
1,375743
0,33853
2,925888 0,341777
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
T0
T0
( HR |T )
TR
TR
T0
T0
A = ( 2CPBdT
TR
CPC dT CPA )
T0
A4
35
(298
T 3 ) 2,0085 10 9 (298 4 T 4 ))
0
Tf
Xa
Pco
507
507
0,3863
4,25746E-06
Ph2
Pch3oh
Ke
(-ra)
1/-ra
507
517
0,3963
6,14567E-06
507
527
0,4063
8,74859E-06
23,55267 60,329
16,11833
507
537
0,4163
1,22912E-05
23,34115 60,01173
507
547
0,4263
1,7055E-05
507
557
0,4363
2,33885E-05
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
507
587
0,4663
5,65477E-05
1,477438 0,676848
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
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
533
537
0,5283
533
542
0,5333
1,45004E-05 20,5891
533
547
0,5383
1,7055E-05
533
552
0,5433
533
557
0,5483
533
562
0,5533
1,360045
1,250157
0,876376 1,141063
37
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
J/mol
Kf
: Equilibrium constant
Ky
Tr
: Reduced Pressure
: Pressure
bar
8,314 J/mol.K
: Temperature
XA
X
Ae
40
41