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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
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
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, %
5MPa 10MPa 30MPa
CO2 conversion, %
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
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)
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)
r o
c t s
t a n
r e a
t s
G 298 = (-162,0)-(-137,2)
J
298K ln K298 =-24800 j/mol
mol K
dInK f H
=
dT
R T2
H
dT
2
T 0 RT
TR
TR
dH = cpdT
H = H298 +
Cp
dT
298
d ln K f =
298
1 T H(T)dT
R 298
T2
R=8,3145 J/mol.K;
ln K 298 = 10,0097
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
Kf
1,619805
0,415906
0,119779
0,03814
0,013267
0,00499
0,002012
0,000863
0,000392
0,000187
9,33E-05
= f / P ( fugacity coefficient)
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 =
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
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
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
0,1538
502
(1, 017) 2 1, 012
30X Ae
100-60X Ae
30-30X Ae 70 60XAe
Ky =
30X Ae
100-60X Ae
30-30X Ae 70 60XAe
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
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
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
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
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 =
30X Ae
100-60X Ae
30-30X Ae 70 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
Ky =
30X Ae
100-60X Ae
30-30X Ae 70 60XAe
Figure 3.1 Xae versus Temperature(K) graph for methanol production at given conditions
14
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
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
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
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 =
19
Q R byflows =
Tf
T0
TR
Q R byflows =
(F C
A
PA
+ F BC PB + F BC PB)dT
TR
Tf
T0
(F
A0
TR
Tf
(F
A0
X A1 =
T0
Tf
(F
A0
TR
Tf
Tf
F
T0 (CPA + FA0B0 CPB )dT
X A1 =
(C
= T0
Tf
(C
PA
FB0
CPB )dT
FA0
(H R |T )
PA
TR
X A1 =
.. 3.5.1
V1
=
FAo
0,1593
dX A
3.5.2
RA
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
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
V2
dX A
=
FA 20 0,1593 R A
Inlet
outlet
A : FA1=FA0-FA0*XA1
B: FB1=FB0-2*FA0*XA1
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
T0
T0
TF
TR
TR
T0
Tf
A0
CPA dT
TR
TF
A0
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
X A2 =
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
PCH3OH
) (mol / kgcat min)
Ke
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
662.43
23
=1,4786 m
1
1120kgcat (1 0.6)m3 catalyst
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
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).
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)
(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
(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
(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
28
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 ) +
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: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;
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
B: FB2=FB0-2*FA0*XA2
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
TF
TR
TR
Tf
X A3
TR
TR
A0
FA0X A 2C PCdT +
C PAdT
A0
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
X A3 =
34
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
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
35
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
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
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
V6
dX A
=
.C.6.1
FA60 0,5243 R A
X A5 =
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
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
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SYMBOLS
Cpi
: Heat capasity
: Fugacity coefficient
J/mol.K
J/mol
J/mol
Kf
: Equilibrium constant
Ky
Tr
: Reduced Temperature
Pr
: Reduced Pressure
: Pressure
bar
8,314 J/mol.K
: Temperature
XA
X Ae
40
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