MAX-PLANCK-INSTITUT FÜR CHEMISCHE ENERGIE KONVERSION
METHANOL SYNTHESIS ON COPPER-BASED
CATALYSTS
M.V. Bukhtiyarova
MAX-PLANCK-INSTITUT FÜR CHEMISCHE ENERGIE KONVERSION
Introduction
1. Methanol production is a large industrial process.
2. Methanol is produced using synthesis gas at 250°C and 50 – 100 bars
CO + 2H2 = CH3OH
Catalyst: Cu/ZnO/Al2O3
3. High emission of CO2 resulted in studying methanol synthesis through CO2
hydrogenation.
4. Methanol can be viewed as a way of hydrogen storage
Methanol synthesis
MAX-PLANCK-INSTITUT FÜR CHEMISCHE ENERGIE KONVERSION
CO2 + 3H2
CH3OH +H2O
Methanol synthesis setup
Gas mixture: H2:CO2 = 3:1
Pressure:
30 and 50 bars
Temperature: 190, 210, 230, 250 and 260°C
GHSV:
4800 and 7200 h-1
Süd-Chemie catalyst : Cu/ZnO/Al2O3 (old generation)
Gas chromatography of liquid sample
MAX-PLANCK-INSTITUT FÜR CHEMISCHE ENERGIE KONVERSION
Sample obtained at 250°C, 30 bar, 7200 h-1
Samples are dissolved in acetone to have reproducible results
400 Wasser #87 [modified by gschmitz]
pA
300
TCD
air
RSG-MS-017-13
Methylformiat
3
50
1
acetone
100
1 - 68 [modified by gschmitz]
100 2 - 62
pA
75
1
200
Reference methylformate solution contains 5% of methanol
2
2
Reference methylformate
25 2
1
2
Sample
1
-5
0,00
min
1,00
2,00
No. Ret.Time Peak Name
min
1
2.50Methanol
2
3.31Wasser
3,00
4,00
Rel.Area
%
48.277
51.723
5,00
-10
0,00
min
1,00
2,00
No. Ret.Time
min
1
1.69
2
2.02
3
2.98
3,00
4,00
Peak Name
5,00
6,00
Rel.Area
%
Methyl formate
0.014
n.a.
0.015
Methanol
99.970
Traces of methylformate are observed during methanol synthesis
7,00
Methanol synthesis
1.4
30
Ratio CH3OH/H2O, ml/ml
40
Volume, ml
MAX-PLANCK-INSTITUT FÜR CHEMISCHE ENERGIE KONVERSION
50
CH3OH
H2O
GHSV = 4800 h
-1
260°C
p = 30 bar
250°C
20
230°C
210°C
10
190°C
0
6
9
12
15
18
21
24
27
30
190°C
210°C
1.2
-1
GHSV = 4800 h
1.0
p = 30 bar
250°C
260°C
0.8
6
9
CO2 + 3H2
12
15
18
Time, h
Time, h
Methanol synthesis:
CH3OH +H2O
H = – 49.7 kJ/mol
230°C
Reverse water gas shift:
CO2 + H2
CO +H2O
H = 41.2 kJ/mol
Ratio of CH3OH/H2O (ml/ml) = 2.24
Increasing temperature promotes water-gas shift reaction
21
24
Dependence on pressure
50
50
30
CH3OH
H2O
GHSV = 4800 h
40
-1
260°C
p = 30 bar
Volume, ml
40
Volume, ml
MAX-PLANCK-INSTITUT FÜR CHEMISCHE ENERGIE KONVERSION
Methanol synthesis
250°C
20
230°C
210°C
10
30
CH3OH
H2O
GHSV = 4800 h
-1
260°C
250°C
p = 50 bar
230°C
20
210°C
10
190°C
190°C
0
0
6
9
12
15
18
21
24
27
30
6
9
12
15
18
21
24
27
Time, h
Time, h
MS:
RWGS:
CO2 + 3H2
CH3OH +H2O
CO2 + H2
CO +H2O
According to Chatelier’s principle increase of pressure results in higher methanol formation
30
Dependence on space velocity
50
30
50
CH3OH
H2O
GHSV = 4800 h
CH3OH
H2O
40
-1
260°C
p = 30 bar
Volume, ml
40
Volume, ml
MAX-PLANCK-INSTITUT FÜR CHEMISCHE ENERGIE KONVERSION
Methanol synthesis
250°C
20
230°C
10
210°C
30
260°C
GHSV = 7200 h
p = 30 bar
-1
250°C
20
230°C
10
210°C
190°C
190°C
0
6
9
12
15
18
Time, h
21
24
27
30
0
6
9
12
15
18
21
24
Time, h
Volume of formed methanol and water depends on reaction conditions
27
30
Dependence on space velocity at high pressure
50
50
30
CH3OH
H2O
GHSV = 4800 h
40
-1
260°C
250°C
p = 50 bar
Volume, ml
40
Volume, ml
MAX-PLANCK-INSTITUT FÜR CHEMISCHE ENERGIE KONVERSION
Methanol synthesis
230°C
20
210°C
10
0
9
12
15
18
Time, h
21
24
27
260°C
250°C
GHSV = 7200 h
-1
p = 50 bar
230°C
20
210°C
10
190°C
6
30
CH3OH
H2O
30
190°C
0
6
9
12
15
18
21
Time, h
Volume of methanol and water does not practically change at
temperature higher than 250°C
24
27
30
Dependence on pressure
GHSV = 4800 h-1
Dependence on space velocity
p = 30 bar
20
16
18
-1
14
12
10
8
6
4
2
0
453
463
473
30 bar
50 bar
14
4800 h
-1
6000 h
-1
7200 h
16
CO2 conversion, %
CO2 conversion, %
MAX-PLANCK-INSTITUT FÜR CHEMISCHE ENERGIE KONVERSION
CO2 conversion
483
493
503
513
Temperature, K
523
533
543
12
10
8
6
4
2
0
453
463
473
483
493
503
513
523
533
Temperature, °C
Conversion of CO2 increase with temperature and decrease with space velocity
543
Dependence on pressure
GHSV = 4800 h-1
Dependence on space velocity
p = 30 bar
80
80
70
70
Selectivity CH3OH, %
Selectivity CH3OH, %
MAX-PLANCK-INSTITUT FÜR CHEMISCHE ENERGIE KONVERSION
Methanol selectivity
60
50
40
-1
4800 h
-1
6000 h
-1
7200 h
30
20
10
0
453
463
473
483
493
503
513
Temperature, K
523
533
543
60
50
40
30 bar
50 bar
30
20
10
0
453
463
473
483
493
503
513
Temperature, K
At high pressure selectivity practically does not change with temperature
523
533
543
Dependence on space velocity
p = 30 bar
Dependence on pressure
GHSV = 4800 h-1
8
8
7
7
-1
4800 h
-1
6000 h
-1
7200 h
6
5
Yield CH3OH, %
Yield CH3OH, %
MAX-PLANCK-INSTITUT FÜR CHEMISCHE ENERGIE KONVERSION
Methanol yield
4
3
2
1
30 bar
50 bar
6
5
4
3
2
1
0
453
463
473
483
493
503
513
Temperature, K
523
533
543
0
453
463
473
483
493
503
513
523
533
543
Temperature, °C
Methanol yield increases with temperature, pressure and decreases with space velocity
Comparison with literature data
-1
0,0
4800 h
-1
6000 h
-1
7200 h
Ea = 48.7 kJ/mol
-0,5
Ea = 48.2 kJ/mol
Ea = 44.9 kJ/mol
-1,0
-1,5
-2,0
1,85
1,90
1,95
2,00
2,05
1/T, 1/K
2,10
2,15
2,20
Activation energy, kJ/mol
0,5
Ln(Rate(CH3OH))
MAX-PLANCK-INSTITUT FÜR CHEMISCHE ENERGIE KONVERSION
Activation energy
50
48
46
44
a
Cu/ZnO/Al2O3
Cu/ZnO
d
a
42
40
38
Cu/ZnO/Al2O3/Cr2O3
b
Cu/ZrO2
c
(a) Our data
(b) H. Arakawa, Energy Conv. Mgmt: 33 (1992) 521
(c) X. Guo, J. Mol. Catal. A: 345 (2011) 60
(d) A. Karelovic, Catal. Today: 197 (2012) 109
36
Obtained activation energy is in the agreement with activation energy presented in literature
Conditions for stability test:
H2:CO2 = 3:1;
30 bar, 230°C; 4800 h-1
10
8
Yield CH3OH, %
MAX-PLANCK-INSTITUT FÜR CHEMISCHE ENERGIE KONVERSION
Methanol synthesis
6
4
2
0
0
50
100 150 200 250 300 350 400 450
Time, h
Productivity of methanol decreases during first 100 after that the catalyst works stable
for another 300 hours
Methanol synthesis
CO2 + 3H2
CH3OH +H2O
Gas mixture: H2:CO2 = 3:1
Pressure:
30 bar
Temperature: 190, 210, 230, 250 and 260°C
GHSV:
4800 h-1
Clariant (Süd-Chemie) catalysts
Old Catalyst
New Catalyst
65
16
60
14
14
12
12
10
10
8
8
6
6
4
4
2
2
0
0
453 463 473 483 493 503 513 523 533 543
Temperature, K
Selectivity CH3OH, %
16
18
Yield CH3OH, %
18
Conversion CO2, %
MAX-PLANCK-INSTITUT FÜR CHEMISCHE ENERGIE KONVERSION
Methanol synthesis:
Old Catalyst
New Catalyst
55
50
45
40
35
30
25
453 463 473 483 493 503 513 523 533 543
Temperature, K
The “old generation” catalyst works better for CO2 hydrogenation at low pressure
MAX-PLANCK-INSTITUT FÜR CHEMISCHE ENERGIE KONVERSION
Conclusions
1. Methanol yield depends on reaction conditions: high pressure results in
formation of higher amount of methanol
2. Practically pure methanol with trace amount of methylformate is produced
3. Clariant (Süd-Chemie) catalyst for methanol synthesis is stable during longterm experiment for 400 hours
4. Clariant (Süd-Chemie) catalyst of old generation is more suitable for
production methanol by CO2 hydrogenation
MAX-PLANCK-INSTITUT FÜR CHEMISCHE ENERGIE KONVERSION
THANK YOU FOR YOUR KIND
ATTENTION
Productivity CH3OH, kgMet/(kgcat*h)
Productivity CH3OH, kgMet/(kgcat*h)
MAX-PLANCK-INSTITUT FÜR CHEMISCHE ENERGIE KONVERSION
Methanol yield
-1
4800 h
-1
6000 h
-1
7200 h
453
463
473
483
493
503
513
Temperature, °C
523
533
543
30 bar
50 bar
453
463
473
483
493
503
513
Temperature, °C
523
533
543
Gas chromatography of liquid samples
Instrument
Column:
Programm
Method
Report
Agilent 6890
Stabilwax 30 m S-1
TCD 60
Wasser
Rep Wasser
Detektor
Injector
Tem.Programm
Gas
Split
Injection Volume
TCD 250°C
250°C
80°C
He 0,93 bar 1 ml
1:20
0.5 µl
Instrument
Column:
Programm
Method
Report
6890
Stabilwax 30m S-69
Stabilwax
Pyrrol
Rep normal
Detektor
Injector
Tem.Programm:
Gas:
Split
FID 300°C
240°C
50°C
H2 0,86 bar 2,3 ml
1:20
Injection Volume: 0.5 µl
The measurement using FID was done for determination organic impurities in methanol. FID does not detect water