MAX-PLANCK-INSTITUT FÜR CHEMISCHE ENERGIE KONVERSION METHANOL SYNTHESIS ON COPPER-BASED CATALYSTS...
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MAX-PLANCK-INSTITUT FÜR CHEMISCHE ENERGIE KONVERSION METHANOL SYNTHESIS ON COPPER- BASED CATALYSTS M.V. Bukhtiyarova
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Transcript of MAX-PLANCK-INSTITUT FÜR CHEMISCHE ENERGIE KONVERSION METHANOL SYNTHESIS ON COPPER-BASED CATALYSTS...
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METHANOL SYNTHESIS ON COPPER-BASED CATALYSTS
M.V. Bukhtiyarova
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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 synthesisM
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CO2 + 3H2 CH3OH +H2O
Süd-Chemie catalyst : Cu/ZnO/Al2O3 (old generation)
Gas mixture: H2:CO2 = 3:1Pressure: 30 and 50 barsTemperature: 190, 210, 230, 250 and 260°CGHSV: 4800 and 7200 h-1
Methanol synthesis setup
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0,00 1,00 2,00 3,00 4,00 5,00-5
100
200
300
400 Wasser #87 [modified by gschmitz] TCDpA
min
1
2
1
2
0,00 1,00 2,00 3,00 4,00 5,00 6,00 7,00-10
25
50
75
100
1 - 68 [modified by gschmitz] RSG-MS-017-132 - 62 MethylformiatpA
min
2
1
1 2
3
Traces of methylformate are observed during methanol synthesis
No. Ret.Time Peak Name Rel.Area min %
1 2.50Methanol 48.2772 3.31Wasser 51.723
No. Ret.Time Peak Name Rel.Area min %
1 1.69 Methyl formate 0.0142 2.02 n.a. 0.0153 2.98 Methanol 99.970
Gas chromatography of liquid sample
Sample obtained at 250°C, 30 bar, 7200 h-1
Reference methylformate solution contains 5% of methanol
Reference methylformate
Sample
acetone
air
Samples are dissolved in acetone to have reproducible results
Methanol synthesisM
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6 9 12 15 18 21 24
0.8
1.0
1.2
1.4
260°C
190°C
Rat
io C
H3O
H/H
2O, m
l/ml
Time, h
210°C
250°C
230°CGHSV = 4800 h-1
p = 30 bar
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10
20
30
40
50
190°C
Vol
ume,
ml
Time, h
CH3OH
H2O
GHSV = 4800 h-1
260°C
250°C
230°C
210°C
p = 30 bar
CO2 + 3H2 CO2 + H2CH3OH +H2O CO +H2O
Methanol synthesis: Reverse water gas shift:
H = – 49.7 kJ/mol H = 41.2 kJ/mol
Increasing temperature promotes water-gas shift reaction
Ratio of CH3OH/H2O (ml/ml) = 2.24
Methanol synthesisM
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CO2 + 3H2
CO2 + H2
CH3OH +H2O
CO +H2O
MS:
RWGS:
According to Chatelier’s principle increase of pressure results in higher methanol formation
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10
20
30
40
50
260°C
190°C
Vo
lum
e,
ml
Time, h
CH3OH
H2O
GHSV = 4800 h-1
p = 50 bar
230°C
250°C
210°C
Dependence on pressure
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10
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30
40
50
190°C
Vol
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ml
Time, h
CH3OH
H2O
GHSV = 4800 h-1
260°C
250°C
230°C
210°C
p = 30 bar
Methanol synthesisM
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Volume of formed methanol and water depends on reaction conditions
6 9 12 15 18 21 24 27 300
10
20
30
40
50
190°C
p = 30 bar
260°C
250°C
230°C
Vo
lum
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ml
Time, h
CH3OH
H2O
210°C
GHSV = 7200 h-1
6 9 12 15 18 21 24 27 300
10
20
30
40
50
190°C
Vol
ume,
ml
Time, h
CH3OH
H2O
GHSV = 4800 h-1
260°C
250°C
230°C
210°C
p = 30 bar
Dependence on space velocity
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10
20
30
40
50
190°C
260°C
Time, hV
olum
e, m
l
210°C
230°C
250°C
CH3OH
H2O
GHSV = 7200 h-1
p = 50 bar
Methanol synthesisM
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Volume of methanol and water does not practically change at temperature higher than 250°C
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10
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260°C
190°C
Vol
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ml
Time, h
CH3OH
H2O
GHSV = 4800 h-1
p = 50 bar
230°C
250°C
210°C
Dependence on space velocity at high pressure
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453 463 473 483 493 503 513 523 533 5430
2
4
6
8
10
12
14
16
18
20
CO
2 co
nve
rsio
n,
%
Temperature, K
4800 h-1
6000 h-1
7200 h-1
453 463 473 483 493 503 513 523 533 5430
2
4
6
8
10
12
14
16
CO
2 con
vers
ion,
%
Temperature, °C
30 bar 50 bar
CO2 conversion
Conversion of CO2 increase with temperature and decrease with space velocity
Dependence on space velocity p = 30 bar
Dependence on pressureGHSV = 4800 h-1
453 463 473 483 493 503 513 523 533 5430
10
20
30
40
50
60
70
80
Sel
ectiv
ity C
H3O
H, %
Temperature, K
4800 h-1
6000 h-1
7200 h-1
Methanol selectivityM
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453 463 473 483 493 503 513 523 533 5430
10
20
30
40
50
60
70
80
Sel
ectiv
ity C
H3O
H, %
Temperature, K
30 bar 50 bar
Dependence on pressureGHSV = 4800 h-1
At high pressure selectivity practically does not change with temperature
Dependence on space velocity p = 30 bar
Methanol yieldM
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453 463 473 483 493 503 513 523 533 5430
1
2
3
4
5
6
7
8
Yie
ld C
H3O
H,
%
Temperature, K
4800 h-1
6000 h-1
7200 h-1
453 463 473 483 493 503 513 523 533 5430
1
2
3
4
5
6
7
8
Yie
ld C
H3O
H,
%
Temperature, °C
30 bar 50 bar
Dependence on pressureGHSV = 4800 h-1
Dependence on space velocity p = 30 bar
Methanol yield increases with temperature, pressure and decreases with space velocity
Activation energyM
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36
38
40
42
44
46
48
50
Cu/ZrO2
Cu/ZnO
Cu/ZnO/Al2O
3/Cr
2O
3
a
Act
ivat
ion
ener
gy, k
J/m
ol
(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
a
bc
d
Cu/ZnO/Al2O
3
Obtained activation energy is in the agreement with activation energy presented in literature
1,85 1,90 1,95 2,00 2,05 2,10 2,15 2,20-2,0
-1,5
-1,0
-0,5
0,0
0,5
Ea = 44.9 kJ/mol
Ea = 48.2 kJ/mol
Ln(R
ate(
CH
3OH
))
1/T, 1/K
4800 h-1
6000 h-1
7200 h-1Ea = 48.7 kJ/mol
Comparison with literature data
Methanol synthesisM
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Conditions for stability test: H2:CO2 = 3:1;
30 bar, 230°C; 4800 h-1
0 50 100 150 200 250 300 350 400 4500
2
4
6
8
10Y
ield
CH
3OH
, %
Time, h
Productivity of methanol decreases during first 100 after that the catalyst works stable for another 300 hours
Methanol synthesisM
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Yie
ld C
H3O
H, %
Con
vers
ion
CO
2, %
Temperature, K
Old Catalyst New Catalyst
0
2
4
6
8
10
12
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18
453 463 473 483 493 503 513 523 533 54325
30
35
40
45
50
55
60
65
Temperature, K
Sel
ectiv
ity C
H3O
H, %
Old Catalyst New Catalyst
CO2 + 3H2 CH3OH +H2OMethanol synthesis:
Clariant (Süd-Chemie) catalysts
Gas mixture: H2:CO2 = 3:1Pressure: 30 barTemperature: 190, 210, 230, 250 and 260°CGHSV: 4800 h-1
The “old generation” catalyst works better for CO2 hydrogenation at low pressure
ConclusionsM
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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 long-term experiment for 400 hours
4. Clariant (Süd-Chemie) catalyst of old generation is more suitable for production methanol by CO2 hydrogenation
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THANK YOU FOR YOUR KIND ATTENTION
Methanol yieldM
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453 463 473 483 493 503 513 523 533 543
Pro
du
ctiv
ity C
H3O
H,
kgM
et/(
kgca
t*h)
Temperature, °C
4800 h-1
6000 h-1
7200 h-1
453 463 473 483 493 503 513 523 533 543
Pro
duct
ivity
CH
3OH
, kg
Met/(
kgca
t*h)
Temperature, °C
30 bar 50 bar
Gas chromatography of liquid samplesInstrument Agilent 6890 Detektor TCD 250°CColumn: Stabilwax 30 m S-1 Injector 250°CProgramm TCD 60 Tem.Programm 80°CMethod Wasser Gas He 0,93 bar 1 mlReport Rep Wasser Split 1:20
Injection Volume 0.5 µl
Instrument 6890 Detektor FID 300°CColumn: Stabilwax 30m S-69 Injector 240°CProgramm Stabilwax Tem.Programm: 50°CMethod Pyrrol Gas: H2 0,86 bar 2,3 mlReport Rep normal Split 1:20
Injection Volume: 0.5 µl
The measurement using FID was done for determination organic impurities in methanol. FID does not detect water
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