Effective catalysts for methanol
synthesis: NPC-RT experience
Saeed Sahebdelfar│ Head of Catalyst Research Group│ NPC-R&T
13th Iran Petrochemical Forum
April 22-23, 2017, Tehran, Iran
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Presentation overview
• Methanol as a basic chemical
• Methanol synthesis catalyst
• NPC-RT approach
• Characterization and performance results
• Some final remarks
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• Methanol as a basic chemical
• Methanol synthesis catalyst
• NPC-RT approach
• Characterization and performance results
• Some final remarks
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Worldwide consumption of methanol
Source: http://www.methanol.org/methanol-basics/the-methanol-industry.aspx
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Methanol synthesis reactions
• Main methanol synthesis reaction:
CO2 + 3H2 ⇌ CH3OH + H2O
ΔHº298 = – 49.47 kJ/mol
ΔGº298 = + 3.30 kJ/mol
• Water gas shift : (provides CO2 for above reaction)
CO + H2O ⇌ CO2 + H2
• Key reactions
• Rapid reactions
ΔHº298 = – 41.47 kJ/mol
ΔGº298 = – 28.64 kJ/mol
• Conversion CO to methanol reaction:
CO + 2H2 ⇌ CH3OH
ΔHº298 = – 90.64 kJ/mol
Slow reaction
ΔGº298 = – 25.34 kJ/mol
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• Methanol as a basic chemical
• Methanol synthesis catalyst
• NPC-RT approach
• Characterization and performance results
• Some final remarks
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Global MeOH synthesis catalyst market
Regions
Approx. Reactor Volume (m3)
1
China
6800
2
Middle East and Africa (MEA)
4900
3
South America
3200
4
Asia Pacific and India
3100
5
Former Soviet Union (FSU)
2800
6
North America
2600
7
Europe (EU)
1600
Approx. Total Market Size
~ 25000 m3
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CuO/ZnO/Al2O3 catalyst preparation outline
Primary solutions
Co-precipitation
Washing
Drying and
Calcination
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Shaping
Reactor Performance test
&
Cat. Characterizations
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• Methanol as a basic chemical
• Methanol synthesis catalyst
• NPC-RT approach
• Characterization and performance results
• Some final remarks
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Industrial innovation process
Academic
Research
Industrial R&T
and Innovation
New
Technology
Users, Suppliers, etc
J.R. Rostrup-Nielsen, in E.G. Deroune et al.(eds) Combinatorial Catalysis and High Throughput Catalyst
Design and Testing, 337-371, 2000
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• Methanol as a basic chemical
• Methanol synthesis catalyst
• NPC-RT approach
• Characterization and performance results
• Some final remarks
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Industrial catalyst performance and key features
• High activity (High Cu surface area)
• High stability and resistance to deactivation (Stable Cu
particle size and surface area)
• Low by-product creation
• Effective interaction between catalyst components
• High mechanical strength and slight shrinkage
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Selected catalyst types
• NPC-RT Reference Method catalyst
• (prepared by conventional method under optimized
condition)
• NPC-RT Novel Method catalyst
• (prepared base on a patented novel method)
• Two authentic and reliable commercial samples
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Catalyst characterization and evaluation
• Bulk properties (composition, phase structure)
• Particle properties (texture, mechanical properties)
• Surface properties (morphology, dispersion)
• Activity (fixed-bed reactor testing under relevant
industrial condition and kinetic controlled
condition)
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N2-physisorption isotherms
• Type IV isotherms
1000
• Mesopores range (2 nm < pore diameter <50 nm)
• Relatively large cavities mesopores
Adsorbed volume (STD cm3/g)
800
• H1 type hysteresis
NPC-RT Novel Method
• Novel method catalyst have high adsorption
volumes compared to that of reference catalyst
being prepared by conventional method
600
NPC-RT Ref. Method
400
Commercial 2
200
For clearness, the isotherms for
catalysts are vertically offset by 200,
400 and 600 cm3g−1, respectively.
Commercial 1
0
0
0.2
0.4
0.6
0.8
1
Relative pressure (P/P0
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TEM of intermediate step in catalyst production
ZnAlO network
• Nanoporous structure
• Hierarchically nanoporous frameworks of
nanocrystalline Zn and Al oxides
• The Cu particles could be ensnared in the Al-Zn 3D
network morphology.
• High CO2/CO adsorption capacity, low diffusion
limitation
Cu addition
TEM image of nanoparticles of the
dyadic Al-Zn intermediate network
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ZnAlO network
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XRD analysis base on Scherrer equation
XRD analysis
Catalyst
CuO mean
crystallite
size (nm)
difference
Used catalyst Cu
mean crystallite between CuO and
(nm)
Cu crystallite (nm)
Relative
change in
crystalite sizes
(%)
NPC-RT Ref. Method
6.1
11.8
5.6
47.9
NPC-RT Novel Method
3.6
6.2
2.7
42.9
Commercial 1
5.5
11.8
6.3
53.3
Commercial 2
5.6
8.5
2.8
33.4
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N2O chemisorption
Nitrous oxide (N2O) chemisorption
Measurement Cu specific surface area
Metallic Cu
specific surface
area (m2/g)
Metallic Cu
dispersion (%)
dCu(N2O)*
NPC-RT Ref. Method
35.4
11.9
8.8
NPC-RT Novel Method
55.4
18.5
5.6
Commercial 1
29.1
9.7
11.2
Commercial 2
28.9
9.7
12.2
Catalyst
*Fresh catalyst Cu crystallite size as estimated from copper specific surface with a
spherical particle model
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Initial and secondary methanol production rates,
selectivity and secondary activity for catalysts
Initial MeOH Rate
Secondary MeOH Rate
Selectivity
Secondary Activity
100%
70
90%
60
MeOH Rate molMeOH/(kgcat.h)
80%
50
70%
60%
40
50%
30
40%
30%
20
20%
10
10%
0%
0
NPC-RT Ref.
Method
NPC-RT Novel
Method
Commercial 1
Commercial 2
Reaction conditions:
• T = 230 °C
• Synthesis gas feedstock ratio: H2/CO/CO2 = 80:12:8 (mol%)
• P = 50 bar
• Max. (CO and CO2) conversion of 40–45%.
−1
• Space velocity = 17250 h
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Catalyst performance results
Primary catalyst performance
Primary
MeOH rate
(molMeOH/
(h.kgcat))
MeOH
reactor
outlet
(mol%)
NPC-RT Ref.
Method
48.12
NPC-RT Novel
Method
Secondary catalyst performance
(%)
Secondary
MeOH rate
(molMeOH/
(h.kgcat))
MeOH
reactor
outlet
(mol%)
Secondary
activity (%)
8.94
93.8
27.19
4.78
56.5
68.65
11.10
97.7
48.85
7.58
71.2
Commercial 1
43.56
8.01
94.3
19.33
3.29
44.4
Commercial 2
44.16
8.36
94.6
23.16
4.03
52.4
MeOH
selectivity
• Novel method catalyst is a very high performance catalyst
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Activity and stability of catalysts versus time
Normalized methanol synthesis
activity over time for catalysts
Methanol production rate versus time
70
1
0.9
NPC-RT Novel Method
50
0.8
NPC-RT Novel Method
0.7
40
NPC-RT Ref. Method
30
Activity
MeOH Rate (molMeOH/(kgcat..h)
60
0.6
NPC-RT Ref. Method
0.5
Commercial 2
0.4
Commercial 2
Commercial 1
0.3
20
Commercial 1
0.2
10
0.1
0
0
0
20
40
60
Time (h)
80
100
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120
0
20
40
60
80
100
120
Time (h)
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Performance of catalyst in MeOH synthesis from
pure CO2
3.5
NPC-RT (Novel method)
CH3OH outlet (mol%)
3.0
Commercial catalyst
2.5
2.0
Pure CO2
T = 235 °C
GHSV = 17250 h-1
H2 : CO2 = 4:1
1.5
1.0
100
110
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Time (h)
130
140
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Some final remarks
Novel method catalyst have:
• High surface area, pore volumes and pore size compared to competitors
• Low diffusion limitation
• Reduced by-product formation
• Highest methanol productivity
• Increased plant throughput
• Significant energy savings in synthesis loop
• High methanol selectivity
• Increased carbon efficiency
• Lower energy consumption in distillation section
• Most durable activity
• Less catalyst replacements
• Good tolerance to high content CO2 in feed or even pure CO2 feedstock
• Feasible preparation method
• Agreement with a producer for commercial production (underway)
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Any Question?
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