08 methanol synthesis
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2011 Synthesis Gas Seminar – Margarita y gMethanol SynthesisNovember 2–4, 2011
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Excellent Catalyst Must Provide:
High ActivityLow-Temperature ActivityHigh SelectivityGood Mechanical StabilityLong Life
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Activity
…which means:
Activity= High Carbon Efficiency, MeOH Yield,
Low Synthesis Gas ConsumptionSelectivity
= Low By-product MakeStabilityStability
= High Activity Retention (resistance againstdeactivation)
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Importance of Catalyst FormulationImportance of Catalyst Formulation
Copper Crystallite Size
Copper surface area (> 50 m²/g)Dispersion (accessibility of active sites)P Si ( b f diff iPore Sizes (absence of diffusionlimitation)
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Low By Product MakeLow By-Product Make
Catalyst Precursor (incl. proper selection of raw materials)raw materials)Catalyst Formulation:
Pore VolumePore Size Distribution
No Fe
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Catalyst Stability - Activity RetentionCatalyst Stability - Activity Retention
Influence of Catalyst Precursor on StabilityR i t t Th l Si t iResistance to Thermal Sintering
(Migration of Copper Crystallites)Resistance to Hydrothermal Aginges sta ce to yd ot e a g g
(Matrix Destruction by Water)
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MEGAMAX Generations, so far…
130 130
,Lab comparison using CO2 rich syngas:
120 120[%]
[%]
Lab Test / Accelerated Aging
110 110
Act
ivity
Act
ivity
MegaMax700
C79-5GL
100 100
Rel
ativ
e
Rel
ativ
e
C79-4GL
900 50 100 150 200 250 300
Time on Stream [hours]
90
C79-4GL
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Time on Stream [hours]
Competition
1.2
1.3
CompetitionSteam reforming syngas:
0.9
1.0
1.1
250°C 250°C
0.6
0.7
0.8
Y / k
g h-1
kg-1
CompetitorMegaMax 700210°C
0.3
0.4
0.5WT 230°C
0.0
0.1
0.2
0 24 48 72 96 120 144 168 192 216 240 264
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0 24 48 72 96 120 144 168 192 216 240 264TOS / h
GNFC Plant II Bharuch IndiaGNFC, Plant II, Bharuch, IndiaARC – ICI QUENCE REACTOR
Continuous Daily Higher Yield Through MegaMax® 700
120125
%
95100105110115120
e Pr
oduc
tion,
%
80859095
1 6 12 18 24 30 36 42
Rela
tive
Months Operation
Competitor´s 5th Charge Productivity Süd Chemie´s 6th Charge Productivity w ith MegaMax® 700
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• Comparison of competitor catalysts and MM 700 at GNFC (Adiabatic Reactor - ARC revamping)
Casale Isothermal Methanol Converter
IMCIMC
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Casale IMC Nevinommyssk Russia
Catalyst Performance since Start-of-Run in 2002
Casale IMC, Nevinommyssk, Russia
y
120
140
t 280
300
]
80
100
120
ve C
atal
yst
ivity
[%]
240
260
280
Rea
ctio
n ra
ture
[°C
]
60
80
Rel
ativ
Act
220
240
Avg
Te
mpe
Rel. Activity Reaction Temp.40
0 10 20 30 40 50
Months on Stream
200
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MegaMax® 800MegaMax® 800The New MegaMethanol Catalyst
Catalyst: MegaMax® 800
Catalyst type: Cu ZnO Al O basedCatalyst type: Cu – ZnO, Al2O3 based
Catalyst shape: 6 x 4 mm tablets
Bulk Density: 1200 kg/m3
Typical operating conditions:Temperature: 190 – 315°C
Bulk Density: 1200 kg/m3
Pressure: 20 -120 bar Space velocity: 25 000 + Nm³/m³/h
(depending on operating conditions)
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MegaMax 800: New MeOH Synthesis Catalyst Generation
1,2
MegaMax 800: New MeOH Synthesis Catalyst Generation
250°C250°C
0 9
1,0
1,1
g-1
0,7
0,8
0,9
MegaMax700MegaMax800
/ kg
h-1
kg
210°C0 4
0,5
0,6
WTY
/
210 C
40 60 80 100 120 140 160 180 200
0,3
0,4
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TOS / h
MegaMethanol® Two-Step SynthesisMegaMethanol Two Step Synthesis
Gas-cooled Water-cooledReactorRecycle
CompressorGas cooled
ReactorReactor
HP-Steam
Make Up Gas
MegaMax® 800
PurgeGas
CrudeMethanol
Boiler FeedWater
MegaMax® 800
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Gas Methanol Water
The New Catalyst not only for the MegaMethanolThe New Catalyst not only for the MegaMethanol
St i d C t l
Z Al OZn-Al-O
Strained Cu metal as active phase
C t d Z OZn-Al-OZn-Al-O Cu supported on ZnO1-xto give a high surface area of strained copper metal
Zn-Al-OSolid solution of Zn-Al-Oas suitably refractory that hinders particlethat hinders particle sintering.
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Continuous improvement of MegaMax catalysts
0,9
1,0 rel. pore volume rel. Cu surface area
0,7
0,8
Δ
0,5
0,6
C79-4 C79-5 MegaMax 700 MegaMax 8000,4
Generation
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Generation
Continuous improvement of MegaMax catalysts
0,95
1,00
at 4
83K
0,85
0,90
rfor
man
ce a
0,75
0,80
rela
tive
per
C79-4 C79-5 MegaMax 700 MegaMax 8000,70
r
Generation
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High Yields – Long LifeHigh Yields Long Life
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Superior Crushing StrengthSide Crush Strength
Superior Crushing Strength
160
180
200
100
120
140
N]
40
60
80
[N
0
20
C79-5 GL MegaMax 700 MegaMax 800 Compet. A Compet. B
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High Throughput Testing
16 parallele microreactors (ID = 2mm, L ~20 cm)
High Throughput Testing
( , )Powder sample (dp = 100 -200 µm)
Independent heating of the reactorsp g
Fast on-line gas analysis by means of 2 µ-GCsGas feed and vapor dosing
Activation, MeOH synthesis and MeOH steam reforming possiblePressure up to 70 bar and temperature up to 550°C
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Stability Tests
Aim: Gain information on stability of methanol synthesis catalysts in a short time period
Stability Tests
synthesis catalysts in a short time period
Thermal stress testThermal stress testIncrease of reaction temperature in increments under methanol synthesis conditions, after each temperature step d t i ti f WTY @ 210°Cdetermination of WTY @ 210°C
Redox stress testAging induced by temperature-programmed oxidation/re-reduction cycles (TPO/TPR) followed by determination of the WTY @ 210°C
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T-program for thermal stress testp g
360stress period
280
320
°C
240
280
T /
°
formationperiod
0 50 100 150 200
200determination of WTY
Conditions: p = 60 bar, Q = 60 Nml min-1, mcat = 0,18 g, dp = 100-200 µm,
0 50 100 150 200TOS / h
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pSyngas High CO2 (N2: 7 %, CO: 6 %, CH4 19,5 %, CO2: 8 %, H2: 59,5 %)
Results of thermal stress test
competitor 1competitor 2
60 80 100 120 140 160 TOS / h
0,5p
Megamax 700 C79-5GL Cu/ZnO Cu/Al2O3
Megamax 800
0 3
0,4
WTY
/ h-1
Megamax 800
0,2
0,3 W
240 260 280 300 320 340 360 3800,0
Aging temperature / °C
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MegaMax 800 more stable than competition
Operation chart for redox stress test
350
20 min2% H2 in N2
repeated twice
250
300
350
Synthesis20 h
Synthesis20 h
3 h5% O2 in N2 TPR
2 °C/min1 atm 2% H2 in N2
Formation48 h60 barSyngas
TPO2 °C/min1 t
150
200
250 20 h60 bar
20 h60 bar
2 2
11 Nml min-1
Cooling
T / °
C
1 atm 5% O2 in N2
22 Nml min-1
50
100
150 Cooling till 30°C
Cooling till 30°C
Methanol synthesis conditions: p = 60 bar, Q = 60 Nml min-1, mKat = 0,18 g, dp = 100-200 µm,
50
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p , , Kat , g, p µ ,Syngas High CO2 (N2: 7 %, CO: 6 %, CH4 19,5 %, CO2: 8 %, H2: 59,5 %)
Results for redox stress test
competitor 1competitor 2
60 80 100 120TOS / h
0,5
1
pMM 700MM 800C79-5GLCu/ZnOC /AlO
0 3
0,4
WTY
/ h-1 Cu/Al2O3
0,2
0,3
0 1 2 30,0
Number of TPO/TPR cycle
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MM 800 has very high redox stability
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CASE STUDY ALTO PARANAHighest Activity Recorded
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CASE STUDY ALTO PARANAOutstanding Operation Stability
Higher Productivity (8%) at SOR condition and at the lower inlet temperature
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MegaMax 800 Performance in Lurgi Steam Raising Rxg g gAlto Parana, Argentina
Date 17-Oct-02 27-Jan-03 10-Sep-03 17-Apr-05 9-Aug-06 8-Nov-06 31-Oct-08 25-Aug-09C t l t A M th 3 6 14 33 0 3 27 1
Higher Catalyst Age, Months 3 6 14 33 0 3 27 1Production Rate, MTPD 143 142 150 150 144 148 145 155
ConditionsMeasured DP, Kg/cm2 0.60 0.60 0.7 0.74 0.41 0.49 0.49 0.42Reactor Inlet Temp, C 220 220 220 222 216 221 230 203
Productivity (8%) at SOR condition and at the lower inlet temperatureReactor Exit Temp, C 245 246 250 256 246 252 262 231
Steam Drum Temp, C 243 244 247 254 246 250 258 225
FlowMUG Feed Rate, Nm3/Hr 19,679 20,008 20,778 21,657 19,098 20,712 21,439 21,235Reactor Inlet, Nm3/Hr 114,028 112,808 122,014 121,711 98,954 102,686 109,369 97,852
temperature
Purge Gas Rate, Nm3/Hr 6,001 6,411 6,269 7,353 5,374 6,656 7,700 6,568Recyle Ratio 4.79 4.64 4.87 4.62 4.18 3.96 4.10 3.61MUG Stoichiometric # 3.05 3.05 3.00 3.00 2.93 2.96 2.99 3.08
Performance IndicatorsSpace Time Yield, mTo/m3h 0.5182 0.5140 0.5440 0.5434 0.5341 0.5501 0.5389 0.5322Space Time Yield, mTo/m h 0.5182 0.5140 0.5440 0.5434 0.5341 0.5501 0.5389 0.5322Space Velocity, Nm3/m3 Cat 9,915 9,809 10,610 10,584 8,835 9,168 9,765 8,087MUG Consumption, kmol/to MeOH 147 151 148 155 142 150 158 147
Total Loop ConversionsCO, % 97.10 95.23 96.19 92.84 96.86 94.17 93.94 97.62
CO2, % 89.25 85.23 90.07 82.19 90.61 81.93 70.74 89.25Carbon Conversion, % 94.76 92.11 94.18 89.67 95.02 90.62 86.72 95.33
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,Catalyst Type C79-7GL C797-GL C7-97GL C79-7GL C79-7GL C79-7GL C79-7GL MM 800
Thank You For Your Attention!
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