2011 Synthesis y Gas Seminar Margarita g Methanol Synthesis

November 24, 2011

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Excellent Catalyst Must Provide:

9 9 9 9 9

High Activity Low-Temperature Activity High Selectivity Good Mechanical Stability Long Life

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which means: 9 Activity = High Carbon Efficiency, MeOH Yield, Low Synthesis Gas Consumption 9 Selectivity = Low By-product Make 9 Stability = High Activity Retention (resistance against deactivation)

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Importance of Catalyst Formulation

Copper Crystallite Size 9 Copper surface area (> 50 m/g) 9 Dispersion (accessibility of active sites) 9 Pore P Si Sizes (absence ( b of f diffusion diff i limitation)

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Low By-Product By Product Make

Catalyst Precursor (incl. proper selection of raw materials) Catalyst Formulation: Pore Volume Pore Size Distribution No Fe

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Catalyst Stability - Activity Retention

Influence of Catalyst Precursor on Stability Resistance R i t t Thermal to Th l Sintering Si t i (Migration of Copper Crystallites) Resistance es sta ce to Hydrothermal yd ot e a Aging g g (Matrix Destruction by Water)

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MEGAMAX Generations, , so far

Lab comparison using CO2 rich syngas:
130 Lab Test / Accelerated Aging 120 MegaMax700 110 C79-5GL 100 C79-4GL 90 0 50 100 150 200 250 Time on Stream [hours] 90 300 100 110 120 Relative Activity [%] Relative Activity [%] 130

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Competition
Steam reforming syngas:
1.3 1.2 1.1 1.0 0.9

250C

250C

WT Y / kg h -1 kg -1

0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 0 24 48 72 96 120 144 168 192 216 240 264

210C 230C

Competitor MegaMax 700

TOS / h

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GNFC Plant II GNFC, II, Bharuch Bharuch, India ARC ICI QUENCE REACTOR
Continuous Daily Higher Yield Through MegaMax 700
125

Relative e Production, %

120 115 110 105 100 95 90 85 80 1 6 12 18 24 30 36 42

Months Operation
Competitors 5th Charge Productivity Sd Chemies 6th Charge Productivity w ith MegaMax 700

Comparison of competitor catalysts and MM 700 at GNFC (Adiabatic Reactor - ARC revamping)

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Casale Isothermal Methanol Converter

IMC

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Casale IMC IMC, Nevinommyssk, Nevinommyssk Russia

Catalyst y Performance since Start-of-Run in 2002
140 Relativ ve Catalyst t Activity [%] 120 100 80 60 40 0 10 20 30 40 50 Rel. Activity Reaction Temp. 300 Avg Reaction ] Temperature [C] 280 260 240 220 200

Months on Stream

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MegaMax 800 The New MegaMethanol Catalyst

Catalyst: Catalyst type:

MegaMax 800 Cu ZnO, ZnO Al2O3 based

Catalyst shape: 6 x 4 mm tablets Bulk Density: 1200 kg/m3

Typical operating conditions:

Temperature: Pressure: Space velocity: 190 315C 20 -120 bar 25 000 + Nm/m/h
(depending on operating conditions)

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MegaMax 800: New MeOH Synthesis Catalyst Generation

1,2 1,1 1,0

250C

WTY / kg h-1 kg g-1

250C

09 0,9 0,8 0,7 0,6 0,5 04 0,4 0,3 40 60 80 100 120 140 160 180 200

MegaMax700 MegaMax800

210C 210 C

TOS / h
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MegaMethanol Two-Step Two Step Synthesis

Recycle Compressor

Gas cooled Gas-cooled Reactor

Water-cooled
Reactor

HP-Steam Make Up Gas

MegaMax 800

Purge Gas

Crude Methanol

Boiler Feed Water

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The New Catalyst not only for the MegaMethanol

Strained St i d Cu C metal t l as active phase

Zn-Al-O Z Al O Zn-Al-O

Cu supported C t d on ZnO Z O1-x to give a high surface area of strained copper metal Solid solution of Zn-Al-O as suitably refractory that hinders particle sintering.

Zn-Al-O

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Continuous improvement of MegaMax catalysts

1,0 0,9 0,8 0,7 0,6 0,5 0,4

rel. pore volume rel. Cu surface area

C79-4

C79-5

MegaMax 700

MegaMax 800

Generation

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Continuous improvement of MegaMax catalysts

1,00

relative per r rformance a at 483K

0,95 0,90 0,85 0,80 0,75 0,70

C79-4

C79-5

MegaMax 700

MegaMax 800

Generation

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High Yields Long Life

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Superior Crushing Strength

Side Crush Strength
200 180 160 140 120 100 80 60 40 20 0

[N N]

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) ) Powder sample (dp = 100 -200 m) p heating g of the reactors Independent Fast on-line gas analysis by means of 2 -GCs Gas feed and vapor dosing Activation, MeOH synthesis and MeOH steam reforming possible Pressure up to 70 bar and temperature up to 550C

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Stability Tests Aim: Gain information on stability of methanol synthesis catalysts in a short time period

Thermal stress test

Increase of reaction temperature in increments under methanol synthesis conditions, after each temperature step d t determination i ti of f WTY @ 210C

Redox stress test

Aging induced by temperature-programmed oxidation/re-reduction cycles (TPO/TPR) followed by determination of the WTY @ 210C

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T-program p g for thermal stress test

stress period

360

320

T/ C

280

formation period

240

200
determination of WTY

50

100

150

200

TOS / h

Conditions: p = 60 bar, Q = 60 Nml min-1, mcat = 0,18 g, dp = 100-200 m, Syngas High CO2 (N2: 7 %, CO: 6 %, CH4 19,5 %, CO2: 8 %, H2: 59,5 %)
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Results of thermal stress test

TOS / h
60 80 100 120 140 160
competitor 1 competitor p 2 Megamax 700 C79-5GL Cu/ZnO Cu/Al2O3 Megamax 800

0,5

WTY / h W

-1

0,4

03 0,3 0,2 0,0 240

260

280

300 320 340 Aging temperature / C

360

380

MegaMax 800 more stable than competition

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Operation chart for redox stress test

repeated twice
20 min 2% H2 in N2 Formation 48 h 60 bar Syngas 3h 5% O2 in N2 Synthesis 20 h 60 bar TPO 2 C/min 1 atm t 5% O2 in N2 22 Nml min
-1

350 300 250

TPR 2 C/min 1 atm 2% H2 in N2 11 Nml min

-1

T / C

Synthesis 20 h 60 bar

200 150 100 50

Cooling till 30C Cooling till 30C

Methanol synthesis conditions: p = 60 bar, , Q = 60 Nml min-1, mKat = 0,18 , g, dp = 100-200 m, , Syngas High CO2 (N2: 7 %, CO: 6 %, CH4 19,5 %, CO2: 8 %, H2: 59,5 %)
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Results for redox stress test

TOS / h
60 0,5 80 100 120
competitor 1 competitor p 2 MM 700 MM 800 C79-5GL Cu/ZnO C /AlO Cu/Al O 2 3

WTY / h

-1 1

0,4

03 0,3 0,2 0,0 0

Number of TPO/TPR cycle

MM 800 has very high redox stability

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CASE STUDY ALTO PARANA Highest Activity Recorded

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CASE STUDY ALTO PARANA Outstanding Operation Stability

Higher Productivity (8%) at SOR condition and at the lower inlet temperature

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MegaMax g 800 Performance in Lurgi g Steam Raising g Rx Alto Parana, Argentina

Date C t l tA Catalyst Age, M Months th Production Rate, MTPD Conditions Measured DP, Kg/cm 2 Reactor Inlet Temp, C Reactor Exit Temp, C Steam Drum Temp, C Flow MUG Feed Rate, Nm 3/Hr Reactor Inlet, Nm 3/Hr Purge Gas Rate, Nm 3/Hr Recyle Ratio MUG Stoichiometric # Performance Indicators Space Time Yield, mTo/m 3h Space Velocity, Nm3/m3 Cat MUG Consumption, kmol/to MeOH Total Loop Conversions CO, % CO2, % Carbon Conversion, ,%
Catalyst Type

17-Oct-02 3 143

27-Jan-03 10-Sep-03 17-Apr-05 9-Aug-06 8-Nov-06 6 14 33 0 3 142 150 150 144 148

31-Oct-08 27 145

25-Aug-09 1 155

0.60 220 245 243

0.60 220 246 244

0.7 220 250 247

0.74 222 256 254

0.41 216 246 246

0.49 221 252 250

0.49 230 262 258

0.42 203 231 225

Higher Productivity (8%) at SOR condition and at the lower inlet temperature

19,679 114,028 6,001 4.79 3.05

20,008 112,808 6,411 4.64 3.05

20,778 122,014 6,269 4.87 3.00

21,657 121,711 7,353 4.62 3.00

19,098 98,954 5,374 4.18 2.93

20,712 102,686 6,656 3.96 2.96

21,439 109,369 7,700 4.10 2.99

21,235 97,852 6,568 3.61 3.08

0.5182 9,915 147 97.10 89.25 94.76

C79-7GL

0.5140 9,809 151 95.23 85.23 92.11

C797-GL

0.5440 10,610 148 96.19 90.07 94.18

C7-97GL

0.5434 10,584 155 92.84 82.19 89.67

C79-7GL

0.5341 8,835 142 96.86 90.61 95.02

C79-7GL

0.5501 9,168 150 94.17 81.93 90.62

C79-7GL

0.5389 9,765 158 93.94 70.74 86.72

C79-7GL

0.5322 8,087 147 97.62 89.25 95.33

MM 800

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Thank You For Your Attention!

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