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© 2007 UOP LLC. All rights reserved.
Considerations around Process Intensification
The role of PI and ‘mini’ in the Processing Industries
Considerations around Process Intensification
The role of PI and ‘mini’ in the Processing Industries
CPAC Satellite WorkshopRome, ItalyMarch 2007
CPAC Satellite WorkshopRome, ItalyMarch 2007
2 File Number
Outline
• Process Intensification• Distributed Production
Case Study 1 : PI to enable small scale production• Micro-technology and PI in a large scale plant
Case study 2• Conclusions
3 File Number
Process Intensification
• Coined in the 70’s by ICI- Colin Ramshaw and his PIN
• A series of tools, aimed at - reducing the capital cost of production for bulk
chemicals - at constant or lower variable cost of production.
• Capex scales roughly with number of unit operations• Achieved by
- Combining syntheses, multiple products- combining unit operations - removing ‘limitations’ (intensifying)
Heat transferMass transferKineticsMomentum/Pressure dropGravity…
4 File Number
Process Intensification PotentialR
elat
ive
Inte
nsity
CURRENT
NO
HYDRAULIC
LIMITATION
ISOTHERMAL
CRUSHED
CATALYST
LESS
ATTENU-ATION
IDEALPTCLUSTERS
33
Process Geometry
1818
2222
3636
6060
??
5 File Number
Years
Rea
ctio
n K
inet
ics T
ime
Con
stan
t
Seconds MonthsDaysHoursMinutes
m-seconds
seconds
minutes
hours
FCC
Fixed-Fluid Bed
Moving Bed Radial Flow Fixed Bed radial Flow Semi-Regen; Platforming, Pacol
Cyclic Fixed Bed axial Flow
Fixed Bed axial Flow;
Circulating Liquid Riser
EbuliatingBed
Mega Scale Dire
ction of R
eactor
Development
Catalyst Deactivation Time Constant
PI trends in reactor technology
6 File Number
PI in catalysis (just 1 example)
• Detailed analysis shows importance of diffusional limitations…Leads to rethinking of the location of the active phase in the catalyst pellet. - Activity increases by factor of 10. - Metal loading drops by factor of 8.
7 File Number
Gas/Solid Mass Transfer and Reaction : Extreme control of Reaction Conditions
Selective hydrogenation of Selective hydrogenation of CDT to CDE would open up CDT to CDE would open up alternative route to Nylon 12alternative route to Nylon 12
Try to achieve selective Try to achieve selective hydrogenation by extreme hydrogenation by extreme
control of reaction conditions control of reaction conditions
Weissmeier and Hoenicke, Proceedings IMRET 2, 1998Weissmeier and Hoenicke, Proceedings IMRET 2, 1998
8 File NumberWeissmeier and Hoenicke, Proceedings IMRET 2, 1998Weissmeier and Hoenicke, Proceedings IMRET 2, 1998
Extremely regular short pores (a) are obtained by anodizing Extremely regular short pores (a) are obtained by anodizing aluminum. These nanostructures are built into regular aluminum. These nanostructures are built into regular
microchannels (b) and stacked (c).microchannels (b) and stacked (c).
aa bb cc
Gas/Solid Mass Transfer and Reaction : Extreme control of Reaction Conditions (2)
9 File NumberWeissmeier and Hoenicke, Proceedings IMRET 2, 1998Weissmeier and Hoenicke, Proceedings IMRET 2, 1998
Extremely regular short pores (a) are obtained by anodizing Extremely regular short pores (a) are obtained by anodizing aluminum. These nanostructures are built into regular aluminum. These nanostructures are built into regular
microchannels (b) and stacked (c).microchannels (b) and stacked (c).
aa bb cc
Gas/Solid Mass Transfer and Reaction : Extreme control of Reaction Conditions (3)
10 File NumberWeissmeier and Hoenicke, Proceedings IMRET 2, 1998Weissmeier and Hoenicke, Proceedings IMRET 2, 1998
Extremely regular short pores (a) are obtained by anodizing Extremely regular short pores (a) are obtained by anodizing aluminum. These nanostructures are built into regular aluminum. These nanostructures are built into regular
microchannels (b) and stacked (c).microchannels (b) and stacked (c).
aa bb cc
Gas/Solid Mass Transfer and Reaction : Extreme control of Reaction Conditions (4)
11 File NumberWeissmeier and Hoenicke, Proceedings IMRET 2, 1998Weissmeier and Hoenicke, Proceedings IMRET 2, 1998
Evolution in Micro Evolution in Micro Engineering of Engineering of catalysts leads to catalysts leads to more precise more precise control of reaction control of reaction conditions, opening conditions, opening up new pathways in up new pathways in chemicals chemicals productionproduction
Effect of regular small pores
Effect of regular Effect of regular small poressmall pores
Removing deadvolumes
Removing deadRemoving deadvolumesvolumes
Base caseBase caseBase case
Gas/Solid Mass Transfer and Reaction : Extreme control of Reaction Conditions (5)
12 File Number
Distributed Production of ChemicalsThe Dilemma of the 0.6 rule
13 File Number
1920s1920s 1960s1960s 20002000
1500015000
100,000100,000
1,000,0001,000,000
BPSDBPSD
Others :Others :
Ethylene : 500 000 KMTAEthylene : 500 000 KMTA
PTA : 700 000 KMTAPTA : 700 000 KMTA
• Reduced Flexibility• Underutilized Capital• Increased Cycle Time for Technology Renewal
Distributed Production of ChemicalsScale Trends in the processing industries
14 File Number
Cost Cost ($)($)
Capital Cost of Production vs Scale
Numbering up
Scaling up
Scale (tons/yr)Scale (tons/yr)
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Distributed Production ?
• Value to the Customer- Alternative chemistry enabled- Synergistic use of existing equipment/energy/mass streams- Vertical integration, decouples from market fluctuations
• Safety : JIT production of hazardous chemicals• However : capital charge almost always overwhelms
- Intensify technology- Maintain low component count- Move to mass manufactured, standardized equipment- Aim to lower installation factors
16 File Number
How intense do we need to be ?
Process Intensification vs Scaledown
1
10
100
1000
1 10 100 1000 10000 100000 1000000Scaledown Ratio
Inte
nsifi
catio
n Ra
tio
0.7 Exponent
0.5 Exponent
17 File Number
Value chain in the Chemical Industry
18 File Number
Natural Gas, LPG or Naphtha
SyngasMethanol
Power
Waste Heat
Integrated Power and Methanol
Add a number of tricks we can not discuss
Methanol for Transportation
Stationary Power
8000 Households would require about 20 MeW power and about 200 T/D Methanol
19 File Number
Economics for Distributed Methanol
Conventional US Large Middle East Distributed
Capacity Tons/ day 2326 5000 195Capital Charge MM US $ 0 490 35
Methanol Production Cost $/ ga l 0.53 0.15 1ROI $/ ga l 0 0.12 0.22Power credit $/ ga l 0 0 -0.62Shipping/ Storage/ Insurance $/ ga l 0.14 0.26 0.1
Total $/ ga l 0.67 0.53 0.7$/ Mton 224 178 235
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Monetizing Natural Gas
0
200
400
600
800
1000
1200
1400
1600
< 0.25 > 0.5 > 1 > 5 > 50
Resource Size, tcf
Num
ber o
f Fie
lds
> 13,800
LNG, GTL
CNG,MeOH
After Morgan Stanley , Marathon
Sub-Scale Resources New Gas Conversion Options
EconomicsAnd feasibilityAt small scale
Scale-limits and efficiency at large scale
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‘Mini-LNG’
Technology by Hamworthy AS
• Simpler Cycles allow for cost effective small scale liquefaction (at the cost of efficiency).
• Small fields, but also on board reliquefaction and peak shaving.
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Impact of process intensification (Steam reforming)
Projections by Velocys and Heatric
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Hydrogen Peroxide
• One of the most common bleaching agents• Environmental concerns with chlorine based bleaching has
spurred H2O2 demand- H2O2 decomposes to water and oxygen
• Pulp & Paper industry is the largest consumer of H2O2- Used in both chemical and mechanical pulp mills- Historically mechanical pulp mills represent 80% of demand
• In petrochemical applications, use of peroxide eliminates byproducts: green chemistry
24 File Number
Anthraquinone Chemistry forH2O2 Synthesis
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Anthraquinone Process
HYDROGEN UNITHYDROGEN UNIT
HYDROGENATORHYDROGENATOR
OXIDIZER FEED TANKOXIDIZER FEED TANK
OXIDIZEROXIDIZER
EXTRACTOREXTRACTOR
CRUDE WASH TOWER AND CRUDE WASH TOWER AND STRIPPERSTRIPPER
30 % H30 % H22OO22
HYDROGENATOR FEED HYDROGENATOR FEED TANKTANK
SOLVENT RECOVERY UNITSOLVENT RECOVERY UNIT
STABILIZERSTABILIZER
PURGEPURGE
Hydrogen Hydrogen RefluxReflux
CatalystCatalyst
Working SolutionWorking Solution
SPENT AIRSPENT AIR
Crude Crude HH22OO22
PRIMARY FILTERPRIMARY FILTER
Working SolutionWorking Solution
AirAir
HH22OO
AnthraquinonAnthraquinone make upe make up
26 File Number
Direct Synthesis Chemistry
• Catalyst is Pd/C, works in acidified aqueous environment
• Oxidation state needs optimization for maximum selectivity- Requires pre-mixing of the feeds in the explosive regime
HH22
OO22
Pd Pd 00
Poor adsorption of O2
Pd Pd 22 ++ HH22
HH22
2 2 HH22OO
OO OO
2e2e 2e2e
Dissociative adsorption of O2
Pd Pd δδ ++
HH22 2e2e
OO22
HH22OO22
Desired
27 File Number
Plate Mixer Design (Micro)
28 File Number
Plate Mixer Design
HydrogenHydrogen
OxygenOxygen
29 File Number
3Phase Radial Flow Reactor
Sparger bar
Catalyst
Collection space
Inner screen
Inner wall
• Annular reactor• Multiple passes• Low pressure drop• Reduced wear on
internals• Allows catalyst
movement for deactivation (discontinuous)
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HYDROGEN UNITHYDROGEN UNIT
MIXER/REACTORMIXER/REACTOR
NEUTR/DEIONNEUTR/DEION
5 % H5 % H22OO22
HydrogenHydrogen
Direct Synthesis Flow Scheme
HH22OOAir/OxygenAir/Oxygen
31 File Number
ECONOMIC ANALYSISGross Margin $MM/yr $/MT product c/lb product % of CCOP % of NCOP
Key Product Value 62.37 385.00 0.17By-product Credit (0.10) (0.60) (0.00) 0.24 0.16Raw Material Cost 12.66 78.17 0.04 31.66 21.13
Gross Margin 49.61 306.23 0.14Variable Cost
Raw Mat'l less By-products 12.76 78.77 0.04 31.90 21.30Consumables 8.06 49.77 0.02 20.16 13.46Utilities 12.07 74.50 0.03 30.17 20.14Inventory Amortization 0.54 3.32 0.00 1.35 0.90
Variable Cost 33.43 206.36 0.09Fixed Cost
Labor 0.35 2.15 0.00 0.87 0.58Maintenance 2.01 12.40 0.01 5.02 3.35Overhead Expense 3.31 20.44 0.01 8.28 5.53Capital Expense 0.90 5.57 0.00 2.25 1.50
Fixed Cost 6.57 40.55 0.02
Cash Cost of Production 40.00 246.92 0.11 100.00 Total 66.75Gross Profit 22.37 138.08 0.06
Capital ChargesCapital recovery charge 19.92 122.98 0.06 33.25Royalty Amortization 0.00 0.00 0.00 0.00
0.00Capital Charges 19.92 122.98 0.06
Net Cost of Production 59.92 369.89 0.17 Total 100.00
Techno-Economics
O2/H2 feed ratio 1.5H2 conversion 0.82H2O2 selectivity 0.78H2O2 plant pressure (psia) 300Peroxide LHSV 1
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Conclusions
• Process Intensification can provide a means of reducing CapEx to - Reduce overall operating cost- escape from the economy of scale.
• Micro-scale equipment opens up interesting avenues for process intensification, particularly where heat/mass transfer and reactions are involved/combined.
• Overcoming the ‘0.6 rule’ by ‘scaling out’ is not trivial, unless mass manufacturing of equipment is possible; Multiscale technology appears to be the most appropriate means for micro-technology to impact the large scale chemical industry.
33 File Number
Acknowledgements
• At UOP :- Anil R. Oroskar, PhD- Gavin P. Towler, PhD- Suheil F. Abdo, PhD- Jason Corradi
• At IMM : - Prof. Dr. Volker Hessel - Prof. Dr. Holger Loewe - Prof. Dr. Steffen Hardt - Christian Hoffman- Dr. Ralf Zapf