considerations around process intensification...3 file number process intensification • coined in...

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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

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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

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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…

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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

??

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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

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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.

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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)




aa bb cc



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


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Distributed Production of ChemicalsThe Dilemma of the 0.6 rule

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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

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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

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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

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Value chain in the Chemical Industry

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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

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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

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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

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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

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Plate Mixer Design (Micro)

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Plate Mixer Design

HydrogenHydrogen

OxygenOxygen

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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

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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.

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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

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