The Role of Fundamentals in Future The Role of Fundamentals in - - PowerPoint PPT Presentation

SLIDE 1

The Role of Fundamentals in Future The Role of Fundamentals in Future Directions for the Chemical Industries Directions for the Chemical Industries

Kurt VandenBussche Kurt VandenBussche UOP LLC UOP LLC CREL 04 meeting CREL 04 meeting

SLIDE 2

2

Outline Outline

• Future Directions

Future Directions

• Fundamentals

Fundamentals

• Conclusions

Conclusions

SLIDE 3

3

Outline Outline

• Future Directions

Future Directions

– – The processing industries today The processing industries today – – Trends Trends

• Cost

Cost

• Environment

Environment

• Feedstock

Feedstock

• Fundamentals

Fundamentals

• Conclusions

Conclusions

SLIDE 4

4

“This ‘telephone’ has too many shortcomings to be seriously

considered as a means of communication” Western Union Memo “Heavier-than-air flying machines are impossible” Lord Kelvin, President Royal Society “The wireless music box (radio) has no imaginable commercial value” David Sarnoffs Associates in response to his urgings for investments in the radio “I think there’s a world market for maybe five computers” Thomas Watson, Chairman IBM “Computers in the future may weigh no more than 1.5 tons” Popular Mechanics forecasting the relentless march of science. “There is no reason anyone would want a computer in their home” Ken Olson, President, Chairman and Founder of Digital Equipment

1876 1895 1920 1943 1949 1977

Past Predictions Past Predictions

SLIDE 5

5

The refining and petrochemical The refining and petrochemical industries today industries today

• Evolution characterized by step

Evolution characterized by step-

• changes

changes

– – 1920 1920 Thermal cracking Thermal cracking – – 1930 1930 Alkylation Alkylation – – 1950 1950 Catalytic Reforming Catalytic Reforming – – 1970 1970 PX/MX/OX separations PX/MX/OX separations – – 1990 1990 Solid Acids for Solid Acids for alkylation alkylation – – 2000 2000 Bio based bulk chemicals Bio based bulk chemicals

• As a rule, technology in the refining and

As a rule, technology in the refining and petrochemical industries is mature, petrochemical industries is mature, growing with GDP growing with GDP

SLIDE 6

6

The Importance of Continuous Improvement The Importance of Continuous Improvement

Octane Barrel Capacity of FCC Octane Barrel Capacity of FCC

New Reactor New Reactor Concepts Concepts Improved Reaction Improved Reaction Systems Systems Octane Catalysts Octane Catalysts Extended Riser Extended Riser Zeolite Catalysts Zeolite Catalysts Amorphous Amorphous Catalysts Catalysts

6,200 6,200 6,000 6,000 5,800 5,800 5,600 5,600 5,400 5,400 5,200 5,200 5,000 5,000 4,800 4,800 1950 1950 1960 1960 1970 1970 1980 1980 1990 1990 1996 1996

Theoretical Octane Barrels

Octane Barrels / 100 Barrels Feed Octane Barrels / 100 Barrels Feed

SLIDE 7

7

Energy & Energy & Feedstocks Feedstocks Profitability Profitability Environmental Environmental Constraints Constraints Product Product Quality Quality

Trends in the Processing Industries

Sustainability

SLIDE 8

8

Process Intensification Process Intensification

• Coined in the 70’s by ICI by Colin

Coined in the 70’s by ICI by Colin Ramshaw Ramshaw

• A series of tools, aimed at

A series of tools, aimed at

– – reducing the capital cost of production for bulk chemicals reducing the capital cost of production for bulk chemicals – – at constant or lower variable cost of production. at constant or lower variable cost of production.

• Capex

Capex scales roughly with footprint or number of unit scales roughly with footprint or number of unit

• perations
• perations
• Achieved by

Achieved by

– – Combining syntheses, multiple products Combining syntheses, multiple products – – combining unit operations combining unit operations – – removing ‘limitations’ (intensifying) removing ‘limitations’ (intensifying)

• Heat transfer

Heat transfer

• Mass transfer

Mass transfer

• Kinetics

Kinetics

• Momentum/Pressure drop

Momentum/Pressure drop

• Gravity…

Gravity…

SLIDE 9

9

PI Techniques PI Techniques

• Just

Just-

• in

in-

• time manufacture

time manufacture – – lower inventories lower inventories

• In

In-

• line mixers

line mixers – – lower inventories lower inventories

• Structured column

Structured column packings packings – – less hold less hold-

• up

up

• Plate heat exchangers

Plate heat exchangers – – lower lower ∆ ∆T, less volume T, less volume

• Monolith catalysts

Monolith catalysts – – lower lower ∆ ∆T, better mass tfr T, better mass tfr

• Micro

Micro-

• channel reactors

channel reactors – – better mass tfr better mass tfr

• HiGee

HiGee fractionation fractionation – – better mass tfr better mass tfr

Increasing Commercial Acceptance

SLIDE 10

10

Relative Intensity Process Geometry

CURRENT NO HYDRAULIC LIMITATION ISO- THERMAL CRUSHED CATALYST LESS ATTEN- UATION IDEAL PT CLUSTERS

3 3 18 18 22 22 36 36 60 60

Process Intensification Potential

Propane Dehydrogenation Propane Dehydrogenation

SLIDE 11

11

Years

Reaction Kinetics Time Constant

Seconds Months Days Hours Minutes 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 Ebuliating Bed Mega Scale Direction of Reactor Development

Catalyst Deactivation Time Constant

PI trends in reactor technology PI trends in reactor technology

SLIDE 12

12

Energy & Energy & Feedstocks Feedstocks Profitability Profitability Environmental Environmental Constraints Constraints Product Product Quality Quality

Trends in the Processing Industries

Sustainability

SLIDE 13

13

Replacing HF Replacing HF Alkylation Alkylation

33.2 52.8 TOTAL 23.4 33.2 HF Acid Makeup 1.9 5.9 Lime 2.0 3.9 KOH 5.9 9.8 Alumina Cost, MM$/yr Amount, MM lbs/yr Material

• Waste generated for

Waste generated for world scale world scale alkylate alkylate plant: plant:

New solid acid catalyst, new reactor

– Inherent safety, Lower waste – Lower capital

SLIDE 14

14

Energy & Energy & Feedstocks Feedstocks Profitability Profitability Environmental Environmental Constraints Constraints Product Product Quality Quality

Trends in the Processing Industries

Sustainability

SLIDE 15

15

Availability of Oil ? Availability of Oil ?

1900 1900 1997 1997 2100 2100 Natural Resources Natural Resources P

• p

u l a t i

• n

P

• p

u l a t i

• n

P

• l

l u t i

• n

P

• l

l u t i

• n

Food Food Oil Oil 2030 2030

Meadows, 1992, p. 133 WRI, 1996

1950 1950

SLIDE 16

16

Evolution of Price of Brent Crude Oil

SLIDE 17

17

Evolution of Quality of Processed Crude Oil

SLIDE 18

18

Natural Gas as a Feedstock

Fuels & Power

Fischer-Tropsch MeOH + MTG Combustion

Demonstrated or Existing To Be Developed / Demonstrated

Indirect Conversion Direct Conversion

CH4

Hydrogen Steam Reform / WGS Cracking Aromatization Combustion Fischer-Tropsch MeOH + MTG

Chemicals

MeOH Synthesis MeOH + MTO Oxyhalogenation Coupling Direct POX Cracking Aromatization

SLIDE 19

19

Hydrogen as a fuel ? Hydrogen as a fuel ?

10 10 20 20 30 30 40 40 50 50 60 60 70 70 80 80 90 90 100 100 MM MT pa MM MT pa Oil Oil Ethylene Ethylene Hydrogen Hydrogen Benzene Benzene Methanol Methanol

200 400 600 800 1000 Price, $/MT Fuel Hydrogen Petrochemicals 200 400 600 800 1000 Price, $/MT Fuel Hydrogen Petrochemicals

Hydrogen currently looks like a Hydrogen currently looks like a petrochemical in scale and value petrochemical in scale and value

Global Consumption /Production Global Consumption /Production Comparable Product Values Comparable Product Values

3500 3500

UOP 4221-11

SLIDE 20

20

Hydrogen as a fuel in 2025 entails : Hydrogen as a fuel in 2025 entails :

Assume 10% World Energy Demand (based on 2025) Assume 10% World Energy Demand (based on 2025) Equivalent to 68 EJ ( Equivalent to 68 EJ (exa exa joules joules -

• 10

1018

18)

)

H2 Quantity New Plants Asset Investment* 7000 @ 100,000 Nm3 per hour each

UOP 4221-12

6x1012 Nm3 per year $1-3 trillion (1012)

* Includes H2 delivery assets

SLIDE 21

21

Evolution of Hydrogen Roadmap Evolution of Hydrogen Roadmap

Where? Where?

Time Time

Source? Source?

H H2

2

Function Function Short Term Medium Term Long Term

Fuel Quality Improvement Primary Fuel Fuel Enhancement

Central Central Distributed Distributed Fossil Renewables Renewables

5 years 5 years 10 10 -

• 20 years

20 years >20 years >20 years

UOP 4221-46

SLIDE 22

22

A Polymer Electrolyte Membrane (PEM) A Polymer Electrolyte Membrane (PEM) Fuel Cell is a Reactive Membrane Process Fuel Cell is a Reactive Membrane Process

Solid Polymer Electrolyte (e.g., Nafion) Microdiffusion Catalyst Layer Graphite Electrode Current Collector Hydrogen Spent Fuel (Depleted Hydrogen) Anode Cathode Air (Oxygen) Cathode Exhaust (Depleted Air) Anode Reaction H2 2H+ + 2e- Cathode Reaction 1/2 O2 + 2H+ + 2e- H2O 2e- Load

SLIDE 23

September 3, 1998 23

Cross-Section

• f PEM Fuel

Cell

M E M B R A N E Gas Diffusion Electrode Gas Diffusion Electrode O2 H2O

e- e- H+

Proton Exchange Membrane Gas Diffusion Electrode O2/ H 2O Electrocatalyst Layer H+ H+

The MEA is a Membrane with Dispersed Pt Catalyst on Both Sides

H2 / H2O Waste Gas

SLIDE 24

24

Fuel Cell i Fuel Cell i-

• V Curve

V Curve

Current Density (amps/cm2) Potential (V)

As the current density is increased As the current density is increased the potential decreases, giving a the potential decreases, giving a characteristic i characteristic i-

• V curve

V curve

SLIDE 25

25

Fuel Cell i Fuel Cell i-

• V Curve

V Curve

Current Density (amps/cm2) Potential (V)

Higher current density is good, as Higher current density is good, as this means less MEA area and lower this means less MEA area and lower cost cost

SLIDE 26

26

Fuel Cell i Fuel Cell i-

• V Curve

V Curve

Current Density (amps/cm2) Potential (V)

But higher potential is also good, as But higher potential is also good, as this means higher efficiency this means higher efficiency

SLIDE 27

27

Fuel Cell i Fuel Cell i-

• V Curve

V Curve

Current Density (amps/cm2) Potential (V)

The shape of the curve is the result The shape of the curve is the result

• f many different processes that
• f many different processes that
• ccur in the fuel cell, and are
• ccur in the fuel cell, and are

influenced by many design influenced by many design parameters parameters

SLIDE 28

28

Fuel Cell i Fuel Cell i-

• V Curve

V Curve

Current Density (amps/cm2) Potential (V)

At low current density V decreases At low current density V decreases rapidly due to kinetics of ionization rapidly due to kinetics of ionization & polarization of double layer & polarization of double layer

SLIDE 29

29

Fuel Cell i Fuel Cell i-

• V Curve

V Curve

Current Density (amps/cm2) Potential (V)

At medium current density, V At medium current density, V decreases slowly due to decreases slowly due to ohmic

• hmic

resistance in the electrical circuit resistance in the electrical circuit

SLIDE 30

30

Fuel Cell i Fuel Cell i-

• V Curve

V Curve

Current Density (amps/cm2) Potential (V)

At high current density, V decreases At high current density, V decreases rapidly due to severe mass transfer rapidly due to severe mass transfer limitations or water management limitations or water management problems in the MEA and flow problems in the MEA and flow channels channels

SLIDE 31

31

Fuel Cell Theory Fuel Cell Theory

Cell voltage, Cell voltage, V = V = V Vo

• -
• η

ηΩ

Ω -

• η

ηCT

CT -

• η

ηMT

MT

η ηΩ

Ω = i

= i ℜ ℜint

int

η ηCT

CT =

= -

• RT

RT ln i ln io

• + RT

+ RT ln ln i i α α nF nF α α nF nF i io

• =

= nF nF k k1

1C

CR

R exp

exp -

• U

Ua

ao

• -
• α

α nF nF ∆ϕ ∆ϕ RT RT η ηMT

MT =

= RT RT ln ln 1 1 -

• i

i α α n F n F i iL

L

i iL

L = D

= D nF C nF Cb

b

δ δ Cell voltage, Cell voltage, V = V = V Vo

• -
• η

ηΩ

Ω -

• η

ηCT

CT -

• η

ηMT

MT

η ηΩ

Ω = i

= i ℜ ℜint

int

η ηCT

CT =

= -

• RT

RT ln i ln io

• + RT

+ RT ln ln i i α α nF nF α α nF nF i io

• =

= nF nF k k1

1C

CR

R exp

exp -

• U

Ua

ao

• -
• α

α nF nF ∆ϕ ∆ϕ RT RT η ηMT

MT =

= RT RT ln ln 1 1 -

• i

i α α n F n F i iL

L

i iL

L = D

= D nF C nF Cb

b

δ δ

SLIDE 32

32

Fuel Cell Theory Fuel Cell Theory

Depends on Depends on electrical electrical resistance of resistance of membrane, membrane, electrodes, electrodes, catalyst/electro catalyst/electro de junctions, de junctions, etc. etc.

Cell voltage, Cell voltage, V = V = V Vo

• -
• η

ηΩ

Ω -

• η

ηCT

CT -

• η

ηMT

MT

η ηΩ

Ω = i

= i ℜ ℜint

int

η ηCT

CT =

= -

• RT

RT ln i ln io

• + RT

+ RT ln ln i i α α nF nF α α nF nF i io

• =

= nF nF k k1

1C

CR

R exp

exp -

• U

Ua

ao

• -
• α

α nF nF ∆ϕ ∆ϕ RT RT η ηMT

MT =

= RT RT ln ln 1 1 -

• i

i α α n F n F i iL

L

i iL

L = D

= D nF C nF Cb

b

δ δ Cell voltage, Cell voltage, V = V = V Vo

• -
• η

ηΩ

Ω -

• η

ηCT

CT -

• η

ηMT

MT

η ηΩ

Ω = i

= i ℜ ℜint

int

η ηCT

CT =

= -

• RT

RT ln i ln io

• + RT

+ RT ln ln i i α α nF nF α α nF nF i io

• =

= nF nF k k1

1C

CR

R exp

exp -

• U

Ua

ao

• -
• α

α nF nF ∆ϕ ∆ϕ RT RT η ηMT

MT =

= RT RT ln ln 1 1 -

• i

i α α n F n F i iL

L

i iL

L = D

= D nF C nF Cb

b

δ δ

SLIDE 33

33

Fuel Cell Theory Fuel Cell Theory

Depends on Depends on intrinsic intrinsic kinetics of kinetics of charge transfer charge transfer at the at the electrocatalyst electrocatalyst

Cell voltage, Cell voltage, V = V = V Vo

• -
• η

ηΩ

Ω -

• η

ηCT

CT -

• η

ηMT

MT

η ηΩ

Ω = i

= i ℜ ℜint

int

η ηCT

CT =

= -

• RT

RT ln i ln io

• + RT

+ RT ln ln i i α α nF nF α α nF nF i io

• =

= nF nF k k1

1C

CR

R exp

exp -

• U

Ua

ao

• -
• α

α nF nF ∆ϕ ∆ϕ RT RT η ηMT

MT =

= RT RT ln ln 1 1 -

• i

i α α n F n F i iL

L

i iL

L = D

= D nF C nF Cb

b

δ δ Cell voltage, Cell voltage, V = V = V Vo

• -
• η

ηΩ

Ω -

• η

ηCT

CT -

• η

ηMT

MT

η ηΩ

Ω = i

= i ℜ ℜint

int

η ηCT

CT =

= -

• RT

RT ln i ln io

• + RT

+ RT ln ln i i α α nF nF α α nF nF i io

• =

= nF nF k k1

1C

CR

R exp

exp -

• U

Ua

ao

• -
• α

α nF nF ∆ϕ ∆ϕ RT RT η ηMT

MT =

= RT RT ln ln 1 1 -

• i

i α α n F n F i iL

L

i iL

L = D

= D nF C nF Cb

b

δ δ

SLIDE 34

34

Fuel Cell Theory Fuel Cell Theory

Depends on Depends on double layer double layer polarization at polarization at the electrode/ the electrode/ membrane membrane interface interface

Cell voltage, Cell voltage, V = V = V Vo

• -
• η

ηΩ

Ω -

• η

ηCT

CT -

• η

ηMT

MT

η ηΩ

Ω = i

= i ℜ ℜint

int

η ηCT

CT =

= -

• RT

RT ln i ln io

• + RT

+ RT ln ln i i α α nF nF α α nF nF i io

• =

= nF nF k k1

1C

CR

R exp

exp -

• U

Ua

ao

• -
• α

α nF nF ∆ϕ ∆ϕ RT RT η ηMT

MT =

= RT RT ln ln 1 1 -

• i

i α α n F n F i iL

L

i iL

L = D

= D nF C nF Cb

b

δ δ Cell voltage, Cell voltage, V = V = V Vo

• -
• η

ηΩ

Ω -

• η

ηCT

CT -

• η

ηMT

MT

η ηΩ

Ω = i

= i ℜ ℜint

int

η ηCT

CT =

= -

• RT

RT ln i ln io

• + RT

+ RT ln ln i i α α nF nF α α nF nF i io

• =

= nF nF k k1

1C

CR

R exp

exp -

• U

Ua

ao

• -
• α

α nF nF ∆ϕ ∆ϕ RT RT η ηMT

MT =

= RT RT ln ln 1 1 -

• i

i α α n F n F i iL

L

i iL

L = D

= D nF C nF Cb

b

δ δ

SLIDE 35

35

Fuel Cell Theory Fuel Cell Theory

Depends on Depends on mass transfer mass transfer properties of properties of electrocatalyst electrocatalyst and stack and stack design design

Cell voltage, Cell voltage, V = V = V Vo

• -
• η

ηΩ

Ω -

• η

ηCT

CT -

• η

ηMT

MT

η ηΩ

Ω = i

= i ℜ ℜint

int

η ηCT

CT =

= -

• RT

RT ln i ln io

• + RT

+ RT ln ln i i α α nF nF α α nF nF i io

• =

= nF nF k k1

1C

CR

R exp

exp -

• U

Ua

ao

• -
• α

α nF nF ∆ϕ ∆ϕ RT RT η ηMT

MT =

= RT RT ln ln 1 1 -

• i

i α α n F n F i iL

L

i iL

L = D

= D nF C nF Cb

b

δ δ Cell voltage, Cell voltage, V = V = V Vo

• -
• η

ηΩ

Ω -

• η

ηCT

CT -

• η

ηMT

MT

η ηΩ

Ω = i

= i ℜ ℜint

int

η ηCT

CT =

= -

• RT

RT ln i ln io

• + RT

+ RT ln ln i i α α nF nF α α nF nF i io

• =

= nF nF k k1

1C

CR

R exp

exp -

• U

Ua

ao

• -
• α

α nF nF ∆ϕ ∆ϕ RT RT η ηMT

MT =

= RT RT ln ln 1 1 -

• i

i α α n F n F i iL

L

i iL

L = D

= D nF C nF Cb

b

δ δ

SLIDE 36

36

Fuel Cell Theory Fuel Cell Theory

All of these All of these depend on depend on temperature temperature and and concentration concentration profiles in the profiles in the electrocatalyst electrocatalyst, , hence “reactor hence “reactor design’ design’

Cell voltage, Cell voltage, V = V = V Vo

• -
• η

ηΩ

Ω -

• η

ηCT

CT -

• η

ηMT

MT

η ηΩ

Ω = i

= i ℜ ℜint

int

η ηCT

CT =

= -

• RT

RT ln i ln io

• + RT

+ RT ln ln i i α α nF nF α α nF nF i io

• =

= nF nF k k1

1C

CR

R exp

exp -

• U

Ua

ao

• -
• α

α nF nF ∆ϕ ∆ϕ RT RT η ηMT

MT =

= RT RT ln ln 1 1 -

• i

i α α n F n F i iL

L

i iL

L = D

= D nF C nF Cb

b

δ δ Cell voltage, Cell voltage, V = V = V Vo

• -
• η

ηΩ

Ω -

• η

ηCT

CT -

• η

ηMT

MT

η ηΩ

Ω = i

= i ℜ ℜint

int

η ηCT

CT =

= -

• RT

RT ln i ln io

• + RT

+ RT ln ln i i α α nF nF α α nF nF i io

• =

= nF nF k k1

1C

CR

R exp

exp -

• U

Ua

ao

• -
• α

α nF nF ∆ϕ ∆ϕ RT RT η ηMT

MT =

= RT RT ln ln 1 1 -

• i

i α α n F n F i iL

L

i iL

L = D

= D nF C nF Cb

b

δ δ

SLIDE 37

37

Renewable Feedstocks

Ethanol Surfactants Biodiesel

PLA

Subsidized

Solvents Hydrogen CHP

Market Value?

Plastics Fibers Chemicals Chemicals Energy Energy F u e l A d d i t i v e s F u e l A d d i t i v e s

• Biofuels subsidized

Biofuels subsidized

– – Drive EtOH cost down Drive EtOH cost down – – Value from by Value from by-

• products

products

• Market Value with higher value added

Market Value with higher value added products products

SLIDE 38

38

Example: Cargill Example: Cargill-

• Dow Natureworks

Dow NatureworksTM

TM PLA

PLA

C H3 O H O OH O O CH3 O O H CH3 O OH O CH3

Lactic Acid Polylactic Acid (PLA)

• 1. Hydrolysis

(enzymatic)

• 2. Fermentation

Corn Starch (or other biomass)

Polymerization

100% Annually Renewable Carbon Source

Life-Cycle Analysis (compared with petroleum derived polymer)

• 20-50% net fossil fuel reduction
• 15–60% reduction in greenhouse gases

140,000 kmta production plant started in 2002 (Blair, NE) 85+ Development Agreements

Cargill Dow Dedicates PLA Refinery April 2002

SLIDE 39

39

Energy & Energy & Feedstocks Feedstocks Profitability Profitability Environmental Environmental Constraints Constraints Product Product Quality Quality

Trends in the Processing Industries

Sustainability

SLIDE 40

40

From Conoco’s Sustainable Growth Report, May 2001

A new set of criteria A new set of criteria

SLIDE 41

41

Outline Outline

• Future Directions

Future Directions

• Fundamentals

Fundamentals

– – Molecular level Molecular level – – Reactions and Catalysis Reactions and Catalysis – – Reactor Selection and Design Reactor Selection and Design – – Process Design and Optimization Process Design and Optimization

• Conclusions

Conclusions

SLIDE 42

42

Knowledge Flow in Technology Delivery Knowledge Flow in Technology Delivery

Layer 4: Process Design and Optimization Layer 1: Molecular Insight Layer 2: Reaction Level Layer 3: Reactor Design

SLIDE 43

43

Use of Computational Chemistry and Use of Computational Chemistry and STEM to Identify Active Sites STEM to Identify Active Sites

• S. Helveg et al., Phys. Rev. Lett., 84, 951 (2000)

HDS activity is believed to take HDS activity is believed to take place on MoS place on MoS2

2 cluster edges.

cluster edges. However, their coordination However, their coordination should make them inert ? should make them inert ? MoS MoS2

2 cluster reorganizes in the

cluster reorganizes in the presence of atomic hydrogen, presence of atomic hydrogen, leading to sulfur vacancies, leading to sulfur vacancies, which are believed to be the which are believed to be the active sites for HDS active sites for HDS

The advent of DFT methods, fast computers and in The advent of DFT methods, fast computers and in-

• situ

situ visualization techniques aids in understanding catalysis and visualization techniques aids in understanding catalysis and designing next generation catalysts designing next generation catalysts

SLIDE 44

44

Molecular Mechanics to Model Potential Energy Molecular Mechanics to Model Potential Energy Surface for Diffusion in Microporous Materials Surface for Diffusion in Microporous Materials

• 35
• 30
• 25
• 20
• 15
• 10
• 5

5 10 15 5 10 15 20 25 30 35 40

POSITION IN CHANNEL (A) RELATIVE ENERGY (kcal/mol)

SLIDE 45

45

Reaction Level : Temperature Reaction Level : Temperature Scanning Reactor (TSR) Scanning Reactor (TSR)

• Integral

Integral Microreactor Microreactor

• Non

Non-

• Steady

Steady-

• State Operation

State Operation

• Special Methodology to Extract Reaction Rates

Special Methodology to Extract Reaction Rates

• Wide Range of Process Variables Studied in

Wide Range of Process Variables Studied in One Experiment One Experiment Original method revised substantially to allow for Original method revised substantially to allow for direct translation to conventional PP data direct translation to conventional PP data

Source : Wojciechowski et al., USP 5593892, 5521095 and 5340745 Source : Wojciechowski et al., USP 5593892, 5521095 and 5340745

SLIDE 46

46

TSR methodology TSR methodology

Catalyst Volume Mapped By Varying Space-Time

C

• n

v e r s i

• n

Feed Product

Rate = F* Rate = F*dX/dV dX/dV

• -> Rate = F*

> Rate = F*dX/dTau dX/dTau

SLIDE 47

47

TSR : Experimental Protocol TSR : Experimental Protocol

25 50 75 100 125 150 25 50 75 100 125 150

SLIDE 48

Space Time, sec. Conversion Product Feed

Many Pilot Plant Runs Many Pilot Plant Runs vs vs Single Single TSR Experiment TSR Experiment

Fractional Catalyst Volume

1.5 1.0 0.5

• 0.5

0.4 0.3 0.2 0.1

R e a c t

• r

I n l e t T e m p e r a t u r e , K

700 750 800 850 900

SLIDE 49

49

Conversion Conversion vs vs T and T and Tau Tau

430 420 410 400 390 380 370 360 350 340 R x

• I

n T ( C ) 2 5 5 7 5 1 TAU 1 1 1.25 1.25 1.5 1.5 1.75 1.75 2 2 2.25 2.25 2.5 2.5

• -Xylene Conversion
• -Xylene Conversion

SLIDE 50

50

Typical Parity Plots for TSR data Typical Parity Plots for TSR data

• 0.14
• 0.12
• 0.1
• 0.08
• 0.06
• 0.04
• 0.02
• 0.05

0.05 0.1 0.15 0.2

• 3.00E-02
• 2.00E-02
• 1.00E-02

0.00E+00 1.00E-02 2.00E-02 3.00E-02 4.00E-02 5.00E-02 6.00E-02 7.00E-02

• 3.00E-02
• 1.00E-02

1.00E-02 3.00E-02 5.00E-02 7.00E-02

Internal Mass Transfer Added To Model

Model without Mass Transfer

1400 data points 1400 data points

SLIDE 51

51

Studying Deactivation : TEOM Studying Deactivation : TEOM

• Measure conversion,

Measure conversion, selectivity,and mass selectivity,and mass changes at process changes at process conditions conditions

• 800 psig

800 psig

• 600

600o

• C

C

• Oscillating Reactor

Oscillating Reactor

– – Frequency related Frequency related to mass to mass

SLIDE 52

52

Typical TEOM Data

50 100 150 200 250 300 350 400 Time on Stream

• Wt. Gain (%)

Conversion (%)

SLIDE 53

53

Reactors to suit every need

Years

Reaction Kinetics Time Constant

Seconds Months Days Hours Minutes m-seconds seconds minutes hours FCC Fixed-Fluid Bed; MTO Moving Bed Radial Flow with CCR; Oleflex, Platforming, Cyclar Fixed Bed radial Flow Semi-Regen; Platforming, Pacol Cyclic Fixed Bed axial Flow; Detal Fixed Bed axial Flow; Hydrocracking Circulating Liquid Riser; SCA Ebulating Bed

Catalyst Deactivation Time Constant

SLIDE 54

54

Alkylene Alkylene Flow Scheme Flow Scheme

Olefin Olefin Feed Feed Alkylene Alkylene Reactor Reactor i iC C4

4/H

/H2

2

Reactivation Reactivation Wash Zone Wash Zone

Isobutane Isobutane Recycle Recycle

H H2

2

Reactivation Reactivation Wash Zone Wash Zone

Alkylate Alkylate LPG LPG Fractionation Fractionation Section Section Feed Feed Treatment Treatment Reactivation Reactivation Vessel Vessel

SLIDE 55

55

Simulated Flow Field for Simulated Flow Field for Alkylene Alkylene Riser with Olefin Injection Riser with Olefin Injection

100 200 300 400

Z

1 0

X

2 0

Y X Z Y 0 .1 2 0 0 .0 9 0 0 .0 6 0 0 .0 3 0 0 .0 2 0 0 .0 1 5 0 .0 1 0 0 .0 0 6 0 .0 0 3

C F D L I B 9 6 . 2 T = 2 . 5 0 0 E+ 0 1 N = 4 7 1 6 8

O le fin V o l. F ra c tio n

A n g le o f In je c tio n = -3 6

• Incorporated

Incorporated Alkylene Alkylene kinetics kinetics to study the to study the effect of poor effect of poor mixing mixing

SLIDE 56

56

Scale up of olefin injection ? Scale up of olefin injection ?

Diameter 1 Nozzle inlet velocity 1 Diameter 2 Nozzle inlet velocity 2

SLIDE 57

57

Alkylene Alkylene modeling cont’d modeling cont’d

• Additional work on

Additional work on

– – Catalyst residence time in injection zones Catalyst residence time in injection zones – – Geometrical studies for disengagement Geometrical studies for disengagement vessel vessel – – Alkylate Alkylate flushing from disengaged catalyst flushing from disengaged catalyst

SLIDE 58

58

Process Level : Proprietary Extensions in Flowsheets

SLIDE 59

59

Overall Process Design: Separations Overall Process Design: Separations

LAB Complex PEP Dividing Wall Column LAB Complex PEP Dividing Wall Column

Depentanizer Bottoms as Benzene feed to the Alkylation Unit

DEPENTANIZER

Purge to Adsorbers Purge from Adsorbers Desorbent from Adsorbers Desorbent Column Bottoms to Storage

DESORBENT COLUMN

PEP Fractionator Sidedraw as Benzene feed to the Alkylation Unit Purge to Adsorbers Purge from Adsorbers Desorbent Column Bottoms to Storage Benzene from Alkylation Unit Benzene from Alkylation Unit Desorbent from Adsorbers Dividing Wall

SLIDE 60

60

MTBE MTBE Packing Packing

• r trays
• r trays

Methanol Methanol recovery recovery section section

Unreacted C Unreacted C4

4

hydrocarbons hydrocarbons Recycle methanol Recycle methanol Reactor Reactor section section C C4

4 olefins

• lefins

Methanol Methanol

MTBE revamp MTBE revamp

SLIDE 61

61

MTBE revamp to InAlk with resin MTBE revamp to InAlk with resin

Reactor Reactor section section

Oxygenate Oxygenate recovery recovery section section

Alkylate product Alkylate product

Light Light ends ends H H2

2

Olefin Olefin saturation saturation section section Recycle oxygenate Recycle oxygenate Packing Packing

• r trays
• r trays

Unreacted C Unreacted C4

4 to

to Direct Alkylation Direct Alkylation

• r Fleximer
• r Fleximer

C C4

4 olefins

• lefins

Olefinic product Olefinic product Water Water Water

SLIDE 62

62

Outline Outline

• Future Directions

Future Directions

• Fundamentals

Fundamentals

• Conclusions

Conclusions

SLIDE 63

63

Conclusions Conclusions

• A new era in the processing industry

A new era in the processing industry

– – Gradual, rather than abrupt change over Gradual, rather than abrupt change over – – New feed New feed-

• stocks and new requirements

stocks and new requirements require a new wave of innovation. require a new wave of innovation.

• Fundamentals

Fundamentals

– – Almost established as the basis of Almost established as the basis of technology development today technology development today – – Critical for rapid innovation and Critical for rapid innovation and

• ptimization in the future
• ptimization in the future

SLIDE 64

64

Acknowledgement Acknowledgement

Stimulating discussions with the following UOP staff Stimulating discussions with the following UOP staff are gratefully acknowledged: are gratefully acknowledged:

• D. Galloway
• D. Galloway
• A. Sachtler
• A. Sachtler
• J. Holmgren
• J. Holmgren
• S. Kumar
• S. Kumar
• P. Sechrist
• P. Sechrist
• G. Towler
• G. Towler
• A. Oroskar
• A. Oroskar
• S. Gembicki
• S. Gembicki
• G. Miller
• G. Miller
• C. Cabrera
• C. Cabrera