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ChE 512 Transport Effects in Chemical Reactors PART 2

Module 1 Introduction to Heterogeneous Reactors and Application Areas

P.A. Ramachandran rama@wustl.edu

Topical Outline

• Introduction • Kinetic models • Transport effects • Gas-solid reactions • Gas-liquid reactions • Three Phase Reactors • Biochemical reactors • Electrochemical reactors

Course Objectives

Course

Objectives

Course Objectives Course Objectives • Review basic multiphase reaction engineering reactor types and applications in petroleum

Review basic multiphase reaction engineering reactor types and applications in petroleum processing, fine chemicals, and specialty chemicals.

Develop basic relationships that describe the coupling between transport effects and kinetics for multiphase systems on a local level.

Derive the basic performance equations for integral reactor performance using ideal flow patterns for the various phases.

Present case studies or examples where the theory is put into practise.

Module 1 Outline

• Industrial Applications and Examples • Review of Common Reactor Types • Guidelines for Reactor Selection

Starting References

Starting

References

Starting References Starting References 1. Doraiswamy L.K. and Sharma. M. M. Heterogenous Reactions, 2. P. A.
  • 1. Doraiswamy L.K. and Sharma. M. M. Heterogenous Reactions,

  • 2. P. A. Ramachandran and R. V. Chaudhari, Three-Phase Catalytic Reactors, Gordon & Breach, London (1983).

  • 3. P. L. Mills, P. A. Ramachandran, and R. V. Chaudhari, Reviews in Chemical Engineering, 8, pp. 1-192 (1992).

  • 4. P. L. Mills and R. V. Chaudhari, “Multiphase catalytic reactor engineering and design for pharmaceuticals and fine chemicals,” Catalysis Today, 37(4), pp. 367-404 (1997).

Multiphase Catalytic

Multiphase

Catalytic Reactions

Reactions

Multiphase Catalytic Multiphase Catalytic Reactions Reactions Reactants Δ Catalyst Products Present • Gases • Liquids •

Reactants

Δ

Multiphase Catalytic Multiphase Catalytic Reactions Reactions Reactants Δ Catalyst Products Present • Gases • Liquids •

Catalyst

Products

Multiphase Catalytic Multiphase Catalytic Reactions Reactions Reactants Δ Catalyst Products Present • Gases • Liquids •

Present

Multiphase Catalytic Multiphase Catalytic Reactions Reactions Reactants Δ Catalyst Products Present • Gases • Liquids •

Gases Liquids Solids Solvent

Homogeneous

Heterogeneous

Enzyme

Bacteria

Cells

Gases Liquids Solids Solvent

Classification Based on Number of Phases

• Gas-Solid Catalytic • Gas-Solid Non-Catalytic • Gas-Liquid • Gas-Liquid Solid Catalytic • Gas-Liquid with Solid Reacting • Liquid-Liquid • Gas-Liquid-Liquid-Solid

Some Examples

Some

Examples ofof

Multiphase Catalytic

Multiphase

Catalytic Processes

Processes

Examples Some of of Multiphase Catalytic Multiphase Catalytic Processes Processes • Hydrogenation of specialty chemicals

Hydrogenation of specialty chemicals Oxidation of glucose to gluconic acid Oxidation of n-paraffins to alcohols Methanol synthesis Fischer-Tropsch (FT) synthesis Hydrodesulfurization (HDS) of heavy residuals Adiponitrile synthesis Production of animal cells Fermentation processes

8
8

Other Emerging

Other

Emerging

Multiphase Catalytic

Multiphase

Catalytic Technologies

Technologies

Other Emerging Other Emerging Multiphase Catalytic Multiphase Catalytic Technologies Technologies • Catalysis by water soluble metal

Catalysis by water soluble metal complexes in biphasic and nonionic liquid media

Reactions in supercritical fluid media Asymmetric catalysis for chiral drugs/agrichemicals Polymerization with precipitating products (e.g., Polyketones) Phase transfer catalysis

Catalysis by adhesion of metal particles to liquid-liquid interfaces

Catalysis by nano-particles and encapsulation of metal complexes

Multiphase

Multiphase Reactor

Reactor Technology

Technology Areas

Areas

Multiphase Multiphase Reactor Reactor Technology Technology Areas Areas Syngas & Natural Gas Conversion Petroleum Refining MeOH,
Syngas & Natural Gas Conversion Petroleum Refining MeOH, DME, MTBE, Paraffins, Olefins, Higher alcohols, …. Value
Syngas & Natural Gas
Conversion
Petroleum
Refining
MeOH, DME, MTBE,
Paraffins, Olefins,
Higher alcohols, ….
Value of Shipments
in $US billions
HDS, HDN, HDM,
Dewaxing, Fuels,
Aromatics, Olefins, ...
450
350
Bulk
Polymer
Chemicals
Manufacture
250
Aldehydes, Alcohols,
Amines, Acids, Esters,
LAB’s, Inorg Acids, ...
150
1987
1989
1991
1993
1995
1997
Polycarbonates,
PPO, Polyolefins,
Specialty plastics
http://www.eia.doe.gov/
Fine Chemicals
& Pharmaceuticals
Environmental
Remediation

Ag Chem, Dyes, Fragrances, Flavors, Nutraceuticals, ...

P. L. Mills NASCRE 1, Houston, Jan 2001

De-NOx, De-SOx, HCFC’s, DPA, “Green” Processes ..

The Global Chemical Industry

The Global Chemical Industry • Generates > $2 trillion gross income 70,000 products - 1000 corporations

Generates > $2 trillion gross income

- 70,000 products - 1000 corporations (many small ones)

Largest contributor to GDP

Balance • Distribution: 10% Japan European Union 13% 35% Asia 15% CS&E USA 27%
Balance
• Distribution:
10%
Japan
European Union
13%
35%
Asia
15%
CS&E
USA
27%

CR&D Chemical Sciences & Engineering P. L. Mills

11

Multiphase Catalytic

Multiphase

Catalytic Reactions

Reactions

-- Business

Business Drivers

Drivers --

Multiphase Catalytic Multiphase Catalytic Reactions Reactions - - Business Drivers - - • Increased globalization of

Increased globalization of markets

Societal demands for higher environmental performance

Financial market demands for increased profitabilty and capital productivity

Higher customer expectations

Changing work force requirements

Technology Vision 2020, The US Chemical Industry, Dec. 1996 http://www.eere.energy.gov/industry/chemicals/pdfs/chem_vision.pdf

Cost Breakdown

Cost

Breakdown for

for Chemical

Chemical Production

Production

Cost Breakdown Cost Breakdown for for Chemical Chemical Production Production • Small < 10 MM lb/yr

Cost Breakdown Cost Breakdown for for Chemical Chemical Production Production • Small < 10 MM lb/yr
Small < 10 MM lb/yr Scale Product Large Scale > 100 MM lb/yr Product * *
Small
< 10 MM lb/yr
Scale
Product
Large
Scale
> 100 MM lb/yr
Product
*
*

70

60

50

40

30

20

10

0

Cost Breakdown Cost Breakdown for for Chemical Chemical Production Production • Small < 10 MM lb/yr
Cost Breakdown Cost Breakdown for for Chemical Chemical Production Production • Small < 10 MM lb/yr
Cost Breakdown Cost Breakdown for for Chemical Chemical Production Production • Small < 10 MM lb/yr
Cost Breakdown Cost Breakdown for for Chemical Chemical Production Production • Small < 10 MM lb/yr
Cost Breakdown Cost Breakdown for for Chemical Chemical Production Production • Small < 10 MM lb/yr

For large-scale processes, research must focus on reducing cost of raw materials and/or capital

Small-scale processes can benefit from almost any improvement

Adapted from Keller & Bryan, CEP, January (2000)

13
13

Process Development

Process

Development Methodology

Methodology

Process Development Process Development Methodology Methodology Lerou & Ng, CES, 51(10) (1996) 14
Process Development Process Development Methodology Methodology Lerou & Ng, CES, 51(10) (1996) 14
Process Development Process Development Methodology Methodology Lerou & Ng, CES, 51(10) (1996) 14

Lerou & Ng, CES, 51(10) (1996)

14

Oxidation ofof pp--Xylene

Oxidation

Xylene toto Terephthalic

Terephthalic Acid

Acid

of of p p - - Xylene Oxidation to to Terephthalic Acid H 2 COOH
H 2 COOH 4-CBA COOH CH 3 CH 3 cat I cat I O 2 CH
H 2
COOH
4-CBA
COOH
CH 3
CH 3
cat I
cat I
O 2
CH 3
CH 3
TPA
O 2
O 2
p-xylene
COOH
COOH
COOH
4-CT
CHO
cat II
cat I

Oxidation:

Cat I: Co-Mn-Br

Temp.: 190-205°C P O2 : 1.5-3.0 MPa Hydrogenation:

Cat II: Pd/support

4-CT

Temp.: 225-275°C

G-L (homogeneous) catalytic oxidation with precipitating solid product.

Oxygen mass transfer limitation, starvation of oxygen (due to safety limits) and exothermicity are key issues in reactor performance

Undesired impurity 4-CBA in ppm level requires a separate hydrogenation step (g-l-s reaction) to purify TPA

Involves dissolution of impurities, hydrogenation and re-crystallization to achieve purified TPA Selection of suitable multiphase reactors has been a major challenge

15

Key Multiphase

Key

Multiphase Reactor

Reactor Types

Types

• Mechanically agitated tanks • Multistage agitated columns • Bubble columns • Draft-tube reactors • Loop reactors

Soluble catalysts & Powdered catalysts

• Packed columns • Trickle-beds • Packed bubble columns • Ebullated-bed reactors

Soluble catalysts & Tableted catalysts

Classification

Classification of

of Multiphase

Multiphase

Gas--Liquid

Gas

Liquid--Solid

Solid Catalyzed

Catalyzed Reactors

Reactors

Classification Classification of of Multiphase Multiphase Gas - - Liquid Gas Liquid - - Solid Solid

1. Slurry Reactors

Catalyst powder is suspended in the liquid

phase to form a slurry.

2. Fixed-Bed Reactors

Catalyst pellets are maintained in place as

a fixed-bed or packed-bed.

Classification Classification of of Multiphase Multiphase Gas - - Liquid Gas Liquid - - Solid Solid

K. Ostergaard, Adv. Chem. Engng., Vol. 7 (1968)

17

Modification of

Modification

of the

the Classification

Classification for

for

Gas--Liquid

Gas

Liquid Soluble

Soluble Catalyst

Catalyst Reactors

Reactors

Modification of Modification of the the Classification Classification for for Gas - - Liquid Gas Liquid
  • 1. Catalyst complex is dissolved in the liquid

phase to form a homogeneous phase.

  • 2. Random inert or structured packing, if used, provides interfacial area for gas-liquid contacting.

Modification of Modification of the the Classification Classification for for Gas - - Liquid Gas Liquid

18

Common types of gas-solid reactors

• Packed bed

Fluid bed

• Monolith

• Riser and Downer

Multiphase

Multiphase Reactor

Reactor Types

Types

Middleton (1992)

Multiphase Multiphase Reactor Reactor Types Types Middleton (1992) a a Glance at 20

at aa Glance

at

Glance

Multiphase Multiphase Reactor Reactor Types Types Middleton (1992) a a Glance at 20

20

Mechanically Agitated

Mechanically

Agitated Reactors

Reactors

--Batch

Batch or

or Semi

Semi--Batch

Batch Operation

Operation--

Mechanically Agitated Mechanically Agitated Reactors Reactors - - Batch Batch or or Semi Semi - -
P G
P
G
Mechanically Agitated Mechanically Agitated Reactors Reactors - - Batch Batch or or Semi Semi - -

(a) Batch “ Dead - Headed “

Gas Gas
Gas
Gas

(b) Semi - Batch

21

Mechanically Agitated

Mechanically

Agitated Reactors

Reactors

-- Continuous

Continuous Operation

Operation --

Mechanically Agitated Mechanically Agitated Reactors Reactors - - Continuous Operation - - L G G L
L
L
G G L G G
G
G
L
G
G
Mechanically Agitated Mechanically Agitated Reactors Reactors - - Continuous Operation - - L G G L

G

Multistage Agitated Column for the Synthesis of Vitamin “carbol” (Wiedeskehr, 1988)

22

Mechanically Agitated

Mechanically

Agitated Reactors

Reactors

-- Pros

Pros and

and Cons

Cons --

Pros Cons
Pros
Cons

• Small catalyst particles

• High effectiveness factor

• Highly active catalysts

• Well-mixed liquid

• Catalyst addition

• Nearly isothermal

• Straightforward scale-up

• Process flexibility

• Catalyst handling

• Catalyst fines carryover

• Catalyst loading limitations

• Homogeneous reactions

• Pressure limitations

• Temp. control (hot catalysts)

• Greater power consumption

• Large vapor space

Mechanically Agitated Mechanically Agitated Reactors Reactors - - Pros and Cons - - Pros Cons •

Source:

P. L. Mills, R. V. Chaudhari, and P. A. Ramachandran

Reviews in Chemical Engineering (1993).

23

The BIAZZI Reactor The BIAZZI Hydrogenation Hydrogenation Reactor
The BIAZZI
Reactor
The
BIAZZI Hydrogenation
Hydrogenation Reactor

Inefficient heat and mass transfer

M
M

Catalyst deposition in low turbulence area

Poor mixing and non- homogeneous conditions in low turbulence area

Inefficient cooling

GG Sealing problems

Conventional Reactor

The BIAZZI Reactor The BIAZZI Hydrogenation Hydrogenation Reactor Inefficient heat and mass transfer M Catalyst deposition
The BIAZZI Reactor The BIAZZI Hydrogenation Hydrogenation Reactor Inefficient heat and mass transfer M Catalyst deposition

Powerful gas dispersion and recirculation:

high mass transfer

No heat transfer

limitations

(up to 20 m 2 /m 3 )

Easy catalyst

The BIAZZI Reactor The BIAZZI Hydrogenation Hydrogenation Reactor Inefficient heat and mass transfer M Catalyst deposition

recycling

Negligible fouling

Safer than the conventional reactors

BIAZZI Reactor

24

Multistage Multistage Agitated Agitated Column Column for for Synthesis Synthesis “Carbol” “Carbol”--Pharmaceutical Pharmaceutical Intermediate Intermediate O
Multistage
Multistage Agitated
Agitated Column
Column for
for Synthesis
Synthesis
“Carbol”
“Carbol”--Pharmaceutical
Pharmaceutical Intermediate
Intermediate
O
(i) aq. KOH
(ii) NH 3 , -5 o C
+
R
R
OH
(iii) H 2 SO 4
α,β-unsaturated
Carbol
ketone
• Continuous reactor system with a cascade
column and multistage agitator ensures
good mixing, long mean residence time and
narrow residence time distribution
• Gas phase voidage is minimum, hence safer
for acetylene handling
• High productivity/smaller volume
25
Chem. Eng. Sci., 43, 1783, 1988
Bubble Column Bubble Column Reactors Reactors a a Glance at Tarhan (1983) 26

Bubble Column

Bubble

Column Reactors

Reactors

at aa Glance

at

Glance

Bubble Column Bubble Column Reactors Reactors a a Glance at Tarhan (1983) 26

Tarhan (1983)

26

Key Types

Key

Types of

of Bubble

Bubble Columns

Columns

Key Types Key Types of of Bubble Bubble Columns Columns G L L G (a) Empty
G L L G
G
L
L
G

(a) Empty

Semi - Batch

G L L
G
L
L

G

Key Types Key Types of of Bubble Bubble Columns Columns G L L G (a) Empty
G L L G
G
L
L
G

(b) Plate

Continuous

(c) Packed

Semi - Batch

Bubble Column

Bubble

Column Reactors

Reactors

-- Pros

Pros and

and Cons

Cons --

Pros Cons
Pros
Cons

• Small catalyst particles

• High effectiveness factor

• Highly active catalysts

• Well-mixed liquid

• Nearly isothermal

• Lower power consumption

• High pressure operation

• Catalyst handling

• Catalyst fines carryover

• Catalyst loading limitations

• Homogeneous reactions

• Selectivity Control

• No guidelines for internals

• More complex scaleup

Bubble Column Bubble Column Reactors Reactors - - Pros and Cons - - Pros Cons •

Source:

P. L. Mills, R. V. Chaudhari, and P. A. Ramachandran

Reviews in Chemical Engineering (1993).

28

Draft

Draft Tube

Tube and

and Loop

Loop Reactors

Reactors

Draft Draft Tube Tube and and Loop Loop Reactors Reactors Internal Circulation External Circulation 29
Draft Draft Tube Tube and and Loop Loop Reactors Reactors Internal Circulation External Circulation 29
Internal Circulation
Internal Circulation

External Circulation

29

Venturi

Venturi Loop

Loop Reactors

Reactors

Venturi Venturi Loop Loop Reactors Reactors Cramers et al. (1994) 30

Cramers et al. (1994)

30

Example:

Example: DuPont

DuPont Butane

Butane toto THF

THF Process

Process

Example: DuPont Butane to to THF Process O O 2 O O n-C 4 Maleic anhydride
O O 2 O O n-C 4 Maleic anhydride H 2 O
O
O 2
O
O
n-C 4
Maleic anhydride
H 2 O

O

OH HO
OH
HO

O

H 2

O O 2 O O n-C 4 Maleic anhydride H 2 O O OH HO O
O O 2 O O n-C 4 Maleic anhydride H 2 O O OH HO O

O

Maleic acid

Tetrahydrofuran

Pilot Plant Reactor Ponca City, OK n-C 4 Oxidation Reactor Maleic acid Hydrogenation Purification Train $$
Pilot Plant Reactor
Ponca City, OK
n-C 4 Oxidation
Reactor
Maleic acid
Hydrogenation
Purification
Train
$$
Reactor
$
$$$$
Commercial Plant
Asturias, Spain
Example: DuPont Butane to to THF Process O O 2 O O n-C 4 Maleic anhydride

31

Other Types

Other

Types of

of Loop

Loop Reactors

Reactors

Other Types Other Types of of Loop Loop Reactors Reactors Internal Recirculation External Recirculation Jet Loop
Other Types Other Types of of Loop Loop Reactors Reactors Internal Recirculation External Recirculation Jet Loop

Internal

Recirculation

External

Recirculation

Jet Loop with

External Recirculation

32
32
Loop Recycle Jet Loop Reactors Jet Recycle Reactors
Loop Recycle
Jet Loop
Reactors
Jet
Recycle Reactors

Batch Operation

Loop Recycle Jet Loop Reactors Jet Recycle Reactors Batch Operation • Higher Productivity/ Continuous Operation Throughput

Higher Productivity/

Continuous Operation

Throughput

Lower Catalyst Consumption

Safer Operation

Higher Yields & Selectivity

Lower Power Consumption

Loop Recycle Jet Loop Reactors Jet Recycle Reactors Batch Operation • Higher Productivity/ Continuous Operation Throughput

Excellent mass & heat transfer performance Uniform catalyst distribution and mixing

Commercially used in hydrogenation, alkylation, oxidation, amination, carbonylation and bio-catalytic reactions

Source : Davy Process Technology

33

Gas--lift

Gas

lift and

and Loop

Loop Reactors

Reactors

-- Pros

Pros and

and Cons

Cons --

Pros Cons
Pros
Cons

• Small catalyst particles

• High effectiveness factor

• Highly active catalysts

• Well-mixed liquid

• Nearly isothermal

• High pressure operation

(Gas-lift reactor)

• Process flexibility

• Modular design

• Catalyst handling

• Catalyst fines carryover

• Catalyst loading limitations

• Homogeneous reactions

• Selectivity control

• Possible pressure limitations

(Loop reactor)

• Greater power consumption

(Loop reactor)

• Catalyst attrition

Gas - - lift Gas lift and and Loop Loop Reactors Reactors - - Pros and

Source:

P. L. Mills, R. V. Chaudhari, and P. A. Ramachandran

Reviews in Chemical Engineering (1993).

34

Fixed

Fixed--Bed

Bed Multiphase

Multiphase Reactors

Reactors

Fixed Fixed - - Bed Bed Multiphase Multiphase Reactors Reactors G GG L L L L

G

GG

Fixed Fixed - - Bed Bed Multiphase Multiphase Reactors Reactors G GG L L L L

L

Fixed Fixed - - Bed Bed Multiphase Multiphase Reactors Reactors G GG L L L L

L

Fixed Fixed - - Bed Bed Multiphase Multiphase Reactors Reactors G GG L L L L

L

Fixed Fixed - - Bed Bed Multiphase Multiphase Reactors Reactors G GG L L L L
Fixed Fixed - - Bed Bed Multiphase Multiphase Reactors Reactors G GG L L L L

L

Fixed Fixed - - Bed Bed Multiphase Multiphase Reactors Reactors G GG L L L L

L

G

Fixed Fixed - - Bed Bed Multiphase Multiphase Reactors Reactors G GG L L L L

G

Fixed Fixed - - Bed Bed Multiphase Multiphase Reactors Reactors G GG L L L L

L

Fixed Fixed - - Bed Bed Multiphase Multiphase Reactors Reactors G GG L L L L

G

(c) Packed - Bubble Flow

(a) Trickle - Bed

(b) Trickle - Bed

Cocurrent

downflow

Countercurrent

flow

Cocurrent

upflow

Fixed Fixed - - Bed Bed Multiphase Multiphase Reactors Reactors G GG L L L L

Trickle

Trickle Bed

Bed Reactors

Reactors

-- Advantages

Advantages --

Trickle Trickle Bed Bed Reactors Reactors - - Advantages - - • Plug flow of gas

• Plug flow of gas and liquid

• High catalyst / liquid ratio

• Stationary catalyst

• Minimal catalyst handling problems

• Operating mode flexibility

• High pressure operation

• Heat of reaction used to volatize liquid

• Large turndown ratio

• Low dissipated power

Lower capital and operating costs

36

Trickle

Trickle Bed

Bed Reactors

Reactors

-- Disadvantages

Disadvantages --

• Larger particles, low catalyst effectiveness

• Possible poor liquid - solid contacting

• High crushing strength required for small particles

• Potential for reactor runaway

• Long catalyst life required

• Inability to handle dirty feeds

• Potential for liquid maldistribution

• More difficult to scale - up

37
37

Packed Bubble

Packed

Bubble Flow

Flow Reactors

Reactors

-- Advantages

Advantages --

• Complete liquid - solid contacting

• Higher liquid holdup

• Better temperature control

• Less problems with liquid maldisdribution

• Higher heat and mass transfer rates

Packed Bubble

Packed

Bubble Flow

Flow Reactors

Reactors

-- Disadvantages

Disadvantages --

• Higher dissipated power than in TBR

• Throughput limited by bed fluidization velocity

• Increased potential for runaway

• Promotion of undesired homogeneous reactions

• Greater pressure drop

Bioreactor

Bioreactor Types

Types

(After Bailey and Ollis, 1986)

Bioreactor Bioreactor Types Types (After Bailey and Ollis, 1986) Mechanical agitation External pumping Gas agitation 40

Mechanical agitation

External pumping

Gas agitation

Bioreactor Bioreactor Types Types (After Bailey and Ollis, 1986) Mechanical agitation External pumping Gas agitation 40
Bioreactor Bioreactor Types Types (After Bailey and Ollis, 1986) Mechanical agitation External pumping Gas agitation 40
Bioreactor Bioreactor Types Types (After Bailey and Ollis, 1986) Mechanical agitation External pumping Gas agitation 40

40

Commercial or or Planned

Commercial

Planned Bioprocesses

Bioprocesses

High Volume

High

Volume Products

Products

Commercial or or Planned Commercial Planned Bioprocesses Bioprocesses High Volume High Volume Products Products Product Carbon

Product

Carbon source

Production, t/year

Lactic acid

corn syrup, whey permeate, agric. waste

300,000

Citric acid

molasses, glucose

550,000

Amino acids

molasses, glucose, corn syrup

250,000

lysine, glutamic acid Ethanol

molasses, corn syrup, cellulose, agric. waste 28,000,000 a

Single cell protein

methane

50,000 b

1,3 Propane diol

corn syrup

NA

Penicillin

glucose, corn steep liquor

25,000

Detergent enzymes c glucose, maltose, starch

a for fuels only (US production 14.5x10 6 t/year in 1996) b a target of 500,000 t/year is projected for Europe for 2010 c yearly product value in excess of 10 9 US$

Leib, Pereira & Villadsden, NASCRE 1, Houston 2001

Biological vsvs Chemical

Biological

Chemical Systems

Systems

vs vs Chemical Biological Systems • Tighter control on operating conditions is essential ( e.g.,

Tighter control on operating conditions is essential (e.g., pH, temperature, substrate and product concentrations, dissolved O 2 concentration)

Pathways can be turned on/off by the microorganism through expression of certain enzymes depending on the substrate and operating conditions, leading to a richness of behavior unparalleled in chemical systems.

The global stoichiometry changes with operating conditions and feed composition; Kinetics and stoichiometry obtained from steady-state (chemostat) data cannot be used reliably over a wide range of conditions unless fundamental models are employed

Long term adaptations (mutations) may occur in response to environment changes, that can alter completely the product distribution

Leib, Pereira & Villadsden, NASCRE 1, Houston 2001

42

Complex

Complex Reactor

Reactor example:

example: para

para--Amino

Amino Phenol

Phenol

NH OH p -Amino phenol 2 NH Aniline

NH 2

NH OH p -Amino phenol 2 NH Aniline
  • OH

p-Amino phenol

H 2

NH 2

NH OH p -Amino phenol 2 NH Aniline

Aniline

byby 44--Phase

Phase Hydrogenation

Hydrogenation

NO 2

Pt/C

H 2

NHOH

Hydrogenation Pt/C 2 NHOH

An intermediate used in the manufacture of several analgesic and antipyretic drugs, e.g., paracetamol, acetanilide, & phenacetin

Gas Aq. Phase Org. Phase PhNHOH PhNHOH PhNO 2 H + H 2 4-PhNH 2 (OH)
Gas
Aq. Phase
Org. Phase
PhNHOH
PhNHOH
PhNO 2
H +
H 2
4-PhNH 2 (OH)
H 2
phase
4-PhNH 3 + (OH)
+
PhNH 2
PhNH 2
PhNH
PhNH
Pt/C
H +
H +
H +
3 3
+
Complex Complex Reactor Reactor example: example: para para - - Amino Amino Phenol Phenol NH OH

Phenyl hydroxyl

amine

Single step process

Intermediate phenylhydroxylamine

rearranged by interfacial reaction to para-aminophenol

Selectivity determined by competing hydrogenation in organic phase and & interfacial rearrangement with aqueous acid catalyst

R.V. Chaudhari et al., CES, 56, 1299, 2001

43

P. L. Mills, CAMURE-5, June 2005

Complex

Complex Reactor:

Reactor: Example

Example 22

Phenyl

Phenyl Acetic

Acetic Acid

Acid byby 33--Phase

Phase Hydroformylation

Hydroformylation

Complex Reactor: Example 2 2 Phenyl Acetic Acid by by 3 3 - - Phase Hydroformylation

Gas--Liquid

Gas

Liquid--Liquid

Liquid w/Soluble

w/Soluble Catalyst

Catalyst

OH

O
O

Phenyl acetic acid

2 Cl CO/H
2
Cl CO/H

Pd-Catalyst

Benzyl chloride

CO H 2 A g B g Gas - Organic Phase Interface CHO Products Reactant CHO
CO
H 2
A g
B g
Gas - Organic
Phase Interface
CHO
Products
Reactant
CHO
Aqueous-
A
B
E
P
or
or
or
or
Organic Phase
Interface
A
B
E
P
aq
aq
aq
aq
SO 3 Na
SO 3 Na
H
OC
P
NaO 3 S
NaO 3 S
SO 3 Na
Rh
P
P
NaO 3 S
Wan & Davis, 1993
SO 3 Na
SO 3 Na
Rh/TPPTS Catalyst
SO 3 Na

Gas Phase

Organic Phase

Aqueous Phase

Soluble catalyst

44

Electrochemical Reactors

• Electrolytic production of chlorine and

NaOH; Chloralkali industry.

• Aluminum production (Halls process)

• Fuel cells

• Monsanto adiponitrile process

• Paired electrosynthesis

• Pollution prevention; Metal recovery

Strategies for

Strategies

for Multiphase

Multiphase Reactor

Reactor Selection

Selection

Strategies for Strategies for Multiphase Multiphase Reactor Reactor Selection Selection ) Reactants Process Requirements Reactor ?

)

Reactants

Process

Requirements

Reactor ?
Reactor ?
“Wish List” • Maximize yield • Ease of scale-up • High throughput • Low pressure drop
“Wish List”
• Maximize yield
• Ease of scale-up
• High throughput
• Low pressure drop
• Lowest Capital cost
• Other requirements
  • Desired Products

  • Undesired Products

  • Unconverted Reactants Environmental

Strategies for Strategies for Multiphase Multiphase Reactor Reactor Selection Selection ) Reactants Process Requirements Reactor ?

and Safety

• Intrinsically safe • “Green” processing • Zero emissions • Sustainable
• Intrinsically safe
• “Green” processing
• Zero emissions
• Sustainable

46

Summary:

Summary: Distinguishing

Distinguishing Features

Features

of

of Multiphase

Multiphase Reactors

Reactors

Summary: Summary: Distinguishing Distinguishing Features Features of of Multiphase Multiphase Reactors Reactors • Efficient contacting of

Efficient contacting of reactive phases and

separation of product phases is key to safety,

operability and performance

Various flow regimes exist, depending on phase

flow rates, phase properties, operating conditions,

and geometry

Reaction and interphase transport time-scales, and

phase flow patterns dictate reactor type, geometry

and scale

Gradual scale-up over several scales may be

required for reliable commercialization

Three--Level

Three

Level Strategy

Strategy for

for Reactor

Reactor Selection

Selection

Three - - Level Three Level Strategy Strategy for for Reactor Reactor Selection Selection Level Level
Level Level I I Catalyst Design Level II Reactant & Energy Injection Strategies Level III Hydrodynamic
Level
Level
I
I
Catalyst Design
Level
II
Reactant
& Energy
Injection
Strategies
Level
III
Hydrodynamic
Flow Regimes

Analyze process on three levels Make decisions on each level

Use fundamentals, data,

Three - - Level Three Level Strategy Strategy for for Reactor Reactor Selection Selection Level Level

& basic models for screening of various reactor alternatives

48

Multiphase

Multiphase Transport

Transport--Kinetic

Kinetic Interactions

Interactions

Multiphase Multiphase Transport Transport - - Kinetic Kinetic Interactions Interactions Time & Length Scales Reactor Eddy

Time & Length Scales

Reactor Eddy or Particle Molecular I Phase I, Q I in Phase I, Q I I
Reactor
Eddy or Particle
Molecular
I
Phase I, Q
I
in
Phase I, Q
I
I
I
I
I
I
e
I
I
= η
I
L
( C
)
R ( C
,T
)
Phase I
T
, C
, P
b
b
b
I
I
I
0
0
0
T
, C , P
I
I
I
I
I
I
L
( T
)
=
(
Δ
H
)
η
R ( C
,T
)
h
b
I
j
j
b
b
R
j
j
I
η =
f (kinetics & transport ) in Phase I
j
II
II
II
II
II
II
L
( C
)
= η
R
( C
,T
)
Phase II
b
b
b
II
II
II
II
II
II
L ( T
)
=
(
Δ
H
)
η
R
( C
,T
)
h
b
II
j
j
b
b
R
j
j
II
II
II
η =
g (kinetics & transport ) in Phase II
Phase II, Q
Phase II, Q
j
e
in
II
II
II
T
, C
, P
II
II
II
T
, C
, P
0
0
0

Reactor Performance Determines Raw Material Utilization, Separations, Recycle Streams, Remediation, and Hence Process Economics & Profitability