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Module 1
Introduction to Heterogeneous Reactors
and Application Areas
P.A. Ramachandran
rama@wustl.edu
1
Topical Outline
Introduction
Kinetic models
Transport effects
Gas-solid reactions
Gas-liquid reactions
Three Phase Reactors
Biochemical reactors
Electrochemical reactors
2
Course Objectives
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.
3
Module 1 Outline
Industrial Applications and Examples
Review of Common Reactor Types
Guidelines for Reactor Selection
Starting References
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).
Products
Catalyst
Present
Gases
Homogeneous
Gases
Liquids
Heterogeneous
Liquids
Solids
Enzyme
Solids
Solvent
Bacteria
Solvent
Cells
Future
Gas-Solid Catalytic
Gas-Solid Non-Catalytic
Gas-Liquid
Gas-Liquid Solid Catalytic
Gas-Liquid with Solid Reacting
Liquid-Liquid
Gas-Liquid-Liquid-Solid
7
Some Examples of
Multiphase Catalytic Processes
Other Emerging
Multiphase Catalytic Technologies
Aldehydes, Alcohols,
Amines, Acids, Esters,
LABs, Inorg Acids, ...
Value of Shipments
in $US billions
450
Bulk
Chemicals
Petroleum
Refining
Polymer
Manufacture
350
250
150
1987
1989
1991
1993
1995
1997
Polycarbonates,
PPO, Polyolefins,
Specialty plastics
http://www.eia.doe.gov/
Fine Chemicals
& Pharmaceuticals
Ag Chem, Dyes,
Fragrances, Flavors,
Nutraceuticals,...
Environmental
Remediation
P. L. Mills
NASCRE 1,
Houston, Jan 2001
De-NOx, De-SOx,
HCFCs, DPA,
Green Processes ..
Balance
10%
Japan
13%
European Union
35%
Asia
15%
CS&E
CR&D Chemical Sciences & Engineering
P. L. Mills
USA
27%
11
Small
Scale
Product
< 10 MM lb/yr
Large
Scale
Product
30
20
10
13
14
CH3
O2
CH3
cat I
O2
cat I
cat I
CH3 O2
H2
p-xylene
cat II
4-CBA COOH
COOH
TPA
CH3
COOH
4-CT
CHO
COOH 4-CT
Oxidation:
Cat I: Co-Mn-Br
Temp.: 190-205C
PO2: 1.5-3.0 MPa
Hydrogenation:
Cat II: Pd/support
Temp.: 225-275C
Soluble catalysts
&
Powdered catalysts
Loop reactors
Packed columns
Trickle-beds
Packed bubble columns
Soluble catalysts
&
Tableted catalysts
Ebullated-bed reactors
16
Classification of Multiphase
Gas-Liquid-Solid Catalyzed Reactors
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.
17
18
Packed bed
Fluid bed
Monolith
Riser and Downer
19
Middleton (1992)
20
Gas
(a) Batch
Dead - Headed
L
G
G
G
Cons
Catalyst handling
Catalyst fines carryover
Catalyst loading limitations
Homogeneous reactions
Pressure limitations
Temp. control (hot catalysts)
Greater power consumption
Large vapor space
23
Catalyst deposition
in low turbulence area
Easy catalyst
recycling
Negligible fouling
Inefficient cooling
G
Sealing problems
Conventional Reactor
BIAZZI Reactor
24
,-unsaturated
OH
Carbol
ketone
25
Tarhan (1983)
26
(a) Empty
Semi - Batch
or Continuous
(b) Plate
Continuous
(c) Packed
Semi - Batch
or Continuous
27
Cons
Catalyst handling
Well-mixed liquid
Homogeneous reactions
Nearly isothermal
Selectivity Control
28
Internal Circulation
External Circulation
29
30
O2
H2
O
O
O
n-C4
Maleic anhydride
OH HO
Maleic acid
n-C4 Oxidation
Reactor
Tetrahydrofuran
Maleic acid
Hydrogenation
$$ Reactor $
Purification
Train
$$$$
Commercial Plant
Asturias, Spain
31
Internal
Recirculation
External
Recirculation
Higher Productivity/
Throughput
Continuous Operation
Lower Catalyst
Consumption
Safer Operation
Higher Yields &
Selectivity
Lower Power
Consumption
33
Cons
Catalyst handling
Catalyst fines carryover
Catalyst loading limitations
Homogeneous reactions
Selectivity control
Possible pressure limitations
(Loop reactor)
Greater power consumption
(Loop reactor)
Catalyst attrition
34
G
L
L
35
36
Bioreactor Types
(After Bailey and Ollis, 1986)
Mechanical agitation
External pumping
Gas agitation
40
Carbon source
Lactic acid
corn syrup, whey permeate, agric. waste
Citric acid
molasses, glucose
Amino acids
molasses, glucose, corn syrup
lysine, glutamic acid
Ethanol
molasses, corn syrup, cellulose, agric. waste
Single cell protein methane
1,3 Propane diol
corn syrup
Penicillin
glucose, corn steep liquor
Detergent enzymesc glucose, maltose, starch
Production, t/year
300,000
550,000
250,000
28,000,000a
50,000b
NA
25,000
42
NH2
NHOH
NO2
H+
OH
Pt/C
H2
H2
Gas
phase
H2
4-PhNH3+(OH)
H+
4-PhNH2(OH)
H+
PhNO2
PhNHOH
NH2
Phenyl hydroxyl
amine
PhNH3+
Aniline
H+
PhNH2
H2
p-Amino phenol
PhNHOH
Pt/C
Org. Phase
PhNH2
Intermediate phenylhydroxylamine
rearranged by interfacial reaction to
para-aminophenol
Aq. Phase
Selectivity determined by competing
hydrogenation in organic phase and
& interfacial rearrangement with
aqueous acid catalyst
R.V. Chaudhari et al., CES, 56, 1299, 2001
P. L. Mills, CAMURE-5, June 2005
43
Cl
OH
CO/H2
Pd-Catalyst
Benzyl chloride
Gas - Organic
Phase Interface
CO H2
Ag Bg
Gas Phase
CHO
Products
Reactant
AqueousOrganic Phase
Interface
CHO
Aor Bor
Eor
Por
Aaq Baq
Eaq
Paq
Organic Phase
SO 3Na
SO 3Na
H
OC
NaO 3 S
P
NaO 3 S
Aqueous Phase
SO 3Na
Rh
SO 3Na
NaO 3S
SO 3Na
Rh/TPPTS Catalyst
SO 3 Na
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
45
Desired Products
Reactants
Reactor ?
Undesired Products
Unconverted Reactants
Process
Requirements
Wish List
Maximize yield
Ease of scale-up
High throughput
Low pressure drop
Lowest Capital cost
Other requirements
Environmental
and Safety
Intrinsically safe
Green processing
Zero emissions
Sustainable
46
Catalyst Design
Level
II
Reactant
& Energy
Injection
Strategies
Level
III
Hydrodynamic
Flow Regimes
L ( C ) = R ( C ,T )
I
T0I , C 0 , P0I
I
b
( H
LIh ( T b ) =
I
I
b
Phase I
I
b
) Ij R Ij ( C b ,TbI )
I
R Ij
Phase I, QeI
I
T I ,C , PI
LII ( C b ) = II R ( C b ,TbII )
II
LIIh ( T b ) =
II
II
( H
Phase II, Q
II
T0II , C 0 , P0II
Phase II
R IIj
II
in
II
T II , C , P II