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BASIC DESIGN EQUATIONS

FOR MULTIPHASE
REACTORS

Starting Reference
1. P. A. Ramachandran and R. V. Chaudhari, ThreePhase Catalytic Reactors, Gordon and Breach
Publishers, New York, (1983).
2. Nigam, K.D.P. and Schumpe, A., “Three-phase
sparged reactors”, Topics in chemical engineering, 8,
11-112, 679-739, (1996)
3. Trambouze, P., H. Van Landeghem, J.-P. Wauquier,
“Chemical Reactors: Design, Engineering, Operation”,
Technip, (2004)

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Objectives
1. Review microkinetic and macrokinetic processes that
occur in soluble and solid-catalyzed systems.
2. Review ideal flow patterns for homogeneous systems
as a precursor for application to multiphase systems.
3. Derive basic reactor performance equations using ideal
flow patterns for the various phases.
4. Introduce non-ideal fluid mixing models.
5. Illustrate concepts through use of case studies.

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Types of Multiphase Reactions Reaction Type Degree of Difficulty • Gas-liquid without catalyst Straightforward • Gas-liquid with soluble catalyst • Gas-liquid with solid catalyst • Gas-liquid-liquid with soluble or solid catalyst • Gas-liquid-liquid with soluble or solid catalyst (two liquid phases) Complex 4 .

Hierarchy of Multiphase Reactor Models Model Type Empirical Implementation Insight Straightforward Very little Ideal Flow Patterns Phenomenological Volume-Averaged Conservation Laws Pointwise Conservation Very Difficult or Impossible Laws Significant 5 .

Macrokinetic Processes in Slurry Reactors Hydrodynamics of the multi-phase dispersion .PDF’s of the various phases Fluid micromixing . fluid-fluid interactions.Fluid and particle specific interfacial areas . stirrers. fluid-to-internal coils. etc.…) 6 .Fluid-to-wall. Energy dissipation .Bubble coalescence & breakage .Catalyst particle agglomeration & attrition Reactor Model Heat transfer phenomena .Fluid holdups & holdup distribution .Liquid evaporation & condensation .Power input from variouis sources (e..Bubble size & catalyst size distributions Fluid macromixing .g.

fluid-fluid interactions.Fluid distribution Fluid macromixing .Macrokinetic Processes in Fixed-Bed Reactors Hydrodynamics of the multi-phase flows . etc. stirrers. fluid-to-internal coils.Pressure drop (e..…) 7 .g.Liquid evaporation & condensation .Fluid-to-wall.Fluid-fluid & fluid-particle specific interfacial areas . Energy dissipation .Flow regimes & pressure drop .Fluid holdups & holdup distribution .PDF’s of the various phases Reactor Model Heat transfer phenomena .

and solids • Interparticle and interphase mass transfer • Hydrodynamics of the gas. liquid. liquid.liquid mass transfer Macro or Global Analysis • Liquid . and solids • Intraparticle and intraphase diffusion • Macro distributions of the gas.Elements of the Reactor Model Micro or Local Analysis • Gas .solid mass transfer • Flow patterns for the gas. liquid and solid • Intraparticle and intraphase heat transfer • Heat exchange • Catalyst particle wetting • Other types of transport phenomena 8 .

Reactor Design Variables Feed Qin Tin Cin Qout Tout Product Cout Reactor Reactor =f Performance Process Variables Rates • Conversion • Flow rates • Kinetics • Selectivity • Inlet C & T • Activity Reaction Flow Patterns • Macro • Transport • Micro • Heat exchange 9 .

Backmixed Flow 10 .Ideal Flow Patterns for Single-Phase Systems Q (m3/s) Q (m3/s) a. Plug-Flow Q (m3/s) Q (m3/s) b.

of the residence time distribution  Tracer mass balance requirement: MT  Q  y(t) dt o 11 .F.D.Impulse Tracer Response x(t) MT t y(t) t Q (m3/s) t Q (m3/s) y(t) dt E(t ) dt   MT / Q Reactor System Fraction of the outflow with a residence time between t and t + dt E(t) is the P.

Plug Flow Q (m3/s) 12 .Fluid-Phase Mixing: Single Phase.

Backmixed Q (m3/s) Mi = Mass of tracer injected (kmol) 13 .Fluid-Phase Mixing: Single Phase.

bed Gas-Lift & Loop Backmixed 14 .Idealized Mixing Models for Multiphase Reactors Model Gas-Phase Liquid Phase Solid-Phase Reactor Type Plug-flow Fixed Trickle-Bed Flooded-Bed 1 Plug-flow 2 Backmixed Backmixed Backmixed Mechanically agitated 3 Plug-Flow Backmixed Bubble column Ebullated .

Ideal Flow Patterns in Multiphase Reactors Example: Mechanically Agitated Reactors (t-g) EG(t) (t) QG XL(t) QL 0 H XG(t) or L L t QL 1 = G + L + C Vr G QG -t/ e EL(t) QG VR = vG + VL + VC G  t t (t) 0 g 0 L  Vr (1   G   L ) QL 0 t 15 .

1 mobile phases: V1 + 1 = K1j  C j  =    C1  equil.First Absolute Moment of the Tracer Response for Multiphase Systems For a single mobile phase in contact with p stagnant phases: V1 + 1 = p  K1j Vj j=2 Q1 For p mobile phases in contact with p . Q1 + p  K1j Vj j= 2 p  K 1j Qj j= 2 is the partition coefficient of the tracer between phase 1 and j 16 .

the PDF of sojourn times in the reaction environment can be obtained from the exit-age PDF for a non-adsorbing tracer that remains confined to the flowing phase external to other phases present in the system.Relating the PDF to Reactor Performance “For any system where the covariance of sojourn times is zero (i.” For a first-order process:  .e.H (k ) t p c 1 .XA =  e Hp(kc) = pdf for the stagnant phase 0  = e 0 Eext ( t ) dt ..(k W W / Q1 ) t Eext ( t ) dt 17 . when the tracer leaves and re-enters the flowing stream at the same spatial position).

Illustrations of Ideal-Mixing Models for Multiphase Reactors Stirred tank Trickle .Bed              z       G   L • Plug-flow of gas • Backmixed liquid & catalyst • Batch catalyst • Catalyst is fully wetted G L • Plug-flow of gas • Plug-flow of liquid • Fixed-bed of catalyst 18 • Catalyst is fully wetted .Bed Bubble Column        z Flooded .

Intrinsic Reaction Rates Reaction Scheme: A (g) + vB (l)  (l) C 19 .

First-order reaction wrt dissolved gas 3. Isothermal operation 6. Constant gas-phase concentration z 4. and intraparticle gradients G L 20 . Liquid is nonvolatile 7. Catalyst concentration is constant 8.Gas Limiting and Plug-Flow of Liquid Key Assumptions 1. Finite gas-liquid. liquid-solid. Gaseous reactant is limiting 2. Plug-flow of liquid 5.

Concentration or Axial Height Gas Limiting and Plug flow of liquid Constant gas phase concentration  valid for pure gas at high flow rate Relative distance from catalyst particle (Net input (Input by Gas.= 0 + by Liquid solid Transport) convection) Transport) Ql Al z  Ql Al  (1)  *  k a A  Al Ar dz.(Loss by Liquid.k s a p  Al  As  Ar dz= 0 l B z  dz (2) Dividing by Ar.dz and taking limit dz   (3) (4) 21 ..

Gas Limiting and Plug flow of liquid 22 .

Gas Limiting and Plug flow of liquid Solving the Model Equations 23 .

Concept of Reactor Efficiency  R Rate of rxn in the Entire Reactor with Transport Effects Maximum Possible Rate 24 .

Conversion of Reactant B (in terms of Reactor Efficiency) 25 .

liquid-solid.Gas Limiting and Backmixed Liquid Key Assumptions Stirred Tank Bubble Column 1. Finite gas-liquid. Liquid and catalyst are backmixed            G 5. Gaseous reactant is limiting        z 2. Isothermal operation    L 6. First-order reaction wrt dissolved gas        3. Liquid is nonvolatile 7. Catalyst concentration is constant 8. Constant gas-phase concentration 4. and intraparticle gradients 26 .

0 oncentration of liquid reactant in the liquid bulk is constant [≠f(z)] [=B A in liquid bulk: Analysis is similar to the previous case 27 .Concentration or Axial Height Gas Limiting and Backmixed Liquid Relative distance from catalyst particle oncentration of dissolved gas in the liquid bulk is constant [≠f(z)] [=Al.

Gas Limiting and Backmixed Liquid A at the catalyst surface: For Reactant B: (Net input = by flow) (Rate of rxn of B at the catalyst surface) (Note: No transport to gas since B is nonvolatile) 28 .

Gas Limiting and Backmixed Liquid Solving the Model Equations 29 .

Fixed beds. packed bubble columns B . ebullated beds 30 . Semi-batch slurries. Trickle-beds. fluidized-beds.Single phase flow of gas or liquid with exchange between a partially backmixed stagnant phase.Flow Patterns Concepts for Multiphase Systems A B A .Single phase flow of gas or liquid with exchange between the mobile phase and stagnant phase.

Flow Patterns Concepts for Multiphase Systems C D C. D . Empty bubble columns and fluidized beds 31 .Cocurrent or E countercurrent two-phase flow with exchange between the phases and stagnant phase. one of which has strong internal recirculation. packed or empty bubble columns E . Trickle-beds.Exchange between two flowing phases.

Axial Dispersion Model (Single Phase) C  2C C  Dax u R 2 t z dz @z=0 Let u0C0  uC  Dax z η L uL Peax  Dax C z Basis: Plug flow with superimposed “diffusional” transport in the direction of flow @z=L C 0 z @  = 1 C 0 η L τ u C 1  2C C τ    τR 2 t Peax η dη @  = 0 1 C C0  C  Peax η 32 .