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INTERNAL DIFFUSION EFFECTS INTERNAL DIFFUSION EFFECTS (8) (8) Marcel Lacroix Marcel Lacroix Universit Universit é é de Sherbrooke de Sherbrooke

INTERNAL DIFFUSION EFFECTS (8) Marcel Lacroix Université ...marcellacroix.espaceweb.usherbrooke.ca/CRE/lecture... · internal diffusion effects: introduction • in a heterogeneous

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  • INTERNAL DIFFUSION EFFECTSINTERNAL DIFFUSION EFFECTS(8)(8)

    Marcel LacroixMarcel LacroixUniversitUniversitéé de Sherbrookede Sherbrooke

  • INTERNAL DIFFUSION EFFECTS:INTERNAL DIFFUSION EFFECTS:INTRODUCTIONINTRODUCTION

    • IN A HETEROGENEOUS REACTION SEQUENCE, MASS TRANSFER OF REACTANTS FIRST TAKES PLACE FROM THE BULK FLUID TO THE EXTERNAL SURFACE OF THE PELLET. THE REACTANTS THEN DIFFUSE FROM THE EXTERNAL SURFACE INTO AND THROUGH THE PORES WITHIN THE PELLET, WITH REACTION TAKING PLACE ONLY ON THE CATALYTIC SURFACE OF THE PORES.

    M. Lacroix Internal Diffusion Effects 2

  • INTERNAL DIFFUSION EFFECTS:INTERNAL DIFFUSION EFFECTS:INTRODUCTIONINTRODUCTION

    • IN THE PREVIOUS DISCUSSION OF SURFACE REACTIONS, WE ASSUMED THAT EACH POINT IN THE INTERIOR OF THE ENTIRE CATALYST SURFACE WAS ACCESSIBLE TO THE SAME REACTANT CONCENTRATION.

    • HOWEVER, WHERE THE REACTANTS DIFFUSE INTO THE PORES WITHIN THE CATALYST PELLET, THE CONCENTRATION AT THE PORE MOUTH WILL BE HIGHER THAN THAT INSIDE THE PORE, AND WE SEE THAT THE ENTIRE CATALYTIC SURFACE IS NOT ACCESSIBLE TO THE SAME CONCENTRATION.

    M. Lacroix Internal Diffusion Effects 3

  • INTERNAL DIFFUSION EFFECTS:INTERNAL DIFFUSION EFFECTS:OBJECTIVEOBJECTIVE

    • TO EXAMINE THE EFFECTS OF DIFFUSION OF THE REACTANTS INTO THE PORES WITHIN THE CATALYST PELLET ON THE OVERALL RATE OF REACTION.

    M. Lacroix Internal Diffusion Effects 4

  • DIFFUSION AND REACTION IN SPHERICAL PELLETS:DIFFUSION AND REACTION IN SPHERICAL PELLETS:MOLE BALANCE EQUATIONMOLE BALANCE EQUATION

    • STEADY-STATE MOLE BALANCE ON SPECIES A AS IT ENTERS, LEAVES AND REACTS IN A SPHERICAL SHELL OF INNER RADIUS

    AND OUTER RADIUS OF THE PELLET:rr ∆+r

    ( ) ( ) ( ) 0___ =+− ∆∆+ rrrr generatedAoutAinAM. Lacroix Internal Diffusion Effects 5

  • DIFFUSION AND REACTION IN SPHERICAL PELLETS:DIFFUSION AND REACTION IN SPHERICAL PELLETS:MOLE BALANCE EQUATIONMOLE BALANCE EQUATION

    • SUBSTITUTION IN THE MOLE BALANCE EQUATION

    YIELDS:

    ( ) 24_ rArr rWinA π⋅=( ) 24_ rrArrr rWoutA ∆+∆+ ⋅= π

    ( ) rrrgeneratedA mcAr ∆=∆ 2' 4_ πρ

    0)( 2'2

    =− rrdr

    rWdcA

    Ar ρ

    RATE OF REACTION PER MASS OF CATALYST (mole/s kg cat.)

    DENSITY OF CATALYST (kg/m3)

    M. Lacroix Internal Diffusion Effects 6

  • DIFFUSION AND REACTION IN SPHERICAL PELLETS:DIFFUSION AND REACTION IN SPHERICAL PELLETS:MOLE BALANCE EQUATIONMOLE BALANCE EQUATION

    • MOREOVER,

    AND

    • :EFFECTIVE DIFFUSIVITY (m2/s)• :RATE OF REACTION PER UNIT SURFACE AREA OF

    CATALYST (mole/s m2)• :SURFACE AREA OF THE CATALYST PER UNIT MASS OF

    CATALYST (m2/g cat.). TYPICAL VALUE: 150 m2/g cat. • :n-ORDER SPECIFIC REACTION RATE CONSTANT

    (m3/mole)n-1(m/s)

    drdCDW AeAr −= a

    nAnaAA SCkSrr =−=−

    '''

    eD''

    Ar

    aS

    nk

    M. Lacroix Internal Diffusion Effects 7

  • DIFFUSION AND REACTION IN SPHERICAL PELLETS:DIFFUSION AND REACTION IN SPHERICAL PELLETS:DIFFERENTIAL EQUATION DIFFERENTIAL EQUATION

    • THUS, THE DIFFERENTIAL EQUATION DESCRIBING DIFFUSION AND REACTION WITHIN A SPHERICAL PELLET BECOMES:

    WITH

    • USING THE DIMENSIONLESS VARIABLES AND, IT BECOMES

    WHERE

    0222

    =−+ nAe

    canAA CDSk

    drdC

    rdrCd ρ ( )

    ( ) AsRrArA

    CCfiniteC

    =

    =

    =

    = ;0

    02 222

    =−+ nndd

    dd ϕφ

    λϕ

    λλϕ

    AsA CC /=ϕRr /=λ

    e

    nAscan

    n DCRSk 122 −= ρφ

    M. Lacroix Internal Diffusion Effects 8

  • DIFFUSION AND REACTION IN SPHERICAL PELLETS:DIFFUSION AND REACTION IN SPHERICAL PELLETS:THIELE MODULUSTHIELE MODULUS

    • IS THE THIELE MODULUS.

    • IS A MEASURE OF THE RATIO OF A SURFACE REACTION RATE TO A RATE OF DIFFUSION THROUGH THE CATALYST PELLET.

    • WHEN THE THIELE MODULUS IS LARGE, INTERNAL DIFFUSION USUALLY LIMITS THE OVERALL RATE OF REACTION; WHEN IT IS SMALL, THE SURFACE REACTION IS USUALLY RATE-LIMITING.

    e

    nAscan

    n DCRSk 122 −= ρφ

    2nφ

    M. Lacroix Internal Diffusion Effects 9

  • REACTION RATES: REMINDERREACTION RATES: REMINDER

    • : RATE OF REACTION PER UNIT VOLUME (mole/m3s)

    • : RATE OF REACTION PER UNIT MASS OF CATALYST (mole/g cat. s)

    • : RATE OF REACTION PER UNIT SURFACE AREA OF CATALYST (mole/m2 s)

    • : SURFACE AREA OF THE CATALYST PER UNIT MASS OF CATALYST (m2/g cat.). TYPICAL VALUE: 150 m2/g cat.

    • THUS, AND FOR FIRST-ORDER REACTION,

    ''Ar

    aS

    'Ar

    Ar

    aAA Srr''' −=−

    AA Ckr 1'' =− k1 :specific reaction rate constant (m/s)

    M. Lacroix Internal Diffusion Effects 10

  • DIFFUSION AND REACTION IN SPHERICAL PELLETS:DIFFUSION AND REACTION IN SPHERICAL PELLETS:SOLUTION FOR A FIRSTSOLUTION FOR A FIRST--ORDER REACTION (ORDER REACTION (n=1n=1))

    • THE SOLUTION TO THE DIFFERENTIAL EQUATION IS

    WITHe

    can

    DRSk 22

    1ρφ =⎟

    ⎞⎜⎝

    ⎛==

    )sinh()sinh(1

    1

    1

    φλφ

    λϕ

    As

    A

    CC

    SMALL VALUES OF THE THIELE MODULUS INDICATE SURFACE REACTION CONTROLS AND A SIGNIFICANT AMOUNT OF THE REACTANT DIFFUSES WELL INTO THE PELLET INTERIOR WITHOUT REACTING. LARGE VALUES OF THE THIELE MODULUS INDICATE THAT THE SURFACE REACTION IS RAPID AND THAT THE REACTANT IS CONSUMED VERY CLOSE TO THE EXTERNAL PELLET SURFACE AND VERY LITTLE PENETRATES INTO THE INTERIOR OF THE PELLET.

    M. Lacroix Internal Diffusion Effects 11

  • DIFFUSION AND REACTION IN SPHERICAL PELLETS:DIFFUSION AND REACTION IN SPHERICAL PELLETS:INTERNAL EFFECTIVENESS FACTORINTERNAL EFFECTIVENESS FACTOR

    • THE INTERNAL EFFECTIVENESS FACTOR IS THE RATIO OF THE ACTUAL OVERALL RATE OF REACTION TO THE RATE OF REACTION THAT WOULD RESULT IF THE ENTIRE INTERIOR SURFACE WERE EXPOSED TO THE EXTERNAL PELLET SURFACE CONDITIONS CAs AND Ts

    • TO DERIVE THE EFFECTIVENESS FACTOR FOR A FIRST-ORDER REACTION, LET US WORK WITH REACTION RATES IN MOLES PER UNIT TIME:

    ''

    ''

    '

    '

    As

    A

    As

    A

    As

    A

    rr

    rr

    rr

    −−

    =−−

    =−−

    η

    As

    A

    As

    A

    As

    A

    MM

    catalystmassrcatalystmassr

    rr

    =⋅−⋅−

    =−−

    =)_()_(

    '

    '

    '

    '

    η

    )10(

  • DIFFUSION AND REACTION IN SPHERICAL PELLETS:DIFFUSION AND REACTION IN SPHERICAL PELLETS:INTERNAL EFFECTIVENESS FACTORINTERNAL EFFECTIVENESS FACTOR

    • IF THE ENTIRE SURFACE WERE EXPOSED TO THE CONCENTRATION AT THE EXTERNAL SURFACE OF THE PELLET, CAs THE RATE FOR A FIRST-ORDER REACTION WOULD BE:

    • THE ACTUAL RATE OF REACTION IS THE RATE AT WHICH THE REACTANT DIFFUSES INTO THE PELLET AT THE OUTER SURFACE:

    • THUS, THE FFECTIVENESS IS

    caAscAsAs RSCkRrM ρπρπ3

    13'

    34

    34

    ⋅=⋅−=

    )1)coth((4)1(4 11 −=== φφπλλϕπ AseAseA CRDd

    dCRDM

    THE SUBSCRIPT s INDICATES THAT THE RATE IS EVALUATED AT THE CONDITIONS PRESENT AT THE EXTERNAL SURFACE OF THE PELLET.

    )1)coth((3 1121

    −== φφφ

    ηAs

    A

    MM

    (8.1)

    M. Lacroix Internal Diffusion Effects 13

  • DIFFUSION AND REACTION IN SPHERICAL PELLETS:DIFFUSION AND REACTION IN SPHERICAL PELLETS:RATE OF REACTIONRATE OF REACTION

    • FOR ,

    • AND FOR A FIRST-ORDER REACTION,

    • THUS TO INCREASE THE RATE OF REACTION, (1) DECREASE THE RADIUS R; (2) INCREASE THE TEMPERATURE; (3) INCREASE THE CONCENTRATION; AND (4) INCREASE THE INTERNAL SURFACE AREA.

    21

    1112

    1

    33)1(3 ⎟⎟⎠

    ⎞⎜⎜⎝

    ⎛=≈−≈

    ca

    e

    SkD

    R ρφφ

    φη

    21 >φ

    Asc

    aeaAsAsA C

    kSDR

    SCkrr2

    1

    11

    '' 3))(()( ⎟⎟⎠

    ⎞⎜⎜⎝

    ⎛==−=−

    ρηη

    M. Lacroix Internal Diffusion Effects 14

  • DIFFUSION AND REACTION IN SPHERICAL PELLETS:DIFFUSION AND REACTION IN SPHERICAL PELLETS:INTERNAL EFFECTIVENESS FACTOR INTERNAL EFFECTIVENESS FACTOR

    AS THE PARTICLE DIAMETER BECOMES VERY SMALL, THE THIELE MODULUS DECREASES, SO THAT THE EFFECTIVENESS FACTOR APPROACHES 1 AND THE REACTION IS SURFACE-REACTION-LIMITED. ON THE OTHER HAND, WHEN THE THIELE MODULUS IS LARGE (>30), THE INTERNAL EFFECTIVENESS FACTOR IS SMALL AND THE REACTION IS DIFFUSION-LIMITED WITHIN THE PELLET.

    M. Lacroix Internal Diffusion Effects 15

  • DIFFUSION AND REACTION IN SPHERICAL PELLETS:DIFFUSION AND REACTION IN SPHERICAL PELLETS:OVERALL EFFECTIVENESS FACTOROVERALL EFFECTIVENESS FACTOR

    • WE NOW CONSIDER A SITUATION WHERE EXTERNAL AND INTERNAL RESISTANCE TO MASS TRANSFER TO AND WITHIN THE PELLET ARE OF THE SAME ORDER OF MAGNITUDE.

    M. Lacroix Internal Diffusion Effects 16

  • DIFFUSION AND REACTION IN SPHERICAL PELLETS:DIFFUSION AND REACTION IN SPHERICAL PELLETS:OVERALL EFFECTIVENESS FACTOROVERALL EFFECTIVENESS FACTOR

    • AT STEADY-STATE, THE TRANSPORT OF THE REACTANT(S) FROM THE BULK FLUID TO THE EXTERNAL SURFACE OF THE CATALYST IS EQUAL TO THE NET RATE OF REACTION OF THE REACTANT WITHIN THE PELLET.

    • THE MOLAR RATE OF MASS TRANSFER FROM THE BULK FLUID TO THE EXTERNAL SURFACE IS

    VaWM cAA ∆⋅=

    MOLAR FLUX (mole/m2s)

    SURFACE AREA PER UNIT REACTOR VOLUME

    REACTOR VOLUME

    (8.2)

    M. Lacroix Internal Diffusion Effects 17

  • DIFFUSION AND REACTION IN SPHERICAL PELLETS:DIFFUSION AND REACTION IN SPHERICAL PELLETS:OVERALL EFFECTIVENESS FACTOROVERALL EFFECTIVENESS FACTOR

    • THE NET (TOTAL) RATE OF REACTION ON AND WITHIN THE PELLET IS:

    • COMBINING (8.2) AND (8.3) AND TAKING INTO ACCOUNT THAT FOR MOST CATALYSTS THE INTERNAL SURFACE AREA IS MUCH GREATER THAN THE EXTERNAL SURFACE AREA,

    VSrVarM caAcAA ∆−−∆−= )1('''' φρ

    EXTERNAL AREA INTERNAL AREA

    )1('' φρ −−= caAcA SraW

    (8.3)

    (8.4)

    M. Lacroix Internal Diffusion Effects 18

  • DIFFUSION AND REACTION IN SPHERICAL PELLETS:DIFFUSION AND REACTION IN SPHERICAL PELLETS:OVERALL EFFECTIVENESS FACTOROVERALL EFFECTIVENESS FACTOR

    • THE RATE OF MASS TRANSPORT IS ALSO GIVEN IN TERMS OF THE MASS TRANSFER COEFFICIENT :

    • ASSUMING THAT THE SURFACE REACTION IS FIRST-ORDER WITH RESPECT TO A, WE CAN UTILIZE THE INTERNAL EFFECTIVENESS FACTOR TO WRITE

    • COMBINING EQUATIONS (8.4)-(8.6) TO ELIMINATE CAs WE OBAIN THE MEASURABLE NET RATE OF REACTION

    (8.5)

    (8.6)

    ck

    VaCCkVaWM cAsAbccAA ∆−=∆⋅= )(

    AsA Ckr 1'' η=−

    Abccca

    A CkakSkr 1

    1

    ''

    )/())1((1 φρηη−+

    =− (8.7)

    M. Lacroix Internal Diffusion Effects 19

  • DIFFUSION AND REACTION IN SPHERICAL PELLETS:DIFFUSION AND REACTION IN SPHERICAL PELLETS:OVERALL EFFECTIVENESS FACTOROVERALL EFFECTIVENESS FACTOR

    • CONSEQUENTLY, THE OVERALL RATE OF REACTION IN TERMS OF THE BULK CONCENTRATION CAb IS

    WHERE (8.8)

    AbAA Ckrr 1'''' )( Ω=−⋅Ω=−

    )/())1((1 1 ccca akSk φρηη−+

    =Ω

    INTERNAL EFFECTIVENESS

    OVERALL EFFECTIVENESS

    M. Lacroix Internal Diffusion Effects 20

  • DIFFUSION AND REACTION IN SPHERICAL PELLETS:DIFFUSION AND REACTION IN SPHERICAL PELLETS:WEISZWEISZ--PRATER CRITERION FOR INTERNAL DIFFUSIONPRATER CRITERION FOR INTERNAL DIFFUSION

    • THE WEISZ-PRATER CRITERION USES MEASURED VALUES OF THE RATE OF REACTION TO DETERMINE IF INTERNALDIFFUSION IS LIMITING THE REACTION.

    • THIS CRITERION IS DEVELOPED INTUITIVELY FROM THE INTERNAL EFFECTIVENESS FACTOR:

    • THE LEFT-HAND SIDE IS THE WEISZ-PRATER PARAMETER

    • IF THERE ARE NO DIFFUSION LIMITATIONS AND CONSEQUENTLY NO CONCENTRATION GRADIENT EXISTS WITHIN THE PELLET.

    )(' obsrA−

    )1coth(3 112

    1 −= φφηφ

    Ase

    cAWP CD

    RobsrC2'

    21

    )( ρηφ −==

    1

  • EXAMPLE No. 1:EXAMPLE No. 1:DIFFUSION AND REACTION IN SPHERICAL PELLETS:DIFFUSION AND REACTION IN SPHERICAL PELLETS:

    WEISZWEISZ--PRATER CRITERIONPRATER CRITERION

    • THE FIRST-ORDER REACTION WAS CARRIED OUT OVER TWO DIFFERENT-SIZED PELLETS. THE PELLETS WERE CONTAINED IN A SPINNING BASKET REACTOR THAT WAS OPERATED AT SUFFICIENTLY HIGH ROTATION SPEEDS THAT EXTERNAL MASS TRANSFER RESISTANCE WAS NEGLIGIBLE. THE RESULTS OF TWO EXPERIMENTAL RUNS MADE UNDER IDENTICAL CONDITIONSARE AS GIVEN IN THE FOLLOWING TABLE. ESTIMATE THE THIELE MODULUSAND EFFECTIVENESS FACTOR FOR EACH PELLET. HOW SMALL SHOULD THE PELLETS BE MADE TO VITUALLY ELIMINATE ALL INTERNAL DIFFUSION RESISTANCE?

    BA→

    MEASURED RATE(mole/g cat. s) X 105

    PELLET RADIUS(m)

    RUN 1 3.0 0.01

    RUN 2 15.0 0.001

    M. Lacroix Internal Diffusion Effects 22

  • DIFFUSION AND REACTION IN SPHERICAL PELLETS:DIFFUSION AND REACTION IN SPHERICAL PELLETS:MEARSMEARS’’ CRITERION FOR EXTERNAL DIFFUSIONCRITERION FOR EXTERNAL DIFFUSION

    • THE MEARS’ CRITERION USES THE MEASURED RATE OF REACTION TO LEARN IF MASS TRANSFER FROM THE BULK GAS PHASE TO THE CATALYST SURFACE CAN BE NEGLECTED.

    • MASS TRANSFER EFFECTS CAN BE NEGLECTED IF

    • :REACTION ORDER• :CATALYST PARTICLE RADIUS (m)• :BULK CONCENTRATION (kmole/m3)• :MASS TRANSFER COEFFICIENT (m/s)• :BED POROSITY

    )(' obsrA−

    15.0)1('

    <−−

    Abc

    cA

    CkRnr ρφ

    nR

    AbCckφ

    M. Lacroix Internal Diffusion Effects 23

  • MASS TRANSFER AND REACTION IN A PACKED BEDMASS TRANSFER AND REACTION IN A PACKED BED

    • WE NOW CONSIDER THE ISOMERIZATION REACTION TAKING PLACE IN A PACKED BED OF CATALYSTS PELLETS:

    • :CROSS-SECTIONAL AREA OF THE TUBE (dm2);• :BULK GAS CONCENTRATION OF A (mole/dm3);• :BULK DENSITY OF THE CATALYST BED ( , kg/m3);• :VOLUMETRIC FLOW RATE (dm3/s);• :SUPERFICIAL VELOCITY ( ,dm/s)

    cρφ )1( −=

    cAAbCbρ

    cAv /0=U0v

    BA→

    M. Lacroix Internal Diffusion Effects 24

  • MASS TRANSFER AND REACTION IN A PACKED BEDMASS TRANSFER AND REACTION IN A PACKED BED

    ( ) ( ) ( ) 0___ =+− ∆+ generatedAoutAinA zzz

    ( ) czAzr AWinA ⋅= )(_WHERE

    ( ) czzAzzr AWoutA ⋅= ∆+∆+ )(_

    ( ) zArgeneratedA cbA ∆= ρ'_

    M. Lacroix Internal Diffusion Effects 25

  • MASS TRANSFER AND REACTION IN A PACKED BEDMASS TRANSFER AND REACTION IN A PACKED BED

    • THE MOLE BALANCE EQUATION BECOMES

    • THE MOLAR FLUX IS THE SUM OF MASS DIFFUSION AND CONVECTION, i.e.,

    • THE RATE OF REACTION

    AbAb

    ABAz UCdzdCDW +−=

    0' =+− bAAz rdzdW ρ (8.9)

    (8.10)

    Ω=Ω−=Ω−=− aAbaAbAbA SkCSrrr'''' (8.11)

    FIRST-ORDER REACTION

    M. Lacroix Internal Diffusion Effects 26

  • MASS TRANSFER AND REACTION IN A PACKED BEDMASS TRANSFER AND REACTION IN A PACKED BED

    • SUBSTITUTION OF (8.10) AND (8.11) IN (8.9) YIELDS

    • IF THE FLOW RATE THROUGH THE BED IS VERY LARGE, AXIAL DIFFUSION CAN BE NEGLECTED

    AND THE SOLUTION TO (8.12) BECOMES FOR CONVERSION X

    022

    =Ω−− AbabAbAb

    AB CkSdzdCU

    dzCdD ρ

    dzdCU

    dzCdD AbAba

  • MASS TRANSFER AND REACTION IN A PACKED BEDMASS TRANSFER AND REACTION IN A PACKED BED

    • YOUNG AND FINLAYSON (Ind. Eng. Chem. Fund., 12, 412 (1973)) HAVESHOWN THAT AXIAL DISPERSION CAN BE NEGLECTED WHEN

    • :SUPERFICIAL VELOCITY• :PARTICLE DIAMETER• :EFFECTIVE AXIAL DISPERSION COEFFICIENT

    a

    p

    Ab

    pbA

    DdU

    CUdr 0

    0

    '

  • EXAMPLE No. 2:EXAMPLE No. 2:MASS TRANSFER AND REACTION IN A PACKED BEDMASS TRANSFER AND REACTION IN A PACKED BED

    • IT IS PROPOSED TO REDUCE THE CONCENTRATION OF NO IN AN EFFLENT STREAM FROM A PLANT BY PASSING IT THROUGH A PACLED BED OF SPHERICAL POROUS CARBONACEOUS SOLID PELLETS. A 2% NO – 98% AIR MIXTURE FLOWS AT A RATE OF 10-6 m3/s THROUGH A TUBE OF CROSS SECTION AREA OF 2.03 x 10-3m2 PACKED WITH POROUS SOLID AT A TEMPERATURE OF 1173 K AND A PRESSURE OF 101.3 kPa. THE REACTION

    IS FIRST-ORDER IN NO, THAT IS,

    AND OCCURS PRIMARILY IN THE PORES INSIDE THE PELLET, WHEREAND

    CALCULATE THE MASS OF POROUS SOLID NECESSARY TO REDUCE THE NO CONCENTRATION TO A LEVEL OF 0.004%, WHICH IS BELOW THE ENVIRONMENTAL PROTECTION AGENCY LIMIT.

    221 NCOCNO +→+

    NOaNO CkSr =−'

    gmSa /5302= smmk 2310 /1042.4 −⋅=

    M. Lacroix Internal Diffusion Effects 29

  • EXAMPLE No. 2:EXAMPLE No. 2:MASS TRANSFER AND REACTION IN A PACKED BEDMASS TRANSFER AND REACTION IN A PACKED BED

    • AT 1173 K, THE FLUID PROPERTIES ARE:

    • THE PROPERTIES OF THE CATALYST AND BED ARE:

    ;/1082.1

    ;/100.2

    ;/1053.1

    28

    28

    28

    smD

    smD

    sm

    e

    AB−

    ⋅=

    ⋅=

    ⋅=υ

    ;0.1;103

    ;/104.1)1(

    ;5.0;/108.2__/8.2

    3

    36

    363

    =⋅=

    ⋅=−=

    =⋅=

    γ

    φρρ

    φρ

    mR

    mg

    mgorcmg

    cb

    c

    M. Lacroix Internal Diffusion Effects 30

  • LIMITING SITUATIONS FROM REACTION DATALIMITING SITUATIONS FROM REACTION DATA

    • FOR EXTERNAL MASS TRANSFER-LIMITED REACTIONS IN PACKED BEDS, THE RATE OF REACTION AT A POINT IN THE BED IS

    • WHEN INTERNAL DIFFUSION LIMITS THE RATE OF REACTION, WE OBSERVE THAT THE RATE OF REACTION VARIES INVERSELY WITH PARTICLE DIAMETER AND IS INDEPENDENT OF VELOCITY.

    AccA Cakr =−

    MASS TRANSFER COEFFICIENT

    EXTERNAL SURFACE AREA PER UNIT REACTOR VOLUME

    (mole/dm3s)

    21

    21

    p

    cd

    Uk ∝p

    c da 1∝

    231

    p

    Ad

    r ∝−

    M. Lacroix Internal Diffusion Effects 31

  • LIMITING SITUATIONS FROM REACTION DATALIMITING SITUATIONS FROM REACTION DATA

    VARIATION OF REACTION RATE WITH:

    TYPE OF LIMITATION

    VELOCITY PARTICLE SIZE

    TEMPERATURE

    EXTERNAL DIFFUSION

    LINEAR

    INTERNAL DIFFUSION

    INDEPENDENT EXPONENTIAL

    SURFACE REACTION

    INDEPENDENT INDEPENDENT EXPONENTIAL

    21

    U 23−

    pd

    1−pd

    M. Lacroix Internal Diffusion Effects 32

    INTERNAL DIFFUSION EFFECTS(8)INTERNAL DIFFUSION EFFECTS:INTRODUCTIONINTERNAL DIFFUSION EFFECTS:INTRODUCTIONINTERNAL DIFFUSION EFFECTS:OBJECTIVEDIFFUSION AND REACTION IN SPHERICAL PELLETS:MOLE BALANCE EQUATIONDIFFUSION AND REACTION IN SPHERICAL PELLETS:MOLE BALANCE EQUATIONDIFFUSION AND REACTION IN SPHERICAL PELLETS:MOLE BALANCE EQUATIONDIFFUSION AND REACTION IN SPHERICAL PELLETS:DIFFERENTIAL EQUATIONDIFFUSION AND REACTION IN SPHERICAL PELLETS:THIELE MODULUSREACTION RATES: REMINDERDIFFUSION AND REACTION IN SPHERICAL PELLETS:SOLUTION FOR A FIRST-ORDER REACTION (n=1)DIFFUSION AND REACTION IN SPHERICAL PELLETS:INTERNAL EFFECTIVENESS FACTORDIFFUSION AND REACTION IN SPHERICAL PELLETS:INTERNAL EFFECTIVENESS FACTORDIFFUSION AND REACTION IN SPHERICAL PELLETS:RATE OF REACTIONDIFFUSION AND REACTION IN SPHERICAL PELLETS:INTERNAL EFFECTIVENESS FACTORDIFFUSION AND REACTION IN SPHERICAL PELLETS:OVERALL EFFECTIVENESS FACTORDIFFUSION AND REACTION IN SPHERICAL PELLETS:OVERALL EFFECTIVENESS FACTORDIFFUSION AND REACTION IN SPHERICAL PELLETS:OVERALL EFFECTIVENESS FACTORDIFFUSION AND REACTION IN SPHERICAL PELLETS:OVERALL EFFECTIVENESS FACTORDIFFUSION AND REACTION IN SPHERICAL PELLETS:OVERALL EFFECTIVENESS FACTORDIFFUSION AND REACTION IN SPHERICAL PELLETS:WEISZ-PRATER CRITERION FOR INTERNAL DIFFUSIONEXAMPLE No. 1:DIFFUSION AND REACTION IN SPHERICAL PELLETS:WEISZ-PRATER CRITERIONDIFFUSION AND REACTION IN SPHERICAL PELLETS:MEARS’ CRITERION FOR EXTERNAL DIFFUSIONMASS TRANSFER AND REACTION IN A PACKED BEDMASS TRANSFER AND REACTION IN A PACKED BEDMASS TRANSFER AND REACTION IN A PACKED BEDMASS TRANSFER AND REACTION IN A PACKED BEDMASS TRANSFER AND REACTION IN A PACKED BEDEXAMPLE No. 2:MASS TRANSFER AND REACTION IN A PACKED BEDEXAMPLE No. 2:MASS TRANSFER AND REACTION IN A PACKED BEDLIMITING SITUATIONS FROM REACTION DATALIMITING SITUATIONS FROM REACTION DATA