تقنية التفاعلات كيميائية

אאאא

٢٦٥٢٦٥

א ٢٦٥

אא

،،אא،אW

אא א א א אאאאאא،אאאאאאא

אאאא אאאאאאאWא

אאK

אאאאאאא א ،א אא

אאאאאא،אאא א ،א אא א א אא א א א א א א א

אא،אאאא،אK

אא?אא???Kאאאאאאאא

אאאאאאא،א ،א א אא

Kאאאאא

؛ א אא אאK

אאאא

א ٢٦٥

אא

אאאאKא

אאאאאאKאאאא،אאאאאאאKא

אאאאאאאאאאאאא

אאאאאאאאאאאאאK

אאאאאאאאאאK

אאאאאKWאאאאאא

אאKWאאאאKאא

אאאאאאאאאאאאאאKאאאאא

אאKאאאאאWאאאא،אאא،אאאאאאאא

אK

אאאא

אא

١

א ٢٦٥ אא אא אא

- ١ -

אא

אא

אאא

אא

אא ١K אאאא ٢K אאאאאא ٣K אאאא ٤K אאא

אא

٤א

אא

אאא אאא


- ٢ -

אא אאא،K

Wא אאFbatchFEאאאE

אcontinuousKאאF١ J١Eאאאאאאאא

אאאאאKאאאאFאאאEאאאא

אאאKאאאאאאאאאאKא

אאאאאאאאאאאא،

אאאאאאK

١ J١Wאא(Batch)


- ٣ -

אאF١ J٢EאאאאאאאאKאאא،אא

אאאאאאאKאאאאאK

١ J٢Wאא(Continuous)

אאאאא(Semibatch) F١ J3Eאאא

אאאאאאאאאאאאK

אאאאאאאאאאאאאאאאאאא

אK


- ٤ -

ReactantA +

Products

١ J٣Wאא(Semibatch)

Wא

אאא،אאאאF(Continuous Stirred Tank Reactor, CSTRאאF

EאF١ J٤Eא،אאאאאאאאאK

אאאאאאאאאאאאא(CSTR) (Steady-state)

KKאאאאאאKאאאאאK

Kאאאאאאא


- ٥ -

١ J٤Wאא

אאאאאא (Plug Flow Reactor, PFR) אאאאא

F١ J٥EKאאאאאKאאאאKא

אאאאאאאאאKאאאאאאKא

אאאאאאKאאאא

אאאאאאF١ J٦KE


- ٦ -

١ J٥Wא(Plug Flow Reactor, PFR)

تغذية

ناتج

١ J٦Wאא

Wאאאא אאאאא

אאאאא(Bubble Column Reactor).


- ٧ -

אאאאאאאאא(Two-Phase Slurry Reactor)אא(Fixed Bed Reactor)

אKאאאאאאF(Three-Phase Slurry ReactorK١א J٧אאK

(A)

(B)

١ J٧W(A) אאK(B) א

אאאאא(Fluidized bed Reactor) אאאאאאאאאא

אאאאאא


- ٨ -

אאאאאא١א J٨K

Cracked products Combustion

gases

Spent Catalyst

Air

Hydrocarbon Feed

Regenerated Catalyst

١ J٨Wאאא(Fluidized Bed)

אאאא אאאאאאאא

אאאאאKאאאא

אאאF١ J٩E


- ٩ -

١ J٩Wאאאא

אאאאאאאאאאאאאF١ J

١٠(K

١ J١٠Wאאאאאא

אאאאאאאאאאF١ J١١E

אאאאKא

א


- ١٠ -


١ J١١Wאאאאאא

א١ J١٢א(CO)K

١ J١٢WאK

אא

א

٢

א ٢٦٥ אא אא א

- ١١ -

אאChemical Kinetics

אא

אאאא

אא

אא ١K אאא ٢K א ٣K אאא

אא

١٠א

אא אאExcelאאא

אא

אאא אאא


- ١٢ -

אאא(Scale-up)אאא

אאאאאאאאאאאאאאאאא،א

אאאKאאאאאFאאאאEאאאא

אאKאאאאאאאא،אאאא

אאאאKאאא(Plug Flow

Reactor, PFR)אאאאאאאKאאאאא(Rate law) א

אאאא(Reactor Design)אאK

אא אאHomogenous Reaction

אK

אאHeterogeneous Reaction

אאאאK

אאIrreversible Reaction

אאאאFBA→KE


- ١٣ -

אאReversible Reaction

אאאאאאאאאאא(Equilibrium)אא

אאFBA↔KE

אאא אאRate of Homogenous Reaction

אאאאאאאאא

אאאW

)12(dt

dnV1r i

ii −=

i ،n ،אVאKאאאא

אאאאCiW

)22(Vn

c ii −=

אW

)42(dtdc

r

)32(dt

)Vn

( dr

ii

i

i

−=

−=


- ١٤ -

אאאאא

אאאאאW

)52(dDcCbBaA −+→+ b, a אאstoichiometric coefficientsאאא

אאאd, cאאאאאאCDא،אא

אאאאאKאW

)62(dtn d

d1

dtn d

c1

dtn d

b1

dtn d

a1- DCBA −==−=

)72(dDr

cCr

bBr-

aAr-

−===

אאF٪E Chemical Conversion אאאאאK

אאAאnAonAt،אאAW

)82(100n

n - n (t)X

Ao

AAoA −×=

،אאאאK

אאא،אא2-1٢ J٢KאאאאאF50 %KEAאאא(Catalyst)،א

BאאאKאאאאאאאאאאא

אאאF١ J2KEאא١ J2،


- ١٥ -

אא25%t1אא45%אאKא١ J2אאאאא

אאא5%אאאאאאK

1J2אא


- ١٦ -

2J2אא

אאאאאאא

אFאEאאאאאW

)92(c c α r- BAA −βα

:αאA

βאBK

:α+βאאK

אאאא)(αאF٩ J٢EאW

)102(c c k Ar- BAA −= βα

אkAאא(Specific reaction rate)،אאK


- ١٧ -

Arhenius equation אאאאW

)112( eA (T)k RTE

−=⎟⎠⎞

⎜⎝⎛ −

אא،אאאאאאאאאאאאאאk

אKאEאאאא،אF

EAאF١١ J٢EKאאאאאאאk אאא

FאאEאא(ln)W

)122(RTE -A ln k ln −=

F(ln kאאא(y)(T/1)א

(x)⎟⎠⎞

⎜⎝⎛−

RE،א(y)(ln A)K

אאאאאאk TFE،אkTאאא

K

אReaction Order ،אאא

אאKאW

אא(Reaction mechanism)אאאאאKאא(Reaction mechanism)א


- ١٨ -

אאKאאK

אאאאאאאאKאא،אא

אאW

H2 + I2 → 2 HI (2-13)

אאאאאKאאאW

NaOH +CH3Br → CH3OH +NaBr (2-14)

אאW 2NO +2H2 → N2 + 2H2O (2-15)

אאאאW 2NO +H2 → N2 +H2 O2 (2-16)

H2O +H2 → 2H2O (2-17) אאאF١٦ J٢Eאא

אאF١٦ J٢Eאא٢א١K(mechanism)

אאאאאאאאאאאK

אאאK


- ١٩ -

אאא אאאאא

אאK،אאאאאאאאKאאא

אא،אאאאאאאאאאאאאK

אאא

אא A → P (2-18)

א

19)-(2k0)A(ck dt

Ac d==−

אF١ J١٩EאאאאW

)202(dtk c

c Ac dt

0

A

Ao−∫=∫−

[ ]

[ ] 22)-(2ktcc

21)-(2ktcc

AA0

A0A

=−

=−−

cAoאאאAcAאאAtKאF٢٢ J٢EאאאאAFcA ((y)א(x)

W


- ٢٠ -

cA

t

cAo

א -k kSImol /m3 sאא

(y)KcAoKאאאאאאאאאאאא

אאאK

אאא

A → P (٢-23)

א

)242(Ack dt

Ac d−=−

[ ] 25)-(2kt ccAc ln A

Ao=−

26)-(2kt cln - cln AAo =

27)-(2kt cc ln

A

Ao =


- ٢١ -

אF٢٧ J٢EאW

ln (cAo/cA)

t

אאאאאkkאSIs-1Kאאא

אאאאאK

אאא

אאאאW

28)-(2P2A →

29)-(2PbBaA →+ אF٢٨ J٢EאאA

)302(2Ack

tdAc d

−=−

)312(dtk cc d

0

c

c2A

AA

Ao

−=− ∫∫t


- ٢٢ -

32)-(2k t c1 Ao

A

c

cA

=⎥⎦

⎤⎢⎣

⎡

33)-(2k t c1

c1

AoA

=−

אאאאא1/cA(y)אt(x)אk(y)1/cAoאW

t

1/cA

1/cAo

אאאא A Bא

אאABאW

34)-(2PbBaA →+

)352(c ck tdc d

BAA −=−

אאW

١K אאאA B(cAo = cBo)b = a


- ٢٣ -

cA = cB

אאF٣٠ J٢EF٣٣ J٢KE

٢K cAo ≠ cBob ≠ aK

אאW

)63(2c ck tdc d

BAA −=−

אאאאcBcAAאאnAoBאאnBoKAא

tnAB אאnBKF٢٩ J٢EW

)73(2)n(n)ab(nn AABB 00

−−−=

אאW

)83(2)c(c)ab(cc AABB 00

−−−=

cBאF٣٥ J٢EאאאאW

)39(2 tdk )c

ab c

ab(cc

c d t

0

c

cAAoBoA

AA

Ao

−=+−

− ∫∫

אאאאאאW

40)-(2k t cc

lncc

lnc

ab - c

1

Ao

Bo

A

B

AoBo

=⎥⎦

⎤⎢⎣

⎡⎟⎟⎠

⎞⎜⎜⎝

⎛−⎟⎟

⎠

⎞⎜⎜⎝

⎛


- ٢٤ -

אאאאאאאאKאאאא

אאאאאאאאאאא

אאKאאאאאKאאאאא

אאאFאאEאאאאאאאאK

אMethod of Half Life אt1/2אאאאא

אאKאאאאאאאאאאKא

אאאאאאאאאאאK

אאאאאאאאאאאאאW

אא

41)-(2PnA →

)422(ck tdc d - n

AA −=

)432( tdk cc d -

t

0

c

cnA

AA

Ao

−= ∫∫

)442(c1

c1

1)-k(n1 t

1-nAo

1-nA

−⎟⎟⎠

⎞⎜⎜⎝

⎛−=


- ٢٥ -

( ) )452(1 - cc

1-n ck 1 t

1n

A

Ao1-n

Ao

−⎥⎥⎦

⎤

⎢⎢⎣

⎡⎟⎟⎠

⎞⎜⎜⎝

⎛=

−

t = t1/2،cAo cA =1/2

( ) )462( c1

1-nk 1- 2 t 1-n

Ao

1-n

21 −⎥

⎦

⎤⎢⎣

⎡=

47)-(2 cln n)-(1 1)k-(n

1- 2ln ln t Ao

1-n

21 +=

אF٤٧ J٢Eאאא(y)אאאא(x)،1-n

אn Kאא(y)אkKאאאאאn=1،אא

אאאW

48)-(2k t ccln

A

Ao =

t = t1/2،cAo cA =1/2

)492(k t c

21cln

21

Ao

Ao −=

)502( tk

2ln 21 −=


- ٢٦ -

אאW

)512( tk 2

c21

Ao −=

אאW

)522( tck l

21

Ao

−=

אאאאKאאאאאא،

אאאK

אאא אאאאאאאאאא

אKאאאאאאאאאאאאKאאאא

אאאאאאאאאW

١. אאאאאאאאאאK ٢. אאאK ٣. אאK

אאאאאאאאאKאאאא

אאאאאאK

- ١١ -

אאאא

א

א

٣


- ٢٧ -

אאHomogeneous Reactors

אא

אאאא

אא

אא ١K אאא ٢K אאאא

אא

٨א אא

אאאאאא

אא

אאא אאא


- ٢٨ -

אאאFW١Eאאא،F٢Eאאאא،F٣EאאאאK

אאאא Reactor design and laboratory rate data

אאא،אאאFאEאFא

אPFR EאFאBatch KEאאא،אא

אא،Kאאא(Feed flow rate)א(Product flow rate)אא Jא Jא

אאאאאאאאאK

אאWF١E،אאאF٢EאאאאFOptimization techniqueE،אא

אאאאאאאאK אאא،אא

אאFStorage tank Eא،אאאFCyclicalEK

אאFReactor controlEאאאאאKאאאאא

אא،(Strategy) (Fluctuations)אאKא

(Manual)אאא،א(Semi-computerized )K،אאאאאאאDirect-

digital)EאאאאFClosed-loopEא،


- ٢٩ -

אאKאאאאK

אאאאא(Iterative)،אאאאאאאK

אאאאאאאKאאW

١K א(Bench-scale laboratory reactor)אKאאאאא(Diffusion)אאאFאאEאא

אאKאאK ٢K אFאאא(Pilot plantK ٣K אאK

אאאאאאא،אא(SO2)K

אאאאאאאKא١אא،א

א(SO3)אאאאאK SO3אאא،אא

אאאאאאKא،אאאא

אאאאאאאאאKאאאאאא

אא(Pilot-plant)א،אאאאאKאאא

אאא،אאKאאאא

אא،אאאK


- ٣٠ -

אא،אאאאאאאא(Diffusion)אאא

אאאאאKאאאאאKאאאאאK

אאאאאאK

אאא،אאאאאאאKא

،אאאאאאאKא

אאאאאאאאאאאאאKא–

Jאאאאאאאאאא(Prediction methods)،אא

אאאאאאK

אאאMass and Energy Balances

אאאאאאאאאKאאא(Single-reaction system)א

א(Limiting reactant)،אאאאאאאא،אא(Limiting

reactant)KאאאאK ،אאאא

אאאא(Conversion)אאאאאאאאא(Stoichiometry)K

אאFMultiple-reaction systems)אאאK


- ٣١ -

א(X)אאאאאאKאאאאאKאאא

(Simultaneous reactions)(Successive reactions) אאאאאאאK

אאאאאKאאא،א

אאאאאK

٣ J١

אאאא(CSTR)KאW

HClClHCClClHCHClClHCClClHCHClClHCClHC

3362246

246256

56266

+→+

+→+

+→+

אאא(NB0)אKאאאאKאאאאא

אKאאאאXMXD

XTאאK

א

אאאא(Limiting reactant)אא،KNBNMNDNTא

אאאאאאKאאאא،אאא٢אאא

،א

)13(2

2

−=CL

DD N

Nx


- ٣٢ -

،א

)23(3

2

−=Cl

TT N

Nx

אאW

)33()31

21(1)(1

2−++−=++−= ClTDMTDMB NxxxNNNN

אאאא[B0](NB0)/Vא،(3-1)(3-2)אאא،Kאאא

אאW

[ ] )43(][)(

2

0

0 −== MClMB xNB

VNN

M

)53(][21][

20 −= DCl xNBD

)63(][31][

20 −= TCl xNBT

)73(]][)31

21(1[

)(][ 02

0 −++−== BNxxxV

NNB ClTDM

BB

אאאאאאאאK،אאאאאאא

Kאאאא

אאאW

)73(322

−++= TDMCl NNNN


- ٣٣ -

אאאאאאאKאאא٣ J١٣ J٢٣ J٣CW

)83(NXNXNXN2222 ClTClDClmCl −++=

9)-(31XXX TDM =++

F٣ J٢E אאאאF200OC250OCE

O(g)HC(g)O21(g)HC 42442 →+

)(2)(2)(3)( 22242 gOHgCOgOgHC +→+

אאאX1X2אאW

11 22

22

1XNor

NX OHC

OHC ==

22 21

21

2

2

XNorN

X CO

CO

==

אאאW OHX 222 =

42211 HCXX =−−

N2 = O.79(air)


- ٣٤ -

)321()(21. 212 XXairoO +−=

אא1211 Xair−+

אאאאאW

4

142

211 XA

XOHC

−+=

4

22

211

2

Xair

XCO−+

=

4

22

211

2

Xair

XOH−+

=

4

2142

211

1

Xair

XXHC−+

−−=

4

2

211

79.0

Xair

airN−+

=

4

24

2

211

)321(21.0

Xair

XXairO

−+

+−=

אאX2HX1KאאאאX1X2LX1אאK

אאW }אאאא{ J}אאאאא{

J}אאאאא{=}אאאאאא{F١٠ J٣E


- ٣٥ -

אאאאאאאאאאאV∆אאא∆Τאאאאא،

Kאאאאאאאא∆ΤאאאאKאאאאאtr ∆∨∆،

rאאאKאr،אאאאF٣ J١٠Eא،אאאא

אאאאאאK אאMass Balance

אF٣ J١٠EF٣ J١١EאV∆אא،אאF٢ J٣KEאאא

אאאאאKאאאFאא،Xא

א،אאאאאאאא(Bulk flow)אאא،F٣ J١٠EW

tXF ∆− )1( Kאאאאאא∆Χ+Xאא

∆Τ∆−− )1( XXFK

אאאאאאאאKאאtVr ∆∆،rאKאאא

אאאאאאV∆Kא،אאאאrא

אאאאK


- ٣٦ -

אא אאאאאאאא

)אאKEאאאאאאאאFאאאאאE،

אאאאKאאאV∆אt∆W

}אאאאא{ J}אאאאאא{H}אאאאאא{=}אאאא{F١١ J٣E

אאאאאאא(Internal energy)אא(Potential energy)אא(Kinetic energy)

אאאKאאאאאאאאאאKאא

אאאאאאאאאאKאאאאאא

אאאאאאאאאFאאKEאאאאאאא

אאאאKאF٣ J١١EאאאאאאK

אF٣ J١٠EF٣ J١١E،אאאאKאאאא

אאMixing)Eא(Diffusion )אאKאאאאאא،אאאאא

אאKאאאאF٣ J١٠EF٣ J١١EאאK


- ٣٧ -

אאאThe Ideal Stirred-tank Reactor אא(CSTR)אא(Steady-

state flow reactor)א،(Batch reactor)א(Semi-batch reactor)FאאKEאאאא

אאאאKאאאFאEאאאא،

אאאאאאאKאאאאאK

אאאSteady-State Flow

אאאאF٣ J١EאאKאאאאאKאאאאא

אF١٠ J٣EאאאאLimiting reactant)Et∆K

אאאKאאאאאאFאאאא،XF

אאאXPאאאאאtXF F ∆− )1(tXF P ∆− )1(אאK

٣א J١WאאאCSTRאא

א


- ٣٨ -

אאאאא،אאאאאKא

אאrPא،E،אאאאאtVrE ∆Kאאאא

אאאאאאאKאF١٠ J٣EאW

0)1()1( =∆−∆−−∆− tVrtXFtXF EEF

E

FE

rXX

FV −=

אאאאאאאXEאXFFאא، rEK

אאאXEאאK،אאאאאאאK

אאאאKאא،אאאאאאKKKא

אאאאאrEאא،אאאVKאאאאF٣ J١١E

אKא(Base state)FאאאאEאאKאאא(Enthalpy)

אאאאאFאEHFHEKאאאאFtא،tHF Ft ∆tHF Et ∆אא

אאW

0)()(1 =∆−+∆− tTTUAtHHF EshEF


- ٣٩ -

0)()(1 =−+− EshEF TTUAHHF

אאאאאאאאאTsאאאאU(Overall-heat-transfer coefficient)

אא(Effective area)אאAhKאאH∆אאKא

אא،אאאאא،אH∆אrאאאHEאK

אאאאHE JHFאאHrT ∆,, אאאאאKאאא

TFTEאאאאאאא،Kא(TE-TF)CpMHXX FE /)( ∆אאW

1

)()()(MFHFXXXXTTeHH FEFEFEPFe

∆−+−+−=−

M אאאא(Limiting reactant)∆ΗאאאאאKאF٥ J٣EF٤ J٣E

0()()( )1 =−+∆Η

−−− EshFEPeF TTUAM

XXFeTTF

אאאאאאאKאאFX J EXאF٣ J٣E

0)()(1 =−+∆Η

−− EshEPEF TTUAM

VreTTF

אF٤ J٣EF٦ J٣EF٧ J٣E،אאאאא(Homogeneous reactors)


- ٤٠ -

אFאאEBatch Operation (Non steady-State) אאאאאאאK

אאא،אאmאא∆Χאt∆،אאאאא

אt∆Xm∆−،אאW

XmtrV ∆=∆−

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- ٤١ -

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- ٤٢ -

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- ٤٥ -

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- ٤٦ -

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- ٤٧ -

אאאDesign Of Heterogeneous Catalytic Reactors

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- ٤٨ -

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- ٤٩ -

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- ٥٧ -

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- ٦٠ -

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- ٦٢ -

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- ٦٣ -

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- ٦٤ -

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- ٦٥ -

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1. Scott, H., Fogler,O., “Elements of Chemical Reaction Engineering”, International edition, Prentice Hall Inc., USA, 1999 2. Smith, J.M., “Chemical Reaction Engineering”, International edition, McGraw-Hill,

USA, 1981

א ٢٦٥ א אא

א ..................................................................................................................... ٣

אא ........................................................................................................... ١

אא ........................................................................................................... ٢

אאChemical Kinetics ............................................................ ١١

אMethod of Half Life ............................................. ٢٤

אאHomogeneous Reactors ........................................................ ٢٧

אאHeterogeneous Reactions ................................................. ٤٤

אCatalysis ................................................................................................ ٦٠

......................................................................................................... ٦٧

א٧٩ ............................................................................................................ א

אא ..................................................................................................... ٨١

א٨٣ .................................................................................................................. א

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