)(Advanced Chemical Reaction Engineering

:

Email:

(Temperature and Pressure Effects)




.




http://en.wikipedia.org/wiki/Chloroplast

.
.

) (.
3



)(Reactor

:

)( )(Reaction rate
...
.
: A

mol
lit.min

rA =kCA

)(Rate constant-k
.



)(Homogeneous1
.


)(Heterogeneous2

1/hm'dins/
.
2/hetr'dns/


:
) (

) (
) (
) (



)(Batch
.
.
)(Continuous
.
.
)(Semi-continuous
.
.

Batch

Continuous

Semi-continuous







...



)(

1 dNi
= ri
V dt

: ) (Intensive.
.


)(
: .
:
)(

10




:i
:i

1 dNi
= ri
V dt
1 dNi
= ri
V dt

.

-
.

Accumulation=Input-Output+ Generation-Consumption

Reaction rate

11



:
.
.
:
.
.
.
... .
.

12

(Batch Reactor) .
(Continuous Stirred Tank Reactor-CSTR) .
(Plug Flow Reactor-PFR) .

Batch
Reactor
-

Continuous Stirred Tank

Reactor (CSTR)
-

Plug Flow
Reactor (PFR)
13

:
dX A
rA V

XA

t=N A0

.
)( :
for A =0

CA dC
dX A
A

CA0 r
rA
A

XA

t=CA0

:
XA
dX A
dX A
CA0
0
rA V0 1+ A X A
rA 1+ A X A

14

XA

t=N A0


)(CSTR
) :(A
V

X A X A
=
=
=
FA0 CA0 -rA
-rA
1 V VCA0 CA0 X A
= = =
=
s v0
FA0
-rA

Levenspiel, P 94, Fig. 5.3.

:
V X A X A X Ai
=
=
FA0 -rA
-rA

15


)(PFR
.
.

.
.
CAf
FAf
X Af
vf

FA +FA

FA

CA0
FA0
X A0 =0
v0

)( :
0=FA - FA +FA +VrA
16


)) (PFR(
0=FA - FA +FA +VrA

:
V 0 0=FA - FA +dFA +dVrA

17

dFA =dVrA

FA =FA0 1-X A dFA =-FA0 dX A

FA0dX A =dV -rA

dX A
-rA

X Af

dV=FA0


)) (PFR(
) :(A
X Af dX
V

A
=
=
FA0 CA0 0 -rA
X Af dX
V VCA0
A
=
=CA0
0
v0
FA0
-rA

:
dX A
-rA

18

X Af

=CA0

X Ai


.

.
.
.

.

19


)(Hr
) (
.

:
:
aA bB rR sS
T a A
b B r R s S T
.

) (
.

20


)) (Hr(
:

H r E1 E2

E2()RA

E1()AR

R
Hr1

21


)) (Hr(
:

H r H R H A

E2()RA
R
A

HR

HA

22


)) (Hr(
:
:

H 298
46,110 J

H 298
92, 220 J

1
3
N 2 H 2 NH 3
2
2
N 2 3H 2 2 NH 3

Ho298 298 K.

23


)(Hr
):(Exothermic
):(Endothermic

H r 0
H r 0

)(Standard Heat of Formation

.
)(Standard Heat of Combustion


: .
24

H r i H fi

i :
i :
:
.

25


: :
:

) 4 HCl ( g ) O2 ( g ) 2 H 2O( g ) 2Cl2 ( g

92,307 J
0 J

fHCl

fO2

H fH 2O 241,818 J
H fCl2 0 J

H 298
2H fH 2O 4H fHCl 2 241,818 4 92,307

114, 408 J

26


:


.
:
)( .
.
.


+
T1
T1 T2

27

T2 T1

T2


aA rR sS
T2

T1

Reactants

Reactants

:( )

Products

Hr1

Products

H r 2 H 2 H1 Reactants H r1 H 2 H1 Products
T2

H r 2 H r1 C p dT
T1

: Nabla
-

C p rC pR sC pS aC pA
-

28


: 25 C
:

50000 J

A B 2 R H r ,298

1025 C
Cp 25 1025 C :

C pR 70 J / mol.K

29

C pB 45 J / mol.K

C pA 35 J / mol.K


)(:
:

H1 H 2 H 3 H 4
nC p T 2 R

nC p T 1A1B H r ,298

1 35 1 45 2 70 1025 25 50000

30


)(:
:

H r ,25 C 50000 J
H r ,1025 C 10000 J

25 C .
1025 C .
:

.
31

G RT ln ai i RT ln K
i

K a fi fi
i
i

ai i .
.
.

32

.
-

k1

rR sS
aA

k2

pR pS
yR yS
CR RT CS RT
p p
p p
p p

a
a
a
pA
y A
C A RT
p
p
p

pRr pSs n yRr ySs

CRr CSs RT
K a p a

pA
yA p
C Aa p

Kp

Ky

KC

33


k1

rR sS
aA

k2

aRr aSs xRr xSs CRr CSs n

K a a
CT
a
aA
xA
CA
n r s a
x : Mole Fraction
CT : Total Molar Concentration

34


) (

ln K H r

T
RT 2

1 1

T2 T1

35

K
H r
ln 2
K1
R


: 0 100 C .

C pA C pR const.

G298
14130 J / mol
A R

H 298 75300 J / mol

.
:

H r H 298
75300 J / mol
:

300

36

K 298 exp G298

/ RT

14130 J / mol
exp
8.314 J / mol.K 298 K


)(:

K
H r 1
1
ln

K 298
8.314 T 298

75300

K exp
24.7
RT

37

CPe
C A0 X Ae
X Ae

C Ae C A0 1 X Ae 1 X Ae
K

1 K

X Ae


)(:

Levenspiel, P 215, Fig. E9.2.

38




.

.
.

.

39

.
:

0 Input Output Generation Consumption

/
.
.
40

J
mol A

H r 0

aA rR

:
0 FAi H Ai FA H A FR H R

) (XA:

r
FAi X A
a

r
FAi X A H R
a

41

FA FAi 1 X A FR

0 FAi H Ai FAi 1 X A H A

r
X AHR
a

0 H Ai H A H A X A

0 H Ai H A X A H A H R
a

H r

0 H Ai H A X A H r
aArR .

42


)(Adiabatic Operating Line
:Cp
:

0 C pA Ti T X A H r
C pA T
H r

XA

a=1 r=1:
C pA T
H r 0 C pR C pA T T0

43

XA

.
.
.
.

44

Levenspiel, P 222, Fig. 9.7.

Q

:

C pA T Q
H r

45

XA

Q T T1.

Levenspiel, P 226, Fig. 9.11.

46


: --

.
65 C 1 min 58.1 % 25 C
10 min 60 % -- .
:

:
XA
dX A
dX A
1 XA
dX A
C A0

0
rA
k1C A k2CR k1 0 1 X A / X Ae

XA

t C A0

k1t
XA
ln 1

X Ae
X Ae

47


)(:

65 C:

X Ae 0.89
:

)k1 (1min
0.581
ln 1

0.89
0.89

k1,338 0.942 min-1

48


)(:

25 C:

k1,298 0.0909 min-1

:

)0.942 k10e E1 / R (338

)0.0909 k10e E1 / R (298

k1,338
k1,298

:
E1 48900 J / mol
k10 :
48900
k10 34 106 k1 34 106 exp

RT
49


)(:

.K=k1/k2 k1 k2 K :

k1
124200

exp 42.04

K
RT

k2

rA k1C A k2CR

rA k1C A0 1 X A k2C A0 X A

-- rA XA T
.
CA0 1 .
CA0 rA CA0 .
50


)(:

Levenspiel, P 219, Fig. E9.3.

51



.
-- .

Levenspiel, P 216, Fig. 9.3.

52



.1
.2
.3
.4

) ( T-XA
XA T
XA-rA
XA-rA

Levenspiel, P 216, Fig. 9.4.

53


)(

Levenspiel, P 216, Fig. 9.4.

54




V/FA0 .
.
.
.
.
.
.

55

.
.
.
.
) ( .
.
:
.
.
.

56



.

.

Levenspiel, P 220, Fig. 9.5.

57

Levenspiel, P 224, Fig. 9.8.

58




.

.


.
.

.

59

Levenspiel, P 224, Fig. 9.9.

60

V/FA0.
T-XA
.
.

.
.
.
) (
CP/-Hr .

61



CP/-Hr ) ( .

CP/-Hr ) (
.

Levenspiel, P 225, Fig. 9.10.

62



: .
.

.


) (...
)(Multistaging
) (

63

Levenspiel, P 227, Fig. 9.12.

64


-

.

.
.
:

0 v0C A0 v0C A VrA

:

0 C pA Ti T X A H r
65


- )(
) (
.
.

Levenspiel, P 228, Fig. 9.13.

66

Levenspiel, P 228, Fig. 9.14.

67

M M .
M .
M M M.
M ) (Ignition .
-

Levenspiel, P 229, Fig. 9.14.

) (
.
.
.
68


:
80 % .

FA0 1000 mol min C A0 4 mol lit Tmax 95 C

:

.
.
.
.
rA CA0 .

69


:( )

Levenspiel, P 230, Fig. E9.4a,b.

C A0 ( area) (4 mol / lit )(0.405 lit.min/mol ) 1.62 min

V FA0 (area) (1000 mol/min)(0.405 lit.min/mol ) 405 lit

70


)(:

: .
71

Levenspiel, P 231, Fig. E9.4c.


: :
( .

( 25 C

X A 0.8

1 kg lit

FA0 1000 mol min C A0 4 mol lit

H r 18000cal mol C p 1000 cal kg.K

CpA :

1000 cal 1 kg 1 lit

cal
.
.
250
kg.K
lit 4 mol A
mol A.K

72

C pA


)(:

rA CA0=4 mol/lit .
XA=0.8:

rA 0.4
:

V
X
A
FA0 rA
0.8
2000 lit
0.4
73

V 1000


)(:

(250 cal / mol A.K

1 1

K
18000 (cal / mol A) 72

Cp
H r

slope

.
XA=0 .

TB 4.4 C

Levenspiel, P 232, Fig. E9.5a.

74


)(:
) (25 C
.

QAB (250 cal / mol A.K )(20 K ) 5000 cal / mol A fed
(5000 cal / mol A)(1000 molA / min) 5000000 cal/min

) (62 C ) (25 C.
:

QCE (250)(37) 9250 cal / mol A fed

(9250)(1000) 9250000 cal/min

75


)(:

)(

)(

.

.

Q T .

: Q .

76




.
.
.

.
.
.

77

A R .

):(Instantaneous Fractional Yield

dCR
dC A

R
A

):(Overall Fractional Yield

in reactor

CRf
C A

CRf
C A0 C Af

A
\ \faI
\ \faI

78

k1 k2
:
k1 k10 e E1 / RT k10 ( E1 E2 ) / RT
( E2 E1 ) / RT

e
k2 k20e E2 / RT k20
E1 E2 k1 k2 :

k1/k2 E1>E2
k1/k2 E1<E2

:
.

79


:

.

E1
k 1> k 2
E2

ln k

k 2> k 1
1/T

80



.
E1>E2 .

Desired product

Unwanted product

k1 R

A k2
S

E1<E2 .

R .

k2

k1

A
R S

E1>E2 .
E1<E2 .
81

- ) (

:
.

Rdesired
Where E1>E2, E1<E3

2
3

T
E1>E2 .
E1<E3 .
:

E3 E1 k30
1
R

ln

Topt E3 E2 E1 E2 k20
82

83

- ) (
:
.
.



: :

: :

84

85


- Levenspiel O., Chemical Reaction Engineering. 3rd ed., John Wiley & Sons: New York, 1999.
- Fogler H. S., Elements of Chemical Reaction Engineering. 4th ed., Prentice-Hall, 2005.
- Froment, G.F., K.B. Bischoff, and J. De Wilde, Chemical Reactor Analysis and Design. 3rd ed.,
Hoboken, N.J., Wiley, 2011.
.

1391-2

86