Phase Equilibria and Drying

Rates

Wet solids
Liquid
Hot air
Material
Moisture
Hot

air

Material

Liquid Necessary condition: pw p

Material
Hot air
Liquid
Driving force
( p p) 0
w

Hot air

Questions: Will (pw-p) remain constant or change during

drying process?
What is the final result(equilibrium) of drying process?
In addition to air conditions, the equilibrium is related to the
property of wet solids.
2

1.Phase Equilibria[Reading: pp.779~782]

Types of water in wet solids:
1)Adsorption water: Characteristic: pw=ps
pw=water vapor pressure on the surface of wet solids;
ps=saturated vapor pressure exerted by liquid water at the
same temperature with pw.
2)Capillary water:
a)Non-hygroscopic substances(or in large
capillary): Characteristic: pw=ps
b)Hygroscopic substances: Characteristic: pw<ps
3)Swelling water: In cell walls.
3

(1)Equilibrium water(moisture) and Free

water(moisture); Equilibrium-moisture curves

Wet solids
Liquid
Hot air
Material
Moisture
Hot air

Material
For air of definite humidity(definite vapor
Liquidpressure), because of fine capillary effect,
Material
liquid water exerts an abnormally low
LiquidHot air
vapor pressure because of the highly
Hot air concave curvature() of the surface, pw
getting lower an lower.

When pw=p, N=0X=X*. Here, X* is the equilibrium water

content
4

Water corresponding to concentrations lower than X*

can not be removed by drying.
Free water(moisture) :
The difference between the total water content of the
solid and the equilibrium water content.
Free water X=total water XT - equilibrium water X*
Equilibrium-moisture curves: Relationship of X*~ ,
under certain temperature (Figure24.3 or figure 5-10).

Factors influencing X*:

1)Kinds of solids: X*hygroscopic > X* non-hygroscopic
2)Air conditions: X*
t X*
(2)Bound and unbound water
Bound water
Characteristic: pw<ps (Water in wet solids exerts a vapor
pressure less than that of liquid water at the same
temperature.)
Bound water may exist in several conditions. 1)In fine
capillaries, because of the highly concave curvature of the
surface; 2)In cell or fiber walls, because of solids dissolved in
water; 3)In natural organic substances,
6

3)In natural organic substances, because water is in

physical and chemical combination, the nature and

strength of which(combination) vary with the
nature and moisture content of the solid
Unbound water. Characteristic: pw=ps. Water is
largely held in the voids of the solid(nonporous
particles, etc.), strength of combination of water and
solid is weak.

The distinction between bound and unbound

water only depends on the material itself.
7

Determining the bound and unbound water (Refer to

Figure 5-11)
If an equilibrium curve is continued to its intersection with
the axis for 100% percent humidity, water corresponding to
concentrations lower than that indicated by the intersection of
the curve with the line for 100 percent humidity is bound
water, water corresponding to concentration greater than that
indicated by the intersection is unbound water. Why?
Because, = 100% means p=ps, corresponding to pw=ps when
in equilibrium;
If <1, pw=p<ps when in equilibrium;[bound water]
If =1, pw=p=ps when in equilibrium.[unbound water]

Relationship among total water, equilibrium and free

water, bound and unbound water(Fig.5-11)

Total water content

Bound waterBound water

Bound water
Bound
water water
Unbound water
Unbound
Unbound water
Equilibrium water
Unbound
water
Equilibriu
m
water
Equilibrium water
Free water
Equilibriu
m
water
Free water
Free water
Free water

2.Drying curves and drying rate curves under

constant drying conditions [Reading: pp.782~788]
(1)Constant drying conditions.
Assume that the temperature, humidity, and velocity and
direction of flow of the air across the drying surface are
constant. This is called drying under constant drying conditions.
For example, when small amount of materials(wet solids) is
dried by large amount of air, conditions in the air-stream can
be considered as constant.
(2)Drying experiment and drying curves

10

t0 , H 0

(2)Drying
experiment
and
drying
curves

Thermocoup
le
(
for

)
t0 , H0
QP
Thermocoup
le( for

Moist
air

Moist air
Thermocoup
leu( for( for
) W
QP
Balance
( for
W ) Balance

preheater
t0 , H 0
Moist
air

preheater
Balance
ule
Thermocoup
(
for

Stopwatch(u for (for

) WW ) ( for
Stopwatch
W
QP
preheater
air

u
Stopwatch
( for
W
( for W )air
t1 , H1 )
Moist air
Moist
air

Balance

H
Materialu airMaterial
t
,
t2 , H 2
1
1 )
Stopwatch
preheater ( for
tpreheater
0, H0
Dryer
W
t0 , H 0 t , H Dryer Material
2
2
u air
u air
Q
P
Dryer t1 , H1
QP
Material
Material
u

t2 , H 2
u
Dryer
Dryer
W
W
dW W
U

[kg water /(m 2 s)]

t1 , H1 rate U:
Drying
t1 , H1
Sd SW

dW
2
t2 , H 2
U

[
kg

/(
m
s)]
t 2 , Hunder
2 t t constant

How to keep the dryer

drying conditions

dW 2
W
1
Sd
U
H H S[kg /(m 2 s)]
2
1
t

t
Sd

2
1
large amount of air versus small amount of materials:
t 2 t1 H 2 H1
H 2 H1

11

Drying curves: X~, ~ (Figure 5-12)

[Here, =drying time h]
(3)Drying rate curves and drying process of solid materials
Definition of drying rate U:

dW W
U

[kg water /(m 2 s)]

Sd
S
t 2 t1
GdX
dW GdX ,U
(5 46)
Sd
H 2 H1
Drying rate curves: X~U curve (Figure 5-13)

12

Drying rate curve: X~U curve (Figure 24.6)

Falling rate period Constant-rate
period

Falling rate
Falling
period
rate period
UC

Three periods of
drying process:
AB
BC
CDE

UC
U

13

ABPreheating period
BCConstant-rate period
CDEFalling-rate period. CD: First falling-rate
period(some fraction of solid surface become dry); DE:
Second falling-rate period(air-water interface recedes).
Falling rate

period

Constant-rate period

Falling rate
Falling
period
rate
UC

UC
U

14

period

(4)Drying mechanism of wet solids and the influencing factors

1)Constant-rate period (Period of controls of surface water
vaporization[BC]
Characteristics: drying rate Uc unchanged, solid very wet(a
continuous film of liquid exists over the entire external
surface), solid surface temperature tw,

tH unchanged t t w
, andH s ,tw Hconst

dW
UC K

50s
[Ut t w
k5H( H
H H stw H
,tw H )
rtw
Sd
dW
dQ S (t t w ) d
[U
k H ( H s ,tw H ) dW

]
Sd
rtw
rtw
S (ttoEqs.(24.9),(24.10),(24.13).
t w ) d
dQ
Eq.(5-50)
is equivalent
dW

] 15
rtw
rtw

[1)Constant-rate period]
Water vaporized is unbound water.
Factors influencing drying rate:
(a)Air conditions(tH);
(b)Air velocity;
(c)Patterns of air-solid interaction in dryers(method
of contacting the solids and air).
Three basic patterns of air-solid interaction in
dryers: (a)air flow is parallel to surface of solids;
(b)air flow is perpendicular to surface of solids;
(c)solids (particles) suspended in air.
16

2)Drying in the falling-rate period (period of

controls of water diffusing from interior to solid

surface)
Characteristics: Water diffusing rate from the solid
interior to surface is less than rate of surface vaporization,
therefore, rate of drying U decreases gradually.
Factors influencing drying rate U:
Mainly the structures and sizes of materials.
Air conditions dont influence much, but air temperature
has certain effect, such as (t-) is heat transfer driving
force. If t is very high, material is deformed easily.

17

(5)Critical water(moisture) content XC and its

influencing factorsXC
The point XC at which the constant-rate period ends is
called the critical water content.
If the initial moisture content of the solid is below the
critical moisture content, there will be no constant-rate
period.
XC is influenced by the property and thickness of material,
and the drying rate.

1) X C ,hygroscopic X C ,nonhygroscopic

2Thickness of material X C
3) Drying rate U X C
( falling rate period comes early).
18

Methods for increasing rate of drying U:

H
t t w
H sConstant-rate
,tw H
1)Drying
in the
period

U C K
t t w
5 50
H H stw H
rtw
a) , k H (uair ) U

) Ub
t t , ( H H ) ( such as t , H ) U
w
s ,tw
( H s ,tw H
) ( such method
as t of
, Hcontacting
) U solids and air(such as particles
c)Improve

ir

3) k
k
suspended in air)

2)Drying in the falling-rate period

a)Decreasing thickness of material;
bt (before material is deformed).
19

UC
X
3.Calculation of
XC

drying time under constant

drying conditions [Reading:
788~790]
O
U [kg /(m 2 s )]
O

Falling-rate period

X [kg / kg
]B
O
A

Constant-rate period

A
B

O A
C
UC
OO
BB
A
C AA

D
C
X
UBC C
D BB
E
D
XC C D
C
X
E
X
C
1
2
U
E
E
C
D
U [kg
/(m s )]
D
X
X1 E D
U CC XX11
XX 2
X [kg
]
E / kg
2
X 2 X 1E
O UX[kg
/(mX
s )]
2
XX2
C
X1
X 2X
2

A X
X[Ckg
water
/
kg
bone

dry
solid
U
[
kg

/(
m

s
)]
1 ]

X2

X2
B U [
kg
/(m 2X [skg
)] /20kg]

UC

(1)Drying time of constant-rateXperiod 1

XC

GdX
G
UC
d
dX
Sd
UC S

U [ kg /(m 2 s )]

O
Falling-rate period

X [ kg / kg
]B Constant rate period
O

A
A
O A
B OO
C
UC
B
B
A
C AA
D
C
X
BC C
U
D BB
E
X C C D
D
X
E CC
X1
2
U
E
E
C
D
U [ kg
D /(m s )]
X
X

X
C
1
X11
UC X
ED
X 2
X [ kg

]
E / kg
2
X 2 X 1E
O U
/(mX
s )]
X
X[ kg
2
X
C
X1 2
X 2X
2

A X
X[Ckg
water
/ kg
bone
solid
U
[ kg
/(m
s )] dry
1 ]

X2

X2
B U [
kg
/(m X [skg
)] / kg]

C X [ kg / kg]

G
Integration : 1
dX
UC S
X1
XC

G
1
( X 1 X C ) (5 51) [Similar to Eq.(24.16)]
UC S
E

X1

UC is determined by drying rate curve or

by the following
X

equation:

UC

rtw

(t t w ) k H ( H s
,tw H )

is determined by Eqs. (5-52),(5-53),(5-54) (p.271).

21

GdX
G
(2)Drying time of falling-rate period

X
2
U
d
X
UC

Sd
O
A
O
X
X [ kg / kg
]B 2
O
G
dX A
A
O A
B
B C
U
A 2B
DS
U C
C
X
XC
B C
U

SU

GdX
G
U
d
dX
Sd

SU

G
dX
G

G
dX
G
X
U
d
dX
U

G 2

dX
dX
SU
Sd
SU
2 Sd

X
X
S
U

G
X C dX

G
dX
22

X
U
U
1)U SS~ X
X

U [ kg /(m 2 s )]

Falling-rate period

Constant rate period

OO
AA
BB

C
D
E
D
D
C
X 2
E CC
X1
U
E
E
D
U [ kg
D /(m s )] C
X
X1 E D
X11
U CC X
XX 2
X [ kg
]
E / kg
2
X 2 X 1E

O U
/(
m

s )]
X
X
X[ kg
2
X
C
X1 2
X 2X
2

A X
X[Ckg
water
/ kg
bone
solid
U
[ kg
/(m
s )] dry
1 ]

X2

X2
B U [
kg /(m X [skg
)] / kg]

C X [ kg / kg]

X
D

XC

2
2

1)U ~ X

C
C
1)If the relation
of U~X is non-linear,
drying
2
U time
k ( X of
X )[
1
))

E
1falling-rate
U
U~
~X
X

period 2 5is 10determined

by graphical
X2
G
dX
X
5-10).
integration
(Example

10

10

2U k ( X X )[]

X
1

2
If UUXk2kX X( X
( XXX )[)[
linear]]
2

G
dX

Here,

2 G XX

dX

G
dX
S
k
(
X

X
)
2
X
X

S
S

kk XX (( X
X
X
X ))

UC 0
, k U

0
U

0
C
C

,
k

X
, k C

X
X CC

XC

(
X

X
)
X

UC 0
kX
XC X

2
2

22

G X C X X C
2
ln

G dX
GU
U
d X dX
Sd
SUX U U GdX d G d
SU
X
X2
(2)Drying time
of fallingOSd
U [ kg /(Xm s )] Falling-rate
G dX
O
AGO X dX
rate
period

O
2 G

2
dX
G
period

X
[
kg

/
kg

U [ kg /(
m
)]
O s
G dXS dU G dX
rate O
A
A
U
2 O B Constant
A
U

dX
XC
X [ kg
O
OA/ kg
S]
U
C

Falling-rate period

period
A
B X
Sd
SU
B
C
Sd
SU
UC
OO
BB O AA C
B
C
B
C OAOA
D
B
1)GU XX~22 dX
X X UA C1C)A
C AA
G
dX
X
BC UB CC U ~DX
U
B
D
E
22

D B BB
E

D
XC C
D
D

X
C
C D

5 10
S
X
X
E C CC 5
E
S XC U
U
EE 2 EE UX UX
Constant rate period

DD
U [/(
kgm

D /(
U [ kg
m
s )] sC)]1 X
D
X
X
C
1
X1
U X
X
X 1 EEDD
X 2X 2]

X [CCkg
/
kg

X
U
E
X
X
1
2
1
2
U]
k ( X XXX2 X E)[
1
U
X [ kg
kg
2
k X ( X X )[
U
[kg
X /(
EO/]
X
X
1))

U~
~X
XU

2 mX s )] X
2
X

O UX[Akg

/(
m

s
)]
X
2 XX 1E
X
2X [1kg
X 2X

C U

X1 ]
water
/
kg
bone

dry
solid
[
kg

/(
m

s
)]

X1 X 2
X2 2

X
X

X2X
water
/Xkg
bone
dry
solid
[skg
/ kg
]
[m
kg
/(m
s )] dX
U [
kg
U
/(
)]

2 1 ]
G

10
10
A XXXB[Ckg

G 2
dX 55

2X/kg
kg

] ]

X
B UC
[skg
/ kg
2X [
[
kg
/(
m
)]
2

S
k
(
X

X
)
2

If
U

k
(
X

X
)[
linear
]

D
Here,

2U kSX X( X kXX( X)[

]
C X [kg / kgX]C X
X
)

XC
E

X
2
D

X1
UC 0
X 2
G
dX
G
dX
UC 0
X 2k X
22

SS, kX kk X (( X
X

X
)

C
X)
X1
XX X
XC
C
X

X2

X
XC
G
U

0
C
U

0
C

C
2

ln

,, kk
G X C X
X

X
C
S57a ) U C
X2
2 X
X
ln

(
5

X CC

XC

X
G

X
G
C

C
ln
22

ln
S
U
S
U CC

X 2 X

X
X CC
X
X (5 57a )
(5 57a)

23
X
1
2

X 22
X
X

XC C X

U CG 0 X C X X C X
,
k 2 G X C X ln X C X (5 57a )
S X UC
X 2 X (5 57a )
X

ln
C
2
(3)Total time S
of drying
T
U
X

X
C
2

XC X
G XC X
2 ln(Continuous
(5 57a)
operation)
TS
1U 2
X2 X
C
1

1
2 2
T 1 2 l &d Batch operation
1
2

T 1Where,
2 l &d

=loading and discharging time

24

XC

UC 0
1)
U ~, X

X
C

5 10

X drying
*4.Calculation of drying2
timeUunder
constant

X C ]
X
G
C X )[

k
(
X

X
2

ln
conditions
XS
UC
X2 X

G 2
dX
2 Problem

Assignments: Problem 24.2;

5-8 or 24.4?
S XC k X ( X X )
Key to Problem 24.2:
T 13U
.5Ch 0
, k

X
1 C 2

Hint of Problem 5-8:

U G(t Xt wC ) X X C X
2 rtw
ln

S
UC
X2 X

1.17( L) 0.37

(5 53)

T 4 .0 h
1 2

Hint of Problem 24.4:

1)Assume
constant
enthalpy
Key to Problem 24.4:

drying process; 2)U is linear in X in falling-rate period.

25

Exercises
1.Is critical water(moisture) content XC the
distinction point between bound and unbound water?
2.In order to increase the rate of drying of materials
mainly containing bound water, must the air velocity
be increased
3.When water in the wet solids is in equilibrium with
the air, what is the relationship between the water
vapor pressure of the solid surface and the partial
pressure of water vapor in the air?
4. What are the equilibrium water contents of kaolin
and wool X* when relative humidity is 60%?
26

5.The air temperature leaving the dryer t2 is

_____________ greater than the entrance air
adiabatic saturation temperature of the dryer tas,
for the purpose of
.
6.Would you explain the relationships among t, tw,
tas, and td?
7.Are the water vapor pressures of different wet
solids all the same when in equilibrium with the air
in the same room? ______. Are their water contents
all the same? _____. Are their temperatures all the
same? _______.
27

8.Some wet solids are dried by air

with temperature t and humidity U C
H. The simplified drying rate
X
UC
curve is showed by the attached X C
figure. Please draw the new dryingU [kgUC /(mX2 s)]

X
rate curves under following drying X [kg / kgX
C
]
X C U [kg /(m 2 s )]
conditions relative to the position
2
X [/(kg
kg]
U [kg
m
s/ )]
of original drying rate curve:
X [kg / kg]

28

(1)Air velocity increases and air temperature t and

humidity H keep unchanged.
(2)Air velocity and temperature unchanged, and
humidity increased; or air velocity and humidity
unchanged, and temperature decreased.
(3) Air velocity and air conditions keep unchanged,
but thickness of materials increases.
(4) Air velocity and temperature unchanged, and
humidity decreased; or air velocity and humidity
unchanged, and temperature increased.
29