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CHE461

SOLID-FLUID OPERATION DRYING

Drying may be defined as the vaporization and removal of water or other

liquids from a solution, suspension, or other solid-liquid mixture to form a dry
solid. Drying is a complex process that involves simultaneous heat and mass
transfer, accompanied by physicochemical transformations. Drying occurs as
a result of the vaporization of liquid by supplying heat to wet feedstocks,
granules, filter cakes and so on. This definition of drying excludes conversion
of a liquid phase into a concentrated liquid phase (evaporation), mechanical
dewatering operations such as filtration, centrifugation, sedimentation,
supercritical extraction of water from gels to produce extremely high porosity
aerogels (extraction) or so called drying of liquids and gases by use of
molecular sieves (adsorption). Phase change and production of a solid phase
as end product are essential features of the drying process. Mass transfer is in
the direction solid to fluid, so that it is a special case of desorption.
Drying is an essential operation in the chemical, agricultural, biotechnology,
food, polymer, ceramics, pharmaceutical, pulp and paper, mineral processing
and wood processing industries. Drying is perhaps the oldest, most common
and most diverse of chemical engineering unit operations. It is often the final
operation in a manufacturing process, carried out immediately prior to
packaging or dispatch. Drying operations often follow evaporation, filtration or
crystallization. Drying of various feedstocks is needed for one or several of the
following reasons:

1. The need for easy to handle free flowing solids

2. Preservation and storage
3. Reduction in cost of transportation, and
4. Achieving deserved quality of product etc.

Improper drying may lead to irreversible damage to product quality and hence
a non-sellable product.
Heat transfer and mass transfer are critical aspects in drying processes. Heat
is transferred to the feedstock to evaporate liquid and mass is transferred as a
vapor into the surrounding gas. The drying rate is determined by the set of
factors that affect heat and mass transfer. Solids drying is generally
understood to follow two distinct drying zones known as the constant-rate
period and the falling-rate period.

1
The two zones are demarcated by a break point called the critical moisture
content. In a typical graph of moisture content versus drying rate and moisture
content versus time (see figure 4.1), section AB represents the constant rate
period. In that zone, moisture is considered to be evaporating from a saturated
surface at a rate governed by diffusion from the surface through the stationary
air film that is in contact with it. This period depends on the air temperature;
humidity and speed of moisture to the surface, which in turn determine the
temperature of the saturated surface. During the constant rate period, liquid
must be transported to the surface at a rate sufficient to maintain saturation.

At the end of the constant rate period (point B in figure 4.1), a break in the
drying curve occurs. This point is called the critical moisture content, and a
linear fall in the drying rate occurs with further drying. The segment BC, is
called the first falling period. As drying proceeds, moisture reaches the surface
at a decreasing rate and the mechanism that controls its transfer will influence
the rate of drying. Since the surface is no longer saturated, it will tend to rise
above the wet bulb temperature. The section represented by segment CD in
fig. 4.1 is called the second falling-rate period, and is controlled by vapor
diffusion. The capacity of the air (gas) stream to absorb and carry away
moisture determines the drying rate and establishes the duration of the drying
cycle. The two elements essential to this process are inlet air temperature and
air flow rate. The higher the temperature of the drying air, the greater its vapor
holding capacity since the temperature of the wet granules in a hot gas
depends on the rate of evaporation, the key to analysing the drying process is
psychrometry defined as the study of the relationships between the material
and energy balances of water vapor and air mixtures.

Drying occurs by effective vaporization of the liquid by supplying heat to the

wet feedstock. Heat may be supplied by convection (direct dryers), by
conduction (contact or indirect dryers), radiation or volumetrically by placing
wave or radio frequency electromagnetic field. Over 85 percent of industrial
dryers are of the convective type with hot air or direct combustion gases as

2
the drying medium. Over 99 percent of the application involve removal of
water.

Drying Theories
Diffusion theory of drying and capillary theory of drying are two theories used
to describe the physical nature of the drying process. Drying of solids in
considered to occur in two stages, a constant rate period followed by a falling
rate period.

In the constant rate period, the rate of drying corresponds to the removal of
water from the surface of the solid, while the falling rate period corresponds to
the removal of the water from the interior of the solid.

The diffusion theory explains that the rate of drying is governed by the rate of
internal movement of the moisture to the surface and that this movement was
assumed to be a process of diffusion and would follow the same Laws as heat
transfer. It is also noted that period and the falling rate period are diffusion
control. In the constant rate period moisture vaporizes into the air stream and
the controlling factor is the transfer coefficient for diffusion across the gas film.

The capillary theory was proposed to explain that the forces controlling the
movement of water are capillary in origin, arising from the minute pore spaces
between the individual particles. This is in consideration with different
materials with different packing arrangement in their cubic structures such as
cubic packing arrangement, Rhombohedral packing and so on. The drying
rate may now be governed by the pore spaces and sizes within the molecules.
The rate of drying however is dependent on a number of factors which
includes the air wet and dry bulb temperatures, flow rate of air, the solid
characteristics and the nature or features of the dryer.

Rate of Drying
Equation for the calculation of the rate of drying in the constant rate period is
given as

W = KGA (Ps – Pw) 4.1

Where

KG = Mass transfer coefficient

Ps = Vapour pressure of the water
Pw = Partial pressure of water vapour in the air stream.

Since the rate of transfer depends on the velocity U of the air stream raised to
a power of about 0.8, them the mass rate of evaporation is:

W = KGA (Ps – Pw) U 0.8 4.2

3
In all drying equipment, care must be taken to ensure that the air or gas used
does not become saturated with moisture at any stage, hence rate of drying in
the constant rate of drying in the constant rate period is given as.

W = dw = hA∆ T = KG A(Ps – Pw) 4.3

dt λ

Where
W = is the rate of loss of water
h = the heat transfer coefficient from air to the wet surface.
∆ T = the temperature difference between the air and the surface,
λ= the latent heat of vaporization per unit mass.
KG = the mass transfer coefficient for diffusion from the wet surface through
the gas film
A = the area of interface for heat and mass transfer and (Ps – Pw) = the
difference between the vapour pressure of water at the surface and the
partial pressure in the air.

Use of rate drying curve in estimating drying time

If a material is dried by passing hot air over a surface which is initially wet, the
rate of drying can be represented by a curve BCE as shown in figure 2.

Where
w = the total moisture
we = equilibrium moisture content (Pt E)
w – we = the free moisture content
wc = the critical moisture content (point C)

For constant-rate period

During the period of drying from the initial moisture content wI to the critical
moisture content wc, the rate of drying is constant, and the time of drying t c is
given by:

tc = wI – wc 4.4
RCA

Where

4
 RC is the rate of drying per unit area in the constant rate period and
A is the area of exposed surface.

For falling-rate period

During this period the rate of drying is, approximately, directly proportional to
the free moisture content (w – we), or

- 1 dw = m(w – we) = mf 4.5

A dt
w
Thus; 1 dw tf
∫
- m.A we (w – we) = o dt ∫
Or

1 In wc – we = tf
mA w – we

and
tf = 1 In fc 4.6
mA f

since f = (w – we).

the total time t of drying from W1 to w is given by t = (tc + tf). The rate of drying
Rc over the constant rate period is equal to the initial time of drying in the
falling rate period, so that

Rc = mfc

Thus: tc = (w1 – wc) 4.7

mAfc

and the total drying time, t is

t = (w1 – wc) + 1 In fc
mAfc mA f

= 1 (f1 – fc) + In fc 4.8

mA fc f

5
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Example 4.1
A wet solid is dried from 25 to 10 percent moisture under constant drying
conditions in 15ks (4.17hr). if the critical and the equilibrium moisture contents
are 15 and 5 per cent respectively, how long will it take to dry the solid from 30
to 8 per cent mositure under the same conditions?

Solution
For the first drying operation

wI = 0.25kg/kg,
w = 0.10kg/kg, wc = 0/15kg/kg
we = 0.05kg/kg
Thus

fI = (wI – we) = (0.25 – 0.05) = 0.20

fc = (wc – we) = (0.15 – 0.05) = 0.10kg/kg
f = (w – we) = (0.10 – 0.05) = 0.05kg/kg

from equation 4.8, total drying time is;

t = (1/mA) [(f1 – fc)/fc + In (fc/f)]

15 = 1 [(0.20-0.10)/0.10+In 0.10 ]
mA 0.05

and mA = 0.0667 (1.0 + 0.693)

= 0.113kg/s

For the second drying operation:

wI = 0.30kg/kg, w = 0.08kg/kg,
wc = 0.15kg/kg and we = 0.05kg/kg

Thus:
fI = (wI – we) = (0.30 – 0.05) = 0.25kg/kg
fc = (wc – we) = (0.15 – 0.05) = 0.10kg/kg
f = (w – we) = (0.08 – 0.05) = 0.03kg/kg

from equation 4.8, total drying time is;

t = (1/mA) [(f1 – fc)/fc + In (fc/f)]

15 = 1 [(0.20-0.10)/0.10+In 0.10 ]
mA 0.05

6
and mA = 0.0667 (1.0 + 0.693)
= 0.113kg/s

For the second drying operation:

wI = 0.30kg/kg, w = 0.08kg/kg,
wc = 0.15kg/kg and we = 0.5kg/kg

Thus:

fI = (wI – we) = (0.30 – 0.05) = 0.25kg/kg

fc = (wc – we) = (0.15 – 0.05) = 0.10kg/kg
f = (w – we) = (0.08 – 0.05) = 0.03kg/kg

the total drying time is then;

t = (1/0.113)[(0.25 – 0.10)/0.10 + In 0.10

0.03
= 8.856(1.5 + 1.204)

t = 23.9ks (6.65hrs)

Example 4.2

A granular material containing 40 per cent moisture is fed to a countercurrent

rotary dryer ar a temperature of 295k and is withdrawn at 305k containing 5
percent moisture. The air supplied which contains 0.006kg water vapor/kg dry
air enters at 385k and leaves at 310k. the dryer handles 0.125kg/s wet stock.
Assuming that radiation losses amount to 20 KJ/kg dry air used, determine the
mass flow rate of dry air supplied to the dryer and the humidity of the exit air.
The latent heat of water vapor at 295k = 249kj/kg specific heat capacity of
dried material = 0.88kj/kg, the speicifc heat capacity of dry air = 1.00kj/kg k,
and the specific heat capacity of water vapour = 2.01kJ/kgK.

Solution
This example involves a heat balance over the system 273k will be chosen as
the datum temperature and it will be assumed that the flow rate of dry air = G
kg/s

Heat in:
(a) Air
G kg/s dry air enter with 0.006
G kg/s water vapor and hence the heat content of this stream = [(1.00G) +
(0.006 G x 2.01)](385 – 273) = 113.35 G KW

7
(B) Wet Solid
0.125kg/s enter containing 0.40kg water/kg wet solid, assuming the moisture
is expressed on a wet basis.

Thus:
Mass flowrate of water = (0.125 x 0.40)
= 0.050 kg/s
And Mass flowrate of dry solid = (0.125-0.05)
= 0.075kg/s

Hence:
The heat content of this stream
= [(0.050 x 4.18) + (0.075 x 0.88)] (295 – 273)
= 6.05KW

Heat out:
(a) Air
Heat in exit air = [(1.00G) + (0.006G x 2.01)](310 – 273)
= 37.45G KW.

Mass flowrate of dry solids = 0.075kg/s containing 0.05 kg water/kg wet solid.
Hence:

Water in the dried solid leaving = (0.05 x 0.075)/(1 + 0.05)= 0.0036

and
The water evaporated into gas stream = (0.050 – 0.0036) = 0.0464kg/s

Assuming evaporation takes place at 295K, then:

Heat in the water vapor
= 0.0464 [(2.01 (310 – 295) + 2449 + 4.18 (295 – 273)]
= 119.3KW

And
The total heat in this stream = (119.30 + 37.45G) kW

(b) Dried Solids

The dried solids contain 0.0036kg/s water and hence heat content of this
stream is:

= (0.075 x 0.88) + (0.0036 x 4.18)

(305 – 275)

= 2.59KW

8
(c) Losses
These amount to 20KJ/kg dry air or 20m kW

Heat balance
(113.35G + 6.05) = (119.30 + 37.45G + 2.59 + 20G)

G = 2.07kg/s

And
Water in the outlet air stream = (0.006 x 2.07) + 0.0464 = 0.0588kg/s
and
The humidity = (0.0588/2.07)
= 0.0284kg/kg dry air

Classification of Dryers
Dryers can be classified based on the following criterion:

Criterion Types
1. Mode of operation Batch or continuous

2. Heat input type convection conduction, radiation,

Electromagnetic folds,
combination of heat transfer
modes, Adiabatic or non-
adeabative

3. State of material in dryer Stationary, Moving agitated,

dispersed

4. Operating pressure Vacuum, Atmospheric

5. Drying Medium (Convection) Air, Superheated steam,

fluegases

6. Drying tempeature Below boiling temperature, above

boiling temp, Below freezing point

7. Relative motion btw. Drying Co-current, Countercurrent,Mixed

Medium & Solids flow

8. Number of stages Single, Multistage Short (<1min),

Medium (1 -60min) Long (>60min)

9
Types of Dryers
Dryer classification or types can be based on the mechanism of heat transfer
as follows.

1. Direct (Convective)
2. Indirect or contact (conduction)
3. Radiant (radiation)
4. Dielectric or microwave (radio-frequency) drying.

Direct or Adiabatic dryers are the type where the solids are dried by direct
contact with gases, usually forced, air. With these dryers, moisture is on the
surface of the solid. The units uses the sensible heat of the fluid that contacts
the solid to provide the heat of vaporization of the liquid.
With adiabatic dryers, solid materials can be exposed to the heated gases
through various methods, some of which are:

1. Gases can be blown across the surface (cross circulation)

2. Gases can be blown through a bed of solids (through circulation). Used
when solids are stationary, such as wood, corn and others.

3. Solids can be dropped slowly through a slow-moving gas stream as in a

rotary dryer.

4. Gases can be blown through a bed of solids that fludized the particles.
In this case, the solids are moving as in a fluidized-bed dryer

5. Solids can enter a high-velocity hot gas stream and can be conveyed
pneumatically to a collector (flash dryer).

Contact dryers or Non-adiabatic involve an indirect method of removal of a

liquid phase from the solid material through the application of heat, such that
the heat transfer medium is separated from the product to be dried by a metal
wall. Heat transfer to the product is predominantly by conduction through the
metal wall and the impeller. Hence these are also called conductive dryers.

Although more than 85% of the industrial dryers are of the convective type,
contact dryers ofter higher thermal efficiency and have economic and
environmental advantages over convective dryers. For convective dryers, the
heat transfer medium is in direct contact with the surface of the material to be
dried resulting in risk of cross contamination. In conductive dryers, this risk is
avoided as the heat transfer medium does not contact the product. Heat
needed to vaporize the solvent is transferred through a wall.

Dryers can also be classified as Batch or Continuous.

10
Batch Dryers
There are various types of batch dryers as described below.

(a) Tray dryers: This dryer types operates by passing hot air over the
surface of a wet solid that is spread over trays arranged in rocks. Tray
dryers are the simplest and least-expensive dryer type. This type is
most widely used in the food and pharmaceutical industries. The chief
advantage of tray dryers, apart from their low initial cost, is their
versatility. With the exception of dusty solids, materials of almost any
other physical form maybe dried. Drying times are typically long say
between 12 to 48 hours.

(b) Vacuum dryers: Vacuum dryers offer low-temperature drying of

thermolabile materials or the recovery of solvents from a bed. Heat is
usually supplied by passing steam or hot water through hollow shelves
drying times are long usually 12 – 48hours.

(c) Fluidized-bed dryers: A gas-fluidized bed may have the apperance of

a boiling liquid. It has bubbles, which rise and appear to burst. The
bubbles result in vigorous mixing. A preheated stream of air enters from
the bottom of the product container holding the product to be dried and
fluidizes it.

The resultant mixture of solids and gas behave like a liquid and thus the
solids are said to be fluidized. The solid particles are continually caught
up in eddies and fall back in a random boilding motion so that each
fluidized particle is surrounded by the gas stream for efficient drying
granulation or coating purposes. In the process of fluidization, intense
mixing occurs between the solids and air, resulting in uniform
condictions of temperature, composition and particle size distribution
throughout the bed.

(d) Freeze dryers: Freeze-drying is an extreme form of vacuum drying in

which the water or other solvent is frozen and drying takes place by
subliming the solid phase. Freeze-drying is extensively used in two
situation: (1) when high rates of decompostion occur during normal
drying and (2) with substances that can be dreid at higher temperatures,
and that are thereby changed in some way.

(e) Microwave Vaccum dryers: High-frequency radio waves with

frequencies from 300 to 30,000MHz are utilized in microwave drying
(2,450MHz is used in batch microwave processed). Combined
microwave – convective drying has be used for a range of applications
at both laboratory and industrial scales. The bulk heating effect of
microwave radiation causes the solvent to vaporize in the pores of the
material. Mass transfer is due majorly to a pressure gradient

11
 established within the sample. The drying regime is very useful for
drying temperature-sensitive materials. Microwave convective
processing typically facilitates a 50% reduction in drying time, compared
to vacuum drying.

Continuous Dryers
Continuous dryers are mainly used in chemical and food industries, due to the
large volume of product that needs to be processed. Most common are
continuous fluid-bed dryers other dryers depending on the product that can be
used in certain industries, for example rotary dryers, drum dryers, kiln dryers
etc. spray dryers are the most widely used in chemical, daing, agrochemical,
ceramic and pharmaceutical industries.

Spray dryers: The spray-drying process can be divided into four sections:
atomization of the fluid, mixing of the droplets, drying and removal and
collection of the dry particles. Atomization maybe achieved by means of
single-fluid or two-fluid nozzles, or by spinning-disk atomizers. The flow of the
drying gas may be concurrent or countercurrent with respect to the movement
of droplets. Good mixing of droplets and gas occurs, and the heat and mass
transfer rates are high. In conjunction with the large interfacial area conferred
by atomization, these factors give rise to very high evaporation rates. The
residence time of a droplet in the dryer is only a few seconds (5-30s) since the
material is at wet-bulb temperature for much of this time, high gas
temperatures of 1508 to 2.008oC may be used even with thermolabile
materials. For these reasons, it is possible to dry complex vegetable extract
such as coffee, milk products, and other labile materials without significant
loss of potency or flavor. The capital and running costs of spray dryers are
high, but if the scale is sufficiently large, they may provide the cheapest
method.

Dryer Design
We shall consider some useful equation necessary for dryer designs. During
drying, heat from the air stream could pass to the solid material during its fall
through the air stream and can also pass to the material from the hot walls of
the shell.
The mechanism of heat pasing through the air directly to the material may be
considered the most important.
The heat transfer equation may be written as:

Q = UaV ΔT 4.9

Where

Q= rate of heat transfer

U= overall heat transfer coefficient
V= Volume of the dryer

12
a= area of contact between the particles and the gas per unit volume of
dryer.
ΔT = mean temperature difference between gas

The combined group Ua has been shown to be influenced by the feed rate of
solids, the air rate and the propperties of the materials, and a useful
approximation is given by

Ua = kGin/D 4.10

Where k is a dimensional coefficient

Typical values for a 300mm diameter dryer revolving at 0.08 – 0.58Hz (5 – 35
rpm) show that n = 0.67 for specific gas rates in the range 0.37 – 1.86kg.m 2.
The coefficient k is a function of the number of flights and this is given to be
approximately as

K = 20(nf – 1) 4.11
Equation (4.11) was derived for a 200mm diameter dryer with between 6 and
16 flights.
Combinding equation (4.10) and (4.11), we have

Ua = 20 (nf – 1) G10.67/D 4.12

And hence for a 1m diameter dryer with 8 flights, Ua would be about

140W/m3K for a gas rate of 1kg/m2s.

For a rotary dryer, the hold-up is said to vary with the feed rate, the number of
flights, the shell diameter and the air rate for zero air flow, the hold-up
according to friedman and Marshall is given as:

X = 25.7F1 percent of dryer volume

SN0.9D

Where,

D, = diameter of the drum (m)

F = feed rate (m3/s m2)
S = slope of the dryer (m/m length)
N = rate of rotation (Hz) and
X = hold up expressed as a percentage of the drum volume.

Example 4.3
A flow of 0.35kg/s of solid is to be drived from 15 percent to 0.5 per cent
moisture on a dry basis. The mean heat capacity of the solid is 2.2KJ/kg deg
K and it is proposed that a co-current adiabatic dryer should be used with the
solids entering at 300k and because of the heat sensitive nature of the solids,

13
leaving at 325k. Hot air is available at 400k with a humidity of 0.01kg/kg dry air
and the maximum allowable mass velocity of the air is 0.95kg/m 2s. what
diameter and length should be specified for the proposed dryer?

Solution
For adiabatic drying, take the inlet air temperature to be 400k, humidity as
0.01kg/kg dry air, inlet wet bulb temperature as 312k. Assume number of
transfer unit to be 1.5 and hence the gutlet air temperature is given as To to be

1.5 = In (400 – 312)/(To – 312) and

To = 331.5k

The solid outlet temperature will be taken as the maximum allowable, 325k.
From steam tables,

 Latent heat of vaporization of water at 312k is 2410KJ/kg

 Specific heat capacity of water vapour is 1.88KJ/kg K
 Specific heat capacity of solid is given as 2.18KJ/kg K

For a mass flow of solids of 0.35kg/s and inlet and outlet moisture contents of
0.15 and 0.005 kg/kg dry solid respectively, the mass of water evaporated is =
0.35(0.15 – 0.005) = 0.0508kg/s

For unit mass of solids, the heat duty includes:

Heat to the solids = 2.18 (325 – 300) = 54.5KJ/kg

Heat to raise the moisture to the dew point = (0.15 x 4.187)(312 – 300) =
7.5KJ/kg heat of vaporization = 2410 (0.15 – 0.005) = 349.5KJ/kg heat to raise
remaining moisture to the solids outlet temperature
= (0.15 x 4. 187) (325 – 312) = 0.3KJ/kg and heat to raise evaporated
moisture to the air outlet temperature = (0.15 – 0.005) 1.88 (331.5 – 312)
= 5.3KJ/kg

A total of (54.5 + 7.5 + 349.5 + 0.3 + 5.3)

= 417.1KJ/kg
Or (417.1 x 0.35) = 146kW

From the chart of humidity – temperature, the humid heat of the entering air is
taken as 1.03KJ/kg K. Making a heat balance, we have.

G1 (1+#1) = Q/Cp (T1 – T2)

Where
G1 (kg/s) = Mass flowrate of inlet air
#1 (kg/kg) = humidity of inlet air

14
Q (kW) = heat duty
Cp (KJ/kg k) = humidity heat of inlet air

And T1 and T2 (k) are the inlet and outlet air temperatures respectively.
For this problem
G1 (1 + 0.01) = 146/(1.03 (400-331.5)
= 2.07kg/s
And
Mass flowrate of dry air,
Ga = (2.07/1.01) = 2.05kg/s

The humidity of outlet air is then #2 = 0.01 + (0.0508/2.05) = 0.0347kg/kg

At a dry bulb temperature of 331.5k, with a humidity of 0.0347kg/kg the air

from humidity temperature chart is 312k, the same as the inlet, which is the
case for adiabatic drying.

The dryer diameter is then found from the allowable mass velocity of the air
and the entering air flow and for a mass velocity of 0.95kg/m 2s, the cross
sectional area of the dryer is:
(2.07/0.95) = 2.18m2
Equivalent to a diameter of [(4 x 2.18) [ π ]0.5 = 1.67m

With a constant drying temperature of 312k.

At the inlet ∆ T1 = (400 – 312) = 88ok and at outlet ∆ T2 = (331.5 - 312) = 19.5ok
and the logarithmic mean ∆ Tm = (88 – 19.5)/In (88/19.5) = 45.5ok

The length of the dryer, L is then:

L = Q/(0.0625 π DG0.067∆ Tm)
Where D is diameter in metre and G is air mass velocity in kg/m 2s for this
problem,
L = 146/(0.0625 π x 1.67 (0.95)0.67 x 45.5
= 10.1m

This gives a length/diameter ratio of (10.1/1.67) = 6 which is a reasonable

value for rotary dryers.

Material and Energy Balances

Purposes includes:
1. Calculation of mass rate of water vaporization W
2. Calculation of mass rate of dry air required L
3. Calculation of mass rate of drying product G2
4. Calculation of heatduty
5. Providing basis for selection of blower, and calculation of heat transfer
area of pre heater and sizes of dryer.

15
Material and Energy Balance
Material Balance for countercurrent and also cocurrent dryers.

W = Mass rate of water vaporization kg/s

L = Mass rate of dry air kg dry air/s
G1 = Feed mass rate of moist solids kg moist solids/s
G2 = Mass rate of final moist solids (product), kg moist solid/s
G = Mass rate of bone dry solids kg/s
Material balance for water:
LH1 + GX1 = LH2 + GX2
L (H2 – H1) = G (X1 – X2)
W = L (H2 – H1) = G (X1 – X2) 4.12

(2) L(Mass rate of dry air required kg dry air/s)

L= W = G(X1 – X2) [kg dry air/s]

H 2 – H1 H 2 – H1

Dry air required per water vaporized:

L= L = 1 [kg dry air/kg water]

W H2 –H1

G2 (mass rate of moist solids out of dryer, kg moist solids/s)

G (mass rate of bone-dry solids,
G = G1 (1 – w1) = G2 (1 – w2)
Where w = mass of water per unit mass of moist solid (water content on the
wet basis),
Hence

W = Mass of water in moist solid x 100%

Total mas of moist solid

Also

X= mass of water per unit

Mass of bone-dry solid (water content on the dry basis)

16
Hence

X= Mass of water in moist solid x 100%

Mass of bone-dry solid in moist solid

In [kg water /kg bone-dry solid]

Heat balances

I11, I12 = KJ/kg bone dry solid

θ1, θ2 = feed and final solids temperature respectively in oC.

heat transfer rate input into preheater Qp (KW)

LIo + Qp = LI1 + Q1L

Where
Q1L = heat losses in preheater, kW (usually neglected)
Hence heat transfer rate input into preheater:

Qp = L (I1 – Io) 4.13

I = (1.01 + 1.88H) t + 2490H

and
H1 = H o

Qp = L (1.01 + 1.88Ho) (t1 – to) = LCHo (t1 – to)

L= 1 = 1 (kg dry air/kg water

H2-H1 H2-Ho

L = f(H2, Ho)

Thermal Efficiency of drying process

ʅ (efficiency) = heat for vaporizing

water Qv x100%

17
total heat required for drying Q

Qv = W (2490 + 1.88t2) – 4.187Wθ1

≈ W (2490 + 1.88t2)

Efficiency can also be given as

Q3
Q1 + Q2 + Q3 + Q4

Where
Q1 = 1.01 L(t2 – to)
Q2 = GCm (θ2 – θ1)
Q3 = W(2490 + 1.88t2)
Q4 = Q1

Dryer efficiency therefore is the ratio of the minimum quantity of heat that will
remove the required water to the energy actually provided for the process.

Methods for increasing efficiency

1. Increasing enthalpy increases efficiency

2. Partial circulation of waste air
3. Pay attention to insulation of drying equipment
4. Selecting advanced drying equipment, or using combining drying
technology
5. Air states when passing through the drying system e.g. through the
preheater, etc.

Adsorption (Definition)
The physical adherence or bonding of ions and molecules onto the surfaces of
another phase (eg reagents adsorbed to a solid catalyst surface)
It can also be defined as the adhesion of atoms, ions, or molecules from a
gas, liquid, or dissolved solid to form a thin film on the surface of a solid.
Adsorption is a surface-based process, the process creates a film of the
adsorbate on the surface of the adsorbent. For examples gases or dissolved
solutes that make water taste bad are strongly adsorbed on charcoal granules
in water filters.

Adsorption is present in many physical, natural, biological and chemical

systems and is widely used in industrial applications.

There are two types of adsorption pheomena, they are physical adsorption or
physisorption and chemical adsorption or chemisorption.

18
The phenomenon of physisorption or vander waals adsorption is reversible. It
is the result of intermolecular forces of attraction between molecules of the
solid and the substance adsorbed. Chemisorption or activated adsorption is
the result of chemical interaction between the solid and the adsorption
substance. The strength of the chemical bond (charateristics of covalent bond)
may vary considerably, and identifiable chemical compounds in the usual
sense may not actually form, but the adhesive force is generally much greater
than that found in pyhsical adsorption. Although the whole adsorption process
is exothermic, the heat liberated during chemisorption is usually large, of the
order of the heat of chemical reaction compared to the heat liberated in
physisorption.

Adsorbent
It is a substance usually a solid that collects molecules of another substance
on its surfaces.
Adsorbent solids are usually used in granular form, varying in size from about
12mm in diameter to as small as 50μm. Chemical nature of solids has much ot
do with its adsorption characteristics, though large surface per unit weight
seems essential to all useful adsorbents. Adsorptive ability of a material also
depends largely on empirical observation. Other characteristics of adsorbents
includes high abrasion resistance, high thermal stability and small pore
diameters, which results in higher exposed surface area and hence high
capacity for adsorption. They must also have a distinct pore structure that
enables fast transport of the gaseous vapors.

Most industrial adsorbents fall into one of three classes

1. Oxygen-containing compounds – typically hydrophilic and polar,
including materials such as silica gel and zeolites.

2. Carbon-based compounds – typically hydrophobic and non-polar,

including materials such as activated carbon and graphite

3. Polymer-based compunds – polar or non-polar functional groups in a

porous polymer matrix.

Silica gel
Silica gel is a chemically inert, non toxic, polar and demensionally stable
(<400oC or 750oF) amorphous form of SiO2. It is prepared by the reaction
between sodium silicate and acetic acid, which is followed by a series of after
– treatment processes such as aging, pickling etc. These after-treatment
methods results in various pore size distributions.

Silica is used for the drying of process air (e.g oxygen, natural gas)
contaminated with NO2 and adsorption of heavy (polar) hydrocarbons from
natural gas.

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Zeolites
Zeolites are natural or synthetic crystalline alluminosilicates, which have a
repeating pore network and release water at high temperature. Zeolites are
polar in nature. Zeolites are applied in drying of process air, CO 2 removal from
natural gas, CO removal from reforming gas, air separation catalytic cracking,
and catalytic synthesis and reforming.

Activated Carbon
Activated carbon is a highly porous, amorphous solid consisting of
microcrystallites with a graphite lattice, usually prepared in small pellets or a
powder. It is non-polar and cheap. One of its drawbacks is that it reacts with
oxygen at moderate temperatures (over 300oC). activated carbon can be
manufactured from carbonaceous materials, including coal (bituminous,
subbituminous and lignited, peat, wood or nutshells, (e.g. coconut). The
manufacturing process consists of carbonization and activation. Other
adsorbents includes Fuller’s earth’s (natural clay made of magnesium
aluminium silicate), Activated clays (chiefly bentonite), Bauxite (hydrated
alumena), Alumina (hard hydrated aluminium oxide) bone char, decolourizing
carbon, synthetic polymeric adsorbed, molecular sieve etc.

Adsorption Isotherms
These are plots of the equilibrium concentration of sample in the mobile phase
per unit volume vs the concentration in the stationary phase per unit length.

Adsorption is usually described through isotherms, that is the amount of

adsorbate on the adsorbent as a function of its pressure (if gas) or
concentration (if liquid) at constant temperature. The quanity adsorbed is a
function of the mass of the adsorbent to allow comparson of different
materials.

Isothern Models
There about fifteen isothern models developed to describe the adsorption
phenomena. We shall dwell on four most popular tones.

1. Linear adsorption isotherm

The linear adsorption isotherm otherwise known as Henry’s adsorption
isotherm is the simplest adsorption isotherm. It explain that the amount
of the surface adsorbate is represented to be proportional to the partial
pressure of the adsorptive gas. It formally resembles Henry’s Law;

X = KHP

20
Where X = surface coverage
P = partial pressure
KH = Henry’s adsorption constant

For solutions, concentration or activities are used instead of the partial

pressures.

The linear isotherm can be used to describe the initial part of many practical
isotherms. It is typically taken as valid for low surface coverages, and the
adsorption energy being independent of the coverage (Lack of
inhomogenetics on the surface). The Henry adsorption constant can be
defined as

KH = Lin Ps
p o p(z)

where
P(z) is the number density at free phase
Ps is the surface number density.

Freundlich adsorption isotherm

Herbert Freundlic gave an expression representing the isothermal variation of
adsorption of a quantity of gas adsorbed by unit mass of solid adsorbent with
pressure. The equation is known as Freundlich adsorption isotherm or
Freundlich adsorption equation. It is an empirical relation between the
concentration of a solute on the surface of an adsorbent to the concentration
of the solute in the liquid with which it is in contact. This equation is entirey
empirical because adsorption behaviour can be properly fit by such isotherms.
Other similar isotherms of this nature are the langmuir and BET adsorption
theories or isotherms. The Freundlich adsorption isotherm is mathematically
expressed as

x = Kp1/n
m

it can also be written as

log x = log k + 1 log p

m n

or

x = Kc 1/n which can also be written as

m

21
where
x = mass of adsorbate
m = mass of adsorbent
p = equilibrium pressure of adsorbate
c = equilibrium concentration of adsorbate in solution

k and n are constants for a given adsorbate and adsorbate at a particular

temperature At high pressure 1/n = O, hence extent of adsorption becomes
independent of pressure.

Example of the Freundlich isotherm showing the amount adsorbed, q (e.g in

mol/kg) as a function of equilibrium concentration in graph is for values of the
constants of k = 4 and 1/n = 0.6.
The Freundlich Isotherm is used in cases where the actual identity of the
solute is not known such as adsorption of colored material from sugar,
vegetable oil etc.

Limitation of Freundlich Adsoprtion Isotherm

It was determined that extent of adsorption varies directly with pressure, and
then it directly varies with pressure raised to the power 1/n unit saturation
pressure Ps is reached. Beyond that point rate of adsorption saturates even
after applying higher pressure. Thus Freundlich adsorption Isotherm failed at
higher pressure.

Langnuir adsorption Isotherm

The Langnuir adsorption model explains adsorption by assuming an
adsorbate behaves as an ideal gas at Isothermal conditions. At thes
conditions the adsorbate partial pressure, P A is related to the volume of it, V,
adsorbed onto a solid adsorbent. The adsorbent is also assumed to be an
ideal solid surface composed of series of distinct sites capable of binding the
adsorbate. The adsorbate binding is treated as a chemical reaction between
the adsorbate molecule Ag and an empty site or adsorption site S. This
reaction yields an adsorbed complex A ad with an associated equilibrium
constant Keq

Ag + S ⇌ Aad 4*

22
Langmuir suggested that adsorption takes place through the mechanism given
in (4*). The direct and inverse rate constants are k and k-1.

The Langnuir Isotherm being a semi-empirical isotherm with a kinetic basis as

the most common isotherm equation used due to its simplicity and its ability to
fit a variety of adsorption data. It has many applications in surface kinetics
(usually called langmuir-Hinshelwood Kinetics) and thermodynamics. It is
based on four assumption which are:

1. All of the adsorption sites are equivalent and each site can only
accommodate one molecule.
2. The surface is energetically homogeneous and adsorbed molecules do
not interact.
3. There are no phase transitions.
4. At the maximum adsorption, only a monoloayer is formed. Adsorption
only occurs on localized sites on the surface, not with other adsorbates.

If we define surface coverage, θ as the fraction of the adsorption sites

occupied, in the equilibrium, we have

K= k = θ
k-1 (1 – θ)P
or
θ = KP
1 + KP

Where P is the partial pressure of the gas or the molar concentration of the
solution. For very low pressures θ ≈ KP and for high pressure experimentally,
usually, the adsorbate is a gas and the quantity adsorbed is given in moles,,
grams, or gas volumes at standard temperature and pressure (STP) per gram
of adsorbent. If we call Vmon the STP volume of adsorbate required to form a
monolayer on the adsorbent (per gram of adsorbent),

θ= V and we obtain an expression for a straight line.

Vmon

1 = 1 1 + 1
V KVmon P Vmon

Through its slope and y – intercept we can obtain V mon and K, which are
constants for each adsorbent/adsorbate pair at a given temperature. V mon is
related to the number of adsorption sites through the ideal gas law. If we
assume that the number of sites is just the whole area of the solid divided into
the cross section of the adsorbate molecules, we can easily calculate the
surface area of the adsorbent. The surface areas of an adsorbent ddependson
its structure, the more pores it has, the greater the area, which has a big

23
influence on reactions on surfaces if more than one gas adsorbs on the
surface, we define θE as the fraction of empty sites and we have:

øE = 1
n
1 + c=1
Σ KiPi

Also we can define øj as the fraction of the sites occupied by the j-th gas:

Øj = KjPj
n
1 + Σ KιPi
ι =1
Where ι is each one of the gases that adsorb.

BET Isotherm
The concept of the theory or Isotherm is an extension of the Langmuir theory,
which is a theory for monolayer molecular adsorption, to multilayer adsorption.
Often molecules do form multiplayers, that is some are adsorbed on already
adsorbed molecules and the Langmuir Isotherm is no longer valid. In 1938,
Stephen Brunauer, Paul Emmett and Edward Teller developed a model
Isotherm that takes that possibility into account. Their theory is called BET
theory, after the initials in their last names. The authors made five
assumptions.

1. Adsorptions occur only on well-defined sites of the sample surface (one

per molecules)
2. The only molecular interaction considered is the following one: a
molecule can act as a simple adsorption site for a molecule of the upper
layer.
3. The uppermost molecule layer is in equilibrium with the gas phase, ie.
Similar molecule adsorption and desorption rates.
4. The desorption is a kinetically limited process, i.e a heat of adsorption
must be provided:

(a) these phenomenon are homogeneous i.e same heat of adsorption for a
given molecule layer
(b) It is E1 for the first layer, i.e the heat of adsorption at the solid sample
surface.
(c) the other layers are assumed similar and can be represented as
condensed species, i.e liquid state. Hence the heat of adsorption is EL is
equal to the heat of liquefaction.
5. at the saturation pressure, the molecule layer number tends to infinity
(i.e equivalent to the sample being surrounded by a liquid phase).

The resulting BET equation is:

24
 1 =c–1 P + 1
ⱱ[(Po/P) – 1] VmC Po VmC 4**

where P and PO are the equilibrium and the saturation pressure of adsorbates
at the temperature of adsorption, V is the adsorbed gas quanitiy in volume
units and Vm is the monolayer adsorbed gas quantity, c is the BET constant.

C = exp E1 – EL 4***
RT

Where E1 is the heat of adsorption for the first layer, and E L is that for the
second and higher layers and is equal to the heat of liquefaction.

Langmuir and BET Isotherms.

The langmuir isotherm is usually better for chemisorption and the BET
isotherm works better for physisorption for non-microporous surfaces.

Equation (4**) is an adsorption isotherm and can be plotted as a straight line

with 1 on the y – axis and Q = P/Po on the x – axis according to
V[Po/P)-1] experimental results.

The plot is called the BET plot. The linear relationship of this equation is
maintained only in the range of 0.05 <P/P o <0.35. The value of the slope A
and the y-intercept L of the line are used to calculate the monolayer adsorbed
gas quantity Vm and the BET constant C. The following equaltion can be
used.

Vm =1
A+I
C=1+A
I

The BET method is sued widely in surface science for the calculation of
surface area of solids by physical adsorption of gas molecules. The total
surface area Stotal and the specific surface area SBET are given by

Stotal = VmNS
V

25
SBET = Stotal
a

where Vm is in units of volume which are the units of the monolayer volume of
the adsorbate gas, N is Avogadro’s number, c the adsorption cross section of
the adsorbing species, V the molar volume of the adsorbate gas and a the
mass of the solid sample or adsorbent.

BET Plot

Example (4*)
Spherical particles of 15nm diameter and density 2290 kg/m3 are pressed to
form a pellet. The following equilibrium data were obtained for the sorption of
nitrogen at 77k. obtain estimates of the surface area of the pellet from the
adsorption isotherm and compare the estimates with the geometric surface.
the density of liquid nitrogen at 77k is 808kg/m3

P/PO M3 liq, N2 x 106 /kg solid

0.1 66.7
0.2 75.2
0.3 83.9
0.4 93.4
0.5 108.4
0.6 130.0
0.7 150.2
0.8 202.0
0.9 348.0

Where P is the pressure of the sorbate and Po is its vapour pressure at 77k.

Use the following data:

Density of liquid nitrogen = 808kgm3 area occupied by one adsorbed molecule
of nitrogen number = 0.162nm2
Avogadro number = 6.02 x 102B molecule/kmol

26
Solution
For 1 m3 of pellet with a viodage E, then:
Number of particles = (1-E)/( π /6)(15x10-9)3

Surface area per unit volume = (1 –E) π (15x10-9)2

( π /6)(15x10-9)3
= 6(1-E)/(15 x 10-9)m2/m3

1m3 of pellet contains 2290(1-E)kg solid and hence:

Specific surface = 6(1-E)/[15x10-9(1-E)x2290]
= 1.747 x 105m2/kg

Using the BET isotherm

(P/PO)/[V(1 – P/PO)] = 1/V1B + (B – 1)(P/PO)V1B

Where V and V1 are the liquid volumes of adsorbed nitrogen.

From the adsorption data given, we have;

P/PO V(m3 liquid N2/kg solid x 106 (P/PO/V) x 106 (P/PO)/[V(1-P/PO)]

0.1 66.7 1500 1666
0.2 75.2 2660 3333
0.3 83.9 3576 5109
0.4 93.4 4283 7138
0.5 108.4 4613 9226
0.6 130.0 4615 11538

Plotting (P/PO)/[V(1-P/PO)] against (P/PO),

We have the intercept, I/V1B = 300, and slope, (B-1)/V1B=13, 902

From which:
B = (13, 902/300) + 1 = 47.34
And

V1 = 1/(300 x 47.34) = 70.4x10-6m3/kg

The total surface area

= [(70.4x10-6 x 808x6.2 x 102 x 0.162 x 10-18)]
28

= 2.040 x 105m2/kg.

(b) Using the langmuir form of the isotherm:

Assuming this applies at low concentrations then, expressing pressure
as the ratio P/Po, and the amount adsorbed as a volume of liquid
adsorbate, then

27
 (P/Po) V = (P/Po)/V1 + 1/(B2V1)

Thus, a plot of (P/Po)/V against (P/Po) will give a slope of (1/V1).

Thus,

1/V1 = 13,902
And V1 = 71.9x10-6m3/kg
Which agress with the value from the BET isotherm.

Adsorption isotherm for example (4*)

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Humidification

In process operation, humidification involves increase in the amount of vapour

present in a gas stream while a decrease or reduction of amount of vapour is
known as dehumidification.

Different definition of terms used in humidification process

Humidity(≇ ¿ Mass of vapour associated with unit mass of dry gas

Humidity of saturated – humidity of the gas (≇ o) = gas when it is saturated with

vapour at a given temperature.

Percentage humidity = 100 (≇ /≇o)

Humid heat (s) = heat required to raise unit mass of dry gas and its associated
vapour through unit temperature difference at constance pressure
or : s = Ca + ≇ Cw

28
where Ca and Cw are the specific heat capacities of the gas and the vapour
respectively.
(for the air-water system the humid heat is approximately s = 1.00 + 1.9≇ /kgk)

Humid volume = Volume occupied by unit mass of dry gas and its associated
vapour

Saturated volume = humid volume of saturated gas

Dew point = temperature at which the gas is saturated with vapour. As a gas
is cooled, the dew point is the temperature at which condensation will first
occur.

Percentage relative Partial Pressure of vap. In gas x 100

Humidity = Partial pressure of vap. In saturated gas 1

Derivation of relationship between the partial pressure of the vapour and the
humidity of gas as as follows:

In unit volume of gas,

Mass of vapour = PwMw
RT

Mass of non-condensable gas = (P – Pw) MA

RT

Where Pw = Partial pressure of vapour in the gas

P = Total pressure
Also Pwo = Partial pressure of vapour in the saturated gas at the
same temperature
R = gas constant (8.314kj/molk)
T = absolute temp in kelvin

The humidity of gas is given as ≇ = Pw Mw - - - *

P-Pw MA

And the humidity of the saturated gas is given as

≇o = Pwo Mw - - - **
P-Pwo MA

Where MA = Mean molecular weight of the dry gas,

Mw = the molecular mass of the vapour

The relationship between the percentage humidity of a gas and the

percentage relative humidity may be derived as

29
Percentage humidity = P – Pwo Pw x 100
P – Pw Pwo 1

= (P – Pwo) x percentage relative humidity - - ***

(P – Pw)

When (P – Pwo)/(P – Pw) ≈ 1, the percentage relative humidity and the

percentage humidity are equal. This is achieved when the partial pressure of
the vapour is a small proportion of the total pressure or when the gas is almost
saturated, that is as Pw Pwo.

Wet – Bulb Temperature

The wet-bulb temperature is the steady state temperature reached by a small
amount of liquid evaporating into a large amount of unsaturated vapour – gas
mixture. This temp. can be used measure the humidity of the mixture.

Dry-bulb temperature
It is the temperature of a vapour-gas mixture as ordinarily determined by
immersion of a thermometer in the mixture.

Example
In a process in which it is used as a solvent, benzene is evaporated into dry
nitrogen. At 297k and 101.3kN/m2, the resulting mixture has a percentage
relative humidity of 60.

It is required to recover 80 percent of the benzene present by cooling to 283k

and compressing to a suitable pressure. What should this pressure be? The
vapour pressure of benzene is 12.2kM/m2 at 297k and 6.0kN/m2 at 283K.

Solution
From the definition of percentage relative humidity (RH) :
Pw = Pwo RH
100

At

297K Pw = (12.2 x 1000) x 60_

= 7320N/m2 100

In the benzene – nitrogen mixture

Mass of benzene = PwMw = 7320 x 78_
RT 8314 x 297
= 0.231kg

Mass of nitrogen = (P – Pw)MA

30
 RT
= (101.3 – 7.32) X 28
8.314 X 297
= 1.066kg

Hence the humidity is ≇ o = (0.217 x 20)

100
= 0.0433kg/kg

This from equation (**),

0.0433 = 6000 78
P – 6000 28

From which P = 3.92 x 195N/m2 = 392KN/m2

Exapmle
In a vessel at 101.3KN/m2 and 300K, the percentage relative humidity of the
water vapour in the air is 25. If the partial pressure of water vapour when air is
saturated with vapour at 300K is 3.6KN/m2.
Calculate:
a) the partial pressure of the water
b) the specific volumes of the air and water vapour
c) the humidity of the air and humid volume and
d) the percentage humidity.

Solution
a) From the definition of percentage relative humidity:
Pw = Pwo RH = 3600 x 25_
100 100

= 900N/m2 = 0.9KN/m2

b) In 1m3 of air
mass of water vapour = 900 x 18__
8314 x 300
= 0.0065kg

Mass of air = [(101.3 – 0.9) x 1000 x 29]

8314 x 3000
= 1.167

Hence specific volume of water vapour at 0.9KN/m2 is

= 1___
0.0065 = 154m3/kg

31
Specific volume of air at 100.4KN/m2
= 1__
1.167
= 0.857m3/kg

c) Humidity ≇ = 0.0065
1.1673
= 0.0056kg/kg

Using the approximate relationship

≇= 18 x 900 = 0.0055kg/kg
29 x 101.3 x 1000

Humid volume = Volume of + Associated 1kg air vapour

= Specific volume of air at 100.4KN/m2
= 0.857m3/kg

d) From equation (***)

percentage humidity = [(101.3 – 3.6) x 1000] x 25
[(101.3 – 0.9) x 1000]
= 24.3 percent

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32