Treatment Technologies Based on Physical Principles.

Broad categories of our interest:

Removal of organic/inorganic gases: Adsorption, Absorption, Membrane, Reactors, and Stripping.

Removal of organic/inorganic liquids from solution: Adsorption, Membrane, Reactors (e.g.

Activated Sludge).

Removal of Particulates:

Dry Wet

Gravitational settling chamber Scrubber/Absorption

Cyclone Sedimentation
Electrostatic precipitator Filtration
Filter

Particulate Pollutants:

Particulate matter emitted in gaseous streams consists of discrete and minute suspended particles
of size 100 to 0.1 µm and even less. The choice of collection devices depends upon a number of
factors: the physical and chemical characteristics of particulates, the particle size and
concentrations in the gas, volume of particulates to be handled, and the temperature and humidity
of gaseous medium. There are several ways to remove particle pollutants:

The basic mechanisms of removing particulate matter from gas streams: 1) gravitational settling,
2) centrifugal impaction, 3) inertial impaction, 4) direct interception, 5) diffusion, and 6)
electrostatic precipitation.

Equipment presently available which make use of one or more of the above mechanisms fall into
the following five broad categories: 1) gravitational settling chambers, 2) cyclone separators, 3)
fabric filters, 4) electrostatic precipitators, and 5) wet scrubbers.
Gravitational Settling Chambers:

Gravitational settling chambers are generally used to remove large, abrasive particles (usually > 50
µm) from gas streams. They offer low pressure drop and require simple maintenance, but their
efficiencies are quite low for particles smaller than 50 µm. The simplest form of horizontal
settling chamber is shown in the following figure.

The efficiency of a settling chamber is given by:

nWLvt
η=
Q
where η = efficiency
n = number of trays including the bottom
surface
W = width of the settler
L = Length of the tank
vt = terminal velocity
Q = volumetric flow rate of the gas stream

The terminal velocity can be calculated as before. At low Reynolds number, Stokes law can be
used.
For turbulent flow, following equation can be used for calculating the collection efficiency,

 − nWLvt 
η = 1 − exp 
 Q 
Cyclones

Cyclones are better for particle size greater than about 10 µm in diameter. This is an inertial
collector with no moving parts. The particle laden gas is accelerated through a spiral motion,
which imparts a centrifugal force to the particles. The particles are thrown out of the spinning gas
and impact on the cylinder wall of the cyclone. They then slide to the bottom of the cone. Here
they are removed through an airtight valving system.

The efficiency of collection of various particle sizes (η) can be determined from an empirical
expression and graph developed by Lapple.

1
 9 µB H  2 2
d0.5 =  ρ Q θ 
 P g 
where
d0.5 = cut diameter, the particle size for which the collection efficiency is 50%.
µ = dynamic viscosity of gas, Pa.s
Β = width of entrance, m
Η = height of entrance, m
ρp = particle density, kg/m3s
Qg = gas flow rate, m3/s
θ = effective number of turns made in transversing the cyclone.
The value of θ may be determined approximately by the following:

θ = π/ H(2L1+ L2)

where L1 and L2 are the length of the cylinder and cone, respectively.

Filters:

When high efficiency control of particles smaller than 5 µm is desired, a filter may be selected as
the control method. Two types are in use: (1) the deep filter, and (2) the baghouse. The deep bed
filter resembles a furnace filter. A packing of fibers is used to intercept particles in the gas stream.
For relatively clean gases and low volumes such as air conditioning systems they are quite
effective. For dirty industrial gas with high volumes, the baghouse is preferable (as shown below).

The mechanisms by which particles are separated from the gas stream are usually inertial
impaction, direct interception, and diffusion. Particle capture mechanisms are shown in the
following figure.
There are empirical correlations available to calculate the efficiency of filter depending on the
mechanism. The advantages of fabric filters are:
i) very high efficiencies, ii) retention of finest particles, iii) collection of particulates in dry form,
and relatively low pressure drop. The main disadvantages are: i) their large size, high
construction costs and iii) their application only to process temperatures generally below 2850C.

Electrostatic Precipitators

Electrostatic precipitation is a physical process by which particles suspended in gas stream are
charged electrically and under the influence of the electrical field, separated from the gas stream
(shown below)
The classic ESP efficiency equation is one proposed by Deutsch,
 Aw 
η = 1 − exp − Q 
 g 

where A = collection area of plates, m2

w = migration velocity of particles, m/s
Qg = gas flow rate, m3/s
The migration velocity of the particle is a function of the electrostatic force. The migration
velocity is described by the following equation:
qEp C
w = 6πrµ

where
q = charge, coloumbs (C)
Ep = collection field intensity, volts/m
r = particle radius
µ = dynamic viscosity of gas, Pa.s
C = Cunningham correction factor.
Wet Scrubber:

When the particulate matter to be collected is wet, corrosive, or very hot, the fabric filter may not
work. Typical scrubbing applications include control of emission of talc dust, phosphoric acid
mist, foundry cupola dust, and open hearth steel furnace fumes.

Liquid scrubbers vary in complexity. Simple spray chambers are used for relatively coarse particle
sizes. For high efficiency removal of fine particles, the combination of a venturi scrubber followed
by a cyclone would be selected. The underlying principle of operation of the liquid scrubbers is
that a differential velocity between the droplets of collecting liquid and the particulate pollutant
allows the particle to impinge onto the droplet. Since the droplet-particle combination is still
suspended in the gas stream, an inertial collection device is placed downstream to remove it.
Because the droplet enhances the size of the particle, the collection efficiency of the inertial device
is higher than it would be for the original particle without the liquid drop.
The most popular collection efficiency equation is that proposed by John-stone, Field, and Tassler:

η = 1 − exp(−κR ψ )
where
η = efficiency
κ = correlation coefficient, m3 of gas/m3 of liquid.
R = liquid flow rate, m3/ m3 of gas.
ψ = inertial impaction parameter

The inertial impaction parameter ψ relates the particle and droplet sizes and relative velocities:

Cρp vg (d p ) 2
ψ = 18d µ
d

where C = Cunningham correction factor

ρp = particle density, kg/m3
vg = speed of gas at throat, m/s
dp = diameter of particle, m
dd = diameter of droplet, m
µ = dynamic viscosity of gas, Pa.s

The Cunningham correction factor accounts for the fact that very small particles do not obey
Stokes settling equation. In this case, Cunningham slip factor is approximated as:

6.21x10−4 (T )
C = 1+ dp

where,
T = temperature, K
dp = diameter of particle, µ

Sedimentation: Particles that will settle within a reasonable period of time can be removed in a
sedimentation basin. Sedimentation basins are usually rectangular or circular with either a radial
or upward water flow pattern. Regardless of the type of basin, the design can be divided into four
zones: inlet, settling, outlet and sludge storage.
The purpose of inlet zone is to evenly distribute the flow and suspended particles across the cross
section of the settling zone. It consists of a series of inlet pipes and baffles.

(a) Horizontal flow clarifier (b) upflow clarifier

Sedimentation concepts

There are two factors to consider for sedimentation:

1) particle settling velocity, vs (downward)

2) overflow rate, vo or liquid velocity (upward)

A particle will be removed 100% if vs is greater

than vo, and 0 percent removal if vs is smaller than vo.

overflow rate/ surface loading (m3/d.m2) is applied to a m2 of surface area and shown below:

Q V hA h
vo = = = =
A tA tA t
As long as vs is greater than vo, the removal of particles is independent of the depth of the tank.
Sedimentation zones vary from a depth of a few centimeters to a depth of 6 m or greater. In a
horizontal sedimentation tank, unlike an upflow clarifier, some percentage of the particles with a vs
less than v0 will be removed. The percentage of particles removed, P, with a settling velocity of vs
in a sedimentation tank designed with an over flowrate of is,

P = 100 vs / v0
Determination of vs

In design of an ideal sedimentation tank, first determine the settling velocity (vs) of the particle to
be removed and then set the overflow rate (v0) at some value less than or equal to vs.
Determination of the particle-settling velocity is different for different types of particles:

Type I sedimentation

Type I sedimentation is characterized by particles that settle discretely at a constant settling

velocity. They settle as individual particles and do not flocculate or stick to other particles during
settling. Type I settling is during pre-sedimentation for sand removal prior to coagulation in a
potable water plant.

Type II sedimentation

Type II sedimentation is characterized by particles that flocculate during sedimentation. Since they
flocculate, their size and velocity constantly are changing (increasing). These types of particles
occur in alum or iron coagulation, in primary sedimentation.

Type III or zone sedimentation

In zone sedimentation the particles are at a high concentration (greater than 1000 mg/L) such that
the particles tend to settle as a mass, and a distinct clear and sludge zone are present. Zone settling
occurs in lime softening sedimentation, activated sludge sedimentation and sludge thickeners.

Determination of overall flow rate, v0:

In the case of Type I sedimentation, the particle settling through a quiescent fluid accelerates until
the frictional resistance, or drag, on the particle is equal to the gravitational force of the particle.
The terminal velocity for spherical particles is given below:

1
 4g (ρ s − ρ )d  2
vs =  
 3C D ρ 
where vs = settling velocity
ρs, ρ = density of the particle and fluid respectively.
d = diameter of the particle
CD = drag coefficient
g = gravitational constant

CD, drag coefficient, is a function of Reynolds number.

For low Reynolds number, (Re<0.5)

CD = 24/Re

For transition range Re between 0.5 and 104, the drag coefficient is
CD = 24/Re + 3/Re +0.34

Substituting the drag coefficient in settling velocity to yield the following equation:

g (ρ s − ρ )d 2
vs =
18µ

Above equation is Stoke’s law to calculate the terminal velocity in laminar flow.

Flocculant sedimentation or Type II sedimentation.

There is no adequate mathematical relationship that can be used to describe type II settling. The
Stokes equation can not be used because the flocculating particles are continually changing in size
and shape. The type II sedimentation is dependent on the depth as well as the properties of the
fluid and the particles.
To determine the settling rates laboratory tests are conducted using a batch settling column as
shown in the following figure A. The settling column has sampling ports at different points, where
samples are withdrawn at regular time intervals and the suspended solids concentration is
determined. The column is typically 100 to 200 mm in diameter with a height equal to the
proposed settling tank height (1 to 3 m). The column is filled initially with a well mixed sample of
known total solids concentration, such that initially the same solids concentration exists for the full
depth. For the samples taken during the settling process, the percentage removal of solids is
computed and plotted as shown in Figure B with equi-percentage removal curves, Ra, Rb etc. The
removal efficiency in an ideal settling tank can be calculated in the following way. For example,
suppose a tank has an overflow rate of v0, where v0=h5/t2. All particles having a settling velocity
equal to or greater than v0 will be removed from the tank, and particles with smaller velocities will
be removed in proportion to v/ v0. From Figure B it can be seen that R0d of the particles have
average settling velocity of v0 or greater, and thus will be completely removed. The remaining
solids between R0d and R0c have settled at an average velocity of ha/t2 and solids between R0e and
R0d have settled at an average velocity of hb/t2. An approximation for the total overall removal is
given by:

ha h
R 0 = Rc0 + ( Rd0 − Rc0 ) + b ( Re0 − Rd0 )
t2 v0 t2 v0
Figure A Figure B

Type III or zone sedimentation

Zone settling occurs when particles aggregate, forming a mass which settles as a blanket with a
distinct interface between the settling sludge and the clarified effluent. Zone settling occurs at
much higher concentration of the particle (greater than 1000 mg/L). It occurs in lime softening
sedimentation, activated sludge sedimentation, and sludge thickeners. A zone sedimentation is
shown in the following figure.
A batch settling test is done in a tube as shown above. The data are plotted as below:

In the region from A to B there is hindered settling, B to C is transition, and C to D is the

compression where the solids are supported from the bottom. The required surface

area for a sedimentation basin for concentrated suspension can be achieved from the above figure.
Clarification zone: A = Q/vs
where s can be derived from the slope of hindered settling.

Thickening zone: A = Qtu/h0

where tu is the time required to obtain a desired sludge concentration Cu and tu is obtained
graphically as shown below.

Removal of organics from liquid and gaseous streams.

Adsorption

The contaminants are removed from the waste stream through adsorption on the internal surface,
where the contaminants prefer to concentrate at the interfacial region between the surface and the
gas or liquid phase.

Rates of adsorption

This is a significant factor to determine the application of this process for water quality control.
There are three steps for adsorption to occur.
i) transport of the adsorbate through a surface film to the exterior of the adsorbent (film diffusion).

ii) diffusion of the adsorbate within the pores of the adsorbent (at this point, some/little adsorption
also occurs at the surface of the adsorbent).

iii) third and final step is the adsorption of the solute or adsorbate on the interior surfaces bounding
the pore and capillary spaces of the adsorbent.

The rate determining step is determined experimentally by varying operating parameters such as
flow rate, concentration, nature and size of adsorbate, temperature, surface area of the adsorbent.
Rate also depends on the mode of operation, in batch reactor, because of continuous agitation, the
rate is determined by the diffusion through pores of the adsorbent. In continuous operation, rate is
limited by the film diffusion.

Factors affecting adsorption:

i) surface area of the adsorbent, more porous the adsorbent, higher the surface area available for
adsorption, higher is the amount of adsorption.

ii) adsorption rate increases monotonously with some function of the inverse of the diameter of
adsorbent particles.

iii) solubility of the solute is an important factor: adsorption of organic acids from aqueous
solution increases in the order formic-acetic-propionic-butyric whereas order is reversed for
adsorption from toluene. Thus adsorption increases with decreasing solubility.

iv) Molecular size of the adsorbate is important when the rate is controlled by intraparticle
transport, in which case the reaction generally will proceed more rapidly the smaller the adsorbate
molecule. However, this may vary with chemical class of the adsorbate.

v) Activated carbon has a negative pH, adsorption is minimum for charged species and maximum
for neutral. Thus it is pH dependent as it dictates the ionization.

vi) Polar solute will be adsorbed from a nonpolar solvent to a polar adsorbent.

vii) Adsorption reactions are exothermic, thus increasing temperature decreases rate of adsorption.

viii) Nature of adsorbent, i.e., the nature of surface group also dictates the rate of adsorption.
Activated carbon, molecular sieves, silica gel, and activated alumina are the most common
adsorbents.
Adsorption models (Isotherms)

Langmuir isotherm

*
bCe aC g
qe = Q 0
; or in another form W =
1 + bCe 1 + bC g*
where qe, W = amount of gas per unit mass of adsorbent, kg/kg.
a, b = constants determined by experiment
Ce,Cg* = equilibrium concentration of gaseous pollutant.
Q0 = number of moles of adsorbate adsorbed per unit mass of adsorbent.

Freundlich isotherm

q=K C
e f
n
e

Where Kf, n are the empirical constants.

Adsorption in column: A typical adsorption/desorption cycle is shown in the attached figure.

Typical operating conditions: low temperature and pressure and moisture must be removed from
air prior to send it through the bed as moisture competes with hydrocarbon for the active sites.
While the bed has sufficient capacity, no pollutant is emitted. At some point in time, the bed will
become saturated with pollutant, and leakage of pollutant from the bed starts. This is called
breakthrough, and at this point, influent becomes equal to the effluent. At this point regeneration
is necessary. To provide continuous service, two beds are provided, while one is adsorbing, the
other is regenerating. Typical breakthrough curve is shown below:

Design of adsorption tower

Maximum capacity of carbon bed =

M = ρ WS* AL
ads b

where Ws* = mass of contaminant that can be sorbed onto the carbon for a given inlet gas
concentration
ρb =bulk density of the carbon
A= cross sectional area
L = length of the bed

Time of regeneration =
 M ρ WS* AL
τ = =
ads b

ads
(Q ) in feed
QC a a0

Qa =volumetric flow rate of air

Ca = concentration of the contaminant at the inlet

Zone of fully utilized or saturated adsorbent grows with a velocity, Vads,

L QC
V = = a a0

τ ρ WS* A
ads

ads b

Using either Langmuir or Freundlich's equation to relate Ws* with the initial concentration Ca0, the
velocity with which the saturated region grows:
1
−

C 
β
QC
V = a a0
  ; where WS is given in the form
*
a0

ρA
ads

b
α 
1

C 
β

W* =   Fruendlich' s equation
a

S α 
or,
1

Qα β

(C )
1

V =
1−
a β
ads
ρA b
a0

In reality, the bed operation time (or breakthrough time) is shorter than given by τads.
The breakpoint is the maximum contaminant concentration that is allowable in the effluent. For
convenience the endpoint is often arbitrarily specified as 95 or 99% of the influent concentration.

Active adsorption length

The thickness of the active adsorption zone, δads by integrating between the concentrations that
span this zone, the breakpoint and endpoint concentrations (Cb and Ce, respectively). If we set Cb
and Ce to be 1% and 99% of the inlet concentration, respectively, then the active zone width is
given as:
  β −1 
q  1 1 − (0.01) 
δ= 4.595 + ln
ka av  β − 1 1 − (0.99) β −1 
 
When the active adsorption zone reaches the outlet of the adsorber, the adsorber must be shut
down and regenerated.

The time to calculate the breakthrough:

L −δ
τ =
ads V
ads

where τads = time for breakthrough/time for regeneration

L= height of the bed
δ = width of adsorption zone
vads = velocity of adsorption zone (m/s)

Absorption:
This is a mass transfer process in which the gas dissolves in the liquid, the dissolution may or may
not be accompanied by a reaction with an ingredient of the liquid. Mass transfer is occurred in
three steps:
1. Diffusion of the pollutant gas to the surface of the liquid.
2. Transfer across the gas/liquid interface (dissolution)
3. Diffusion of the dissolved gas away from the interface into the liquid.

Structures such as spray chambers (Fig a) and towers or columns (Fig b) are two classes of devices
employed to absorb pollutant gases.
Scrubbers such as spray chamber uses liquid droplets to absorb the gas. In towers, a thin film of
liquid is used as the absorption medium. Scrubbers are relatively inefficient absorbers but have
the advantage of being able to simultaneously remove particulates. Towers are much more
efficient absorbers but they become plugged by particulate matter.

Applications in environmental engineering:

Removal of H2S, SO2, HCl, NH3 and other toxic organic vapors from gas streams. The solvent can
be water or organic. Organic solvents need to be regenerated which is done by heat-treating by air
or steam and the process is called stripping. The opposite process of absorption is stripping.

The amount of absorption that can take place for a nonreactive solution governed by the partial
pressure of the pollutant. For dilute solutions, as we have in pollution control systems, the
relationship between partial pressure and the concentration of the gas in solution is given by
Henry’s law:

P* = HC*

where P* = equilibrium partial pressure of pollutant

gas, kPa
H = Henry’s law constant, kPa.m3/g
C* = concentration of pollutant gas in the liquid phase, g/m3

As before adsorbtion in column, countercurrent flow is advantageous for the absorption tower
where the high concentration gas is absorbed into a liquid with a high pollutant concentration and
the lower concentration gas is absorbed by clean liquid with no pollutants in it.
Factors for choice of solvent for absorption:

a) Gas Solubility: the gas solubility should be high, thus increasing the rate of absorption and
decreasing the quantity of the solvent. Generally solvents of chemical nature similar to that of the
solute to be absorbed will provide good solubility.

b) Volatility: The solvent should have a low vapor pressure since the gas leaving an absorption
operation is ordinarily saturated with the solvent and much may thereby be lost.

c) Corrosiveness: the material of construction required should not be expensive

d) Cost: the solvent should be inexpensive

e) Viscosity: low viscosity is preferred for reasons of rapid absorption rates, low pressure drops.

Design of the Absorption tower:

A mass balance on the above diagram is shown below:

(Gm1 )( y1 ) − (Gm2 )( y2 ) = ( Lm1 )(x1 ) − Lm2 )(x2 )

where
Gm1, Gm2 = total gas flow (air + pollutant) into and out of the column respectively, kg.mole/h.
y1, y2 = mole fraction of pollutant in the gas phase at inlet and outlet of column, respectively.
Lm1, Lm2= total liquid flow (solvent + absorbed pollutant) out of and into the column respectively,
kg.mole/h.
x1, x2 = mole fraction of pollutant in the liquid phase at outlet and inlet of the column, respectively.

Consider the differential height of the absorber, dz, as shown in the above figure, the total
interfacial area open to mass transfer is defined as:

area for mass transfer = (a) (A dz)

where a = area per unit volume of packing

A = cross sectional area of column
Rate of mass transfer of a gas,i, into solution is given as:

dC
Ni = dt = Ky ( y − y*)

where Ky = overall mass transfer coefficient for gas

y,y* = mole fraction of gaseous pollutant and equilibrium mole fraction respectively. The
rate of transfer of species i then is :

rate of mass transfer = (Ni) (A) (dz)

Air Stripping

Used mostly for removal of volatile compounds such as chlorinated hydrocarbons, which has low
molecular weight and low solubility in water. Possible designs are:
1. Spray towers inject water into a tower with air flow with high rate of mass transfer.
Design parameters include nozzle size/type, and allowable pressure drop.
2. Packed towers packing provides greater area for mass transfer. Design parameters
include packing type, size depth, column diameter and air-water ratio.
3. Diffused aeration-air is injected into the water through a sparger. Design parameters
include depth of tank, bubble size and air water ratio.

The last method (diffused aeration) can also be used for removal of volatile organic
compounds from ground water, and is called air sparging.

Design equations:

(i) P =HC*

− ∆H 0
(ii) log H A = +K
RT
Temperature correction for Henry's constant

(iii) Rate of mass transfer:

dC A
V = J A A = AK L (C *A − C A )
dt

JA = Kmol/m2.s
KL = m/s
A =m2
CA, CA* = kmol/m3

The packing volume is needed for the design. V =Adz

Where dz= height of the bed.

Thus, rate of mass transfer =

aK L (C *A − C A )V
Membrane technology

Dissolved solids can be removed from water or wastewater by membranes with pore diameters as
small as 30A. Following two processes occur in the industry.
1. When the separation is effected by passing water through the membrane, the process is
termed osmosis
2. When solute molecules and ions pass through membrane, it is called dialysis.

Reverse Osmosis:

When two solutions with different solute concentrations are separated by semipermeable
membrane, a difference in chemical potential will exist across the membrane, and water will tend
to diffuse through the membrane from the lower concentration to the higher concentration side.
Flow continues until the pressure difference (osmotic pressure) balances the chemical potential.

Flux of water through the membrane:

Fw = w(∆Pa − ∆Po )
where Fw = flux of water, kg/m2.s
w = flux rate coefficient, s/m
∆Pa = imposed pressure gradient, kPa
∆Po = osmotic pressure gradient, kPa

Some solute passes through the membrane in all cases. Solute flux is described by

N i = K i ∆Ci

Ni = flux of solute, kg/m2.s

w = flux rate coefficient, s/m
∆Ci = salt concentration difference between the feed, Cf and the permeate Cp.

Solute rejection: is defined as the efficiency of rejection from the permeate of a specific solute i:

Cif −C ip
ζi =
Cif

where Cif and Cip are solute concentrations in the feed and permeate.