Industrial Waste

Waste generated by manufacturing or industrial processes that is not hazardous waste (US-EPA). It represents waste
generated from 17 different industry groups representing the Standard Industrial Classification (SIC codes) such as:
 Electric power generation  Nonferrous metals manufacturing/foundries
 Fertilizer/ agricultural chemicals  Organic chemicals
 Food and related products/ by-products  Plastics and resins manufacturing
 Inorganic chemicals  Pulp and paper industry
 Iron and steel manufacturing  Rubber and transportation equipment
 Leather and leather products  Water treatment

Special Waste
These wastes typically are generated in large volumes and, at the time, were believed to possess less risk to human
health and the environment than the wastes being identified for regulation as hazardous waste.
 Cement kiln dust
 Mining waste
 Oil and gas drilling muds and oil production brines
 Mineral processing waste; beneficiation
 Utility waste (i.e., fossil fuel combustion waste)

WASTE CHARACTERIZATION
Waste characterization efforts can facilitate ground-water risk and air emissions analyses. It can be the starting point for
facility-wide waste reduction, recycling, or pollution prevention efforts.
1. Obtain sufficient process knowledge to assess the physical state of the waste from the following:
a. Chemical engineering designs or plans
b. Material Safety Data Sheets (MSDS)
c. Manufacturer’s literature
d. Previous waste analyses
e. Literature on similar processes
f. Preliminary testing results
2. Determine what is reasonably expected to be in the waste through proper sampling and analysis, so that it is not
necessary to test for unspecified constituents. The following are factors to consider:
a. Physical state of the waste – is the sample liquid, solid, gas, or multiphasic. The sampling device will also vary
according to whether the liquid is viscous or free-flowing, or whether the solid is hard, soft, powdery,
monolithic, or clay-like
b. Composition of the waste – the samples should represent the average concentration and variability of the
waste in time or over space. The Toxicity characteristic leachate procedure (TCLP) test method is used to
determine the leaching capacity of the waste and if it is hazardous due to its characteristics.
c. Waste generation and handling processes.
i. Is the waste generated in batches;
ii. Is there a change in the raw materials;
iii. Does waste composition vary substantially as a function of process temperatures or pressures;
iv. Does storage time affect the waste’s characteristics/ composition
d. Transitory events – start-up, shut-down, slow-down, and maintenance transients can result in the generation
of a waste that is not representative of the normal waste stream. If a sample was unknowingly collected at
one of these intervals, incorrect conclusions could be drawn
3. Asses the environment in which the waste will be placed.
4. Consult with state and local regulatory agencies to determine any specific testing requirements.
5. Select an appropriate leachate test or organic constituent analysis based on the above information.

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COAGULATION & FLOCCULATION
These constitute the backbone processes in most water and advanced wastewater treatment plants; they serve as
conditioning for treatment systems that are designed to:
 Remove infectious agents,
 Remove toxic compounds that have adsorbed to the surface of the particles,
 Remove precursors to the formation of disinfection by products (DBPs),
 Make the water palatable

Objectives
 Agglomerate colloidal particles and other finely divided matter
 Enhance the separation of particulate species in downstream processes
 Preparatory stage in order to remove specific contaminants

COAGULATION
Coagulation is commonly achieved by adding different types of chemicals (coagulants) to the wastewater to promote
destabilization of the colloid dispersion and agglomeration of the resulting individual colloidal particles
Inorganic coagulants:
aluminum- or iron-based salts, and/or synthetic organic polymers commonly known as polyelectrolytes

Primary Effect
 Agglomeration and eventual removal of colloids (primarily responsible for wastewater turbidity)
Secondary Effects
 Precipitation of some chemical species in solution such as phosphate
 Entrapment of larger particles in the floc

Specific Applications of Coagulation

A. Water Treatment
1. Enhancing the effectiveness of subsequent treatment
processes
2. Removal of turbidity
3. Control of taste and odor
4. Coagulation of materials causing color
5. Removal of bacteria and viruses
6. Removal of Giardia and Cryptosporidium
7. Coagulation of natural organic matter and humic
8. Removal of arsenic and radionuclides
B. Municipal Wastewater Treatment
1. Improving efficiency of primary treatment plants
2. Obtaining removals intermediate between primary and
secondary treatments
3. Tertiary treatment of secondary effluents for water
reuse
4. Handling of seasonal loads
6. Conditioning of bio-solids before dewatering
C. Industrial Waste Treatment
1. Improving removals from secondary effluents
2. Removal of metals
3. Treatment of toxic wastes
4. Control of color
5. Handling seasonal wastes
6. Providing treatment to meet stream and disposal
requirements at lower capital cost
D. Combined Sewer Overflow
1. Removal of particulate matter and BOD (biochemical
oxygen demand)
2. Handling irregular occurrence of storm events
3. Preventing treatment upset by varying water quality
4. Meeting seasonal requirements in receiving streams

COLLOIDS
Range in size from 0.001 to 10 μm resulting in a very small ratio of mass to surface area. The consequence of this smallness in
size and mass and largeness in surface area is that in colloidal suspensions:
1. Gravitational effects are negligible, and
2. Surface phenomena predominate
The developed electrostatic repulsive forces prevent the colloids from coming together and, consequently, contribute to their
dispersion and stability.

Electrokinetic Properties
The electrokinetic properties of colloids can be attributed to the following three processes:
 Ionization of groups within the surface of particles.
 Adsorption of ions from water surrounding the particles.
 Ionic deficit or replacement within the structure of particles.
ChE 513: Industrial Waste Management & Control
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Organic substances and bacteria acquire their surface charges as a result of the ionization of the amino and carboxyl groups as
shown
𝑅 − 𝑁𝐻3 + → 𝑅 − 𝑁𝐻2 + 𝐻 +
𝑅 − 𝐶𝑂𝑂𝐻 → 𝑅 − 𝐶𝑂𝑂− + 𝐻 +

The resulting charge on the surface of such particles is a function of the pH. At high pH values or low hydrogen ion
concentrations, the above reactions shift to the right and the colloid is negatively charged; at low pH, the reactions shift to
the left, the carboxyl group is not ionized, and the particle is positively charged due to the ionized amino group.

Hydration
Water molecules may also be adsorbed on the surface of colloids, in addition to or in place of, other molecules or ions.
The extent of this hydration depends on the affinity of particles for water.
Colloidal particles that have water-soluble groups on their surface such as hydroxyl, carboxyl, amino, and sulfonic exhibit high
affinity for hydration and cause a water film to surround the particles.

Brownian Movement
Colloids exhibit a continuous random movement caused by bombardment by the water molecules in the dispersion
medium. This action, called Brownian movement, imparts kinetic energy to the particles that tends to cause an increase in the
frequency of collisions, thus promoting coagulation. Elevated temperature increases molecular velocity resulting in more
kinetic energy and more intense Brownian movement.

Tyndall Effect
Colloidal particles have an index of refraction different from water, light passing through the dispersion medium and
hitting the particles will be reflected. The turbid appearance due to this interference with the passage of light is termed the
Tyndall effect.

Filterability
Colloids are small enough to pass through ordinary filters, such as paper and sand, but are large relative to ions in
size, diffuse very slowly, and will not pass through membranes. As a result, colloidal particles can be readily removed by
ultrafiltration but require coagulation prior to their efficient removal by ordinary filtration.

DESTABILIZATION OF COLLOIDS
Destabilization of colloidal particles is accomplished by coagulation through the addition of hydrolyzing electrolytes
such as metal salts and/or synthetic organic polymers.
Mechanisms of coagulation:
1. Adsorption and charge neutralization.
2. Entrapment of particles in precipitate.
3. Adsorption and bridging between particles.

Adsorption & charge neutralization

 Coagulants dissociate, thus yielding metallic ions, which undergo hydrolysis and form positively charged metallic
hydroxyl-oxide complexes (aquometal complex)

 Electrostatic repulsion is decreased or eliminated resulting in the destabilization of the colloids and hence their
agglomeration.
 An overdose of metallic salts could reverse the colloidal charge and restabilize the particles

Entrapment of particles in precipitate

 When the coagulants alum Al2(SO4)3 or ferric chloride FeCl3 are added in high enough concentration, they will react
with hydroxides (OH−) to form metal hydroxide precipitates, Al(OH)3 or Fe(OH)3 respectively
 The colloidal particles get entrapped in the precipitates either during the precipitate formation or just after. This type
of coagulation by enmeshment of colloids in precipitates is commonly called sweep coagulation

Adsorption and bridging between particles

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  Polymers destabilize colloidal particles through the formation of bridges that extend between them through
reactive groups
 When a group on a polymer molecule attaches to a colloid, the remainder of the long-chain molecule extends
away into the water. Once the extended portion of the polymer gets attached to another colloidal particle, the two
particles become tied together or bridged by the polymer.
 Re-stabilization can also occur due to aggressive mixing or extended agitation, which may break the inter-particle
bridging

PROCESS STEPS
1. Flash Mixing
 In the flash mixer, coagulant chemicals are added to the water and the water is mixed quickly and violently to evenly
distribute the chemicals through the water.
 Flash mixing typically lasts a minute or less. If the water is mixed for more than 60 seconds, the mixer blades will
shear the newly forming floc back into small particles.

2. Coagulation
 During coagulation, the coagulant chemicals neutralize the electrical charges of the fine particles in the water,
allowing the particles to come closer together and form large clumps.

3. Flocculation
 Gentle mixing brings the fine particles formed by coagulation into contact with each other; typically lasts for about 30-
45 minutes.
 The flocculation basin often has a number of compartments with decreasing mixing speeds as the water advances
through the basin. This compartmentalized chamber allows increasingly large floc to form without being broken
apart by the mixing blades.

COMMON COAGULANTS
Necessary characteristics of Coagulants
 They are non-toxic at the working dosage
 They have a high charge density (usually trivalent metallic cations)
 They are insoluble in the neutral pH range

Molecular Weight Density (lb/ft3)

Substance Chemical Formula
(g/mol) Dry Liquid
Aluminum Sulfate Al2(SO4)3· 18H2O 666.7 60-75 78-80 (49%)
(Alum) Al2(SO4)3· 14H2O 594.3 60-75 83-85 (49%)
Ferric Chloride FeCl3 162.1 84-93
Fe2(SO4)3 400
Ferric Sulfate
Fe2(SO4)3·3H2O 454 70-72
Ferrous Sulfate FeSO4·7H2O 278 62-66
Limewater Ca(OH)2 56 as CaO 35-50

ALUMINUM SALTS
The chemistry of metallic salts involves dissolution, hydrolysis, and polymerization reactions

1. Dissolution: All metal cations in water are present in a hydrated form as aquocomplexes.
• The simple aluminum variety Al3+ does not exist as such in an aqueous solution, but is present in its aquometal
form as Al(H2O)63+

2. Hydrolysis: The aquometal ions formed in the dissolution of alum in water are acidic or proton donors in the following
hydrolytic reactions:

ChE 513: Industrial Waste Management & Control

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3. Polymerization: The hydroxocomplexes formed as products of hydrolysis may combine to form a variety of hydroxometal
polymers such as Al6(OH)153+, Al7(OH)174+, Al8(OH)204+, and Al13(OH)345+
• The net result of adding alum to an aqueous environment is the formation of large positively charged complexes
that are insoluble and the generation of hydrogen ions.
• The net effect is a drop in pH or the consumption of present alkalinity. Reaction with calcium and magnesium
bicarbonate alkalinity:
Al2(SO4)3· xH2O + 3Ca(HCO3)2  3CaSO4 + 2Al(OH)3 + 6CO2 + xH2O

• The optimum pH for coagulation with alum is around 6 with an effective operational range between pH 5-8
• Series of steps involved as dosage increases

Aluminum
Hydroxometal
Hydroxocomplexes hydroxide
polymers
precipitates

IRON SALTS
• Ferric salts (ferric chloride and ferric sulfate) when added to water behave in a similar fashion to alum:

Ferric sulfate is effective over a wider pH range, usually from pH 4 to 9. However, best performance is between pH 3.5 and 6.5
and above 8.5.
• A strong and heavy floc is produced, which can settle rapidly.
• Ferric salts are more effective for removing color, taste, and odor-producing matter (NOM)
Fe2(SO4)3 + 3Ca(HCO3)2  2Fe(OH)3 + 3CaSO4 + 6CO2

Ferrous sulfate and lime. In most cases, ferrous sulfate cannot be used alone as a precipitant because lime must be added at
the same time to form a precipitate.
FeSO4·7H2O + Ca(HCO3)2  Fe(HCO3)2 + CaSO4 + 7H2O

If limewater is added: Fe(HCO3)2 + 2Ca(OH)2  Fe(OH)2 + 2CaCO3 + 2H2O

4Fe(OH)2 + O2 + 2H2O  4Fe(OH)3

SODIUM ALUMINATE
• The main difference between sodium aluminate and other common coagulants, alum, and iron salts, is its being
alkaline rather than acidic in solution. It reacts with the natural carbon dioxide acidity and produces aluminum
hydroxide floc.
2NaAlO2 + CO2 + 3H2O  2Al(OH)3 + Na2CO3

• Sodium aluminate is most commonly used in combination with alum in the treatment of boiler water and produces
aluminum hydroxide floc in a similar fashion to the previous reaction
6NaAlO2 + Al2(SO4)3 ·14.3H2O 8Al(OH)3 + 3Na2SO4 + 2.3H2O

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 • Sodium aluminate can be produced by dissolving alumina in sodium hydroxide. The main deterrent to the wide scale
use of this coagulant is its relatively high cost

POLYMERIC INORGANIC SALTS

• Polyaluminum chloride (PACl) is used on a large scale in the treatment of potable water in Japan, France, and
Germany.
• Although commercial preparations are available, they are more commonly prepared on site by the addition of a base
to neutralize concentrated solutions of ferric and aluminum salts.

ORGANIC POLYMERS
• Polymers that contain ionizable groups such as carboxyl, amino, or sulfonic groups are called polyelectrolytes. They
may be cationic, anionic or ampholytic (contains both positive and negative groups).
• Polymers function as excellent coagulants due to their ability to destabilize particles by charge neutralization, inter-
particle bridging, or both.
• Anionic and nonionic polymers destabilize negatively charged colloidal particles through their bridging effect.
Cationic polymers, on the other hand, are able to destabilize and coagulate such particles by both charge
neutralization and inter-particle bridging.

Coagulant Aids
 Add density to slow-settling flocs and add toughness to the flocs so that they will not break up during the mixing and
settling processes.
 The aim is to obtain faster floc formation, produce denser and stronger flocs, decrease the coagulant dosage, broaden
the effective pH band, and improve the removal of turbidity and other impurities
 Coagulant aids include four typical types to achieve optimum conditions:
• Alkalinity addition (lime, soda ash)
• pH adjustment (sulfuric acid, phosphoric acid, lime, soda ash)
• Particulate addition (bentonite clays, activated silica)
• Polymers

LIMEWATER
• When natural alkalinity is not sufficient to react with the alum dosage, lime or soda ash can be added to cover the
deficit. Lime is the most commonly used chemical because of its lower cost. However, soda ash has an advantage over
lime in that it does not increase water hardness.

The principles of clarification for limewater as precipitant:

Ca(OH)2 + H2CO3  CaCO3 + 2H2O
Ca(OH)2 + Ca(HCO3)2  2CaCO3 + 2H2O

Additional reactions:
Ca(OH)2  CaO + H2O
Ca(HCO3)2  CaCO3 + H2O + CO2

COAGULATION CONTROL
TYPES OF COLLOIDAL SYSTEMS
Type I: High colloidal concentration, low alkalinity (pH 4-6).
 The high concentration of particulate material provides an ample opportunity for contact and building of good flocs.
 As a result, one has to determine only one variable—the optimum coagulant dosage.

Type II: High colloidal concentration, high alkalinity.

 Destabilization can be accomplished as in Type I by adsorption and charge neutralization.
 Feed a high coagulant dosage that is sufficient to consume the excess alkalinity as well as to form the positively
charged hydroxometal polymers.
 Alternative is to add an acid to lower the pH before feeding the coagulant
 In this case one has to determine two variables— the optimum coagulant dosage and optimum pH.

Type III: Low colloidal concentration, high alkalinity.

 The feasible approach in this case is to achieve sweep coagulation by feeding a high coagulant dosage

ChE 513: Industrial Waste Management & Control

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  A second alternative approach is to add a coagulant aid that will increase particle concentration and hence the rate of
inter-particle contact
 A lower coagulant dosage will then be needed to achieve coagulation by charge neutralization

Type IV: Low colloidal concentration, low alkalinity.

 The low colloidal concentration and depressed rate of inter-particle contacts do not allow effective coagulation by
adsorption and charge neutralization
 Also, the low alkalinity and low pH of the suspension do not enable rapid and effective destabilization by sweep
coagulation
 Coagulation can be achieved by: addition of a coagulation aid (increase colloidal concentration), addition of lime or
soda ash (increase alkalinity), or both at low concentrations

JAR TEST
The jar test is intended to simulate the coagulation/flocculation process in a water treatment plant. The results that it
produces are used to help optimize the performance of the plant.
 developing design criteria for new plants
 for optimizing plant operations,
 for the evaluation and control of the coagulation process

The jar test can be run to select each of the following:

1. Type of coagulants.
2. Dosage of coagulants.
3. Coagulant aid and its dosage.
4. Optimum operating pH.
5. Sequence of chemical addition.
6. Optimum energy and mixing time for rapid mixing.
7. Optimum energy and mixing time for slow mixing.

Example of typical dosage optimization:

1. Samples of water/wastewater are poured into a series of jars, and various dosages of the coagulant are fed into the
jars;
2. The coagulants are rapidly mixed at a speed of 60–80 rpm for a period of 30–60 s
3. Then they are allowed to flocculate at a slow speed of 25–35 rpm for a period of 15–20 min.
4. The suspension is finally left to settle for 20–45 min under quiescent conditions

Evaluation
 Rate of Floc Formation
 Type of Floc Particles
 Clarity of the Water
 Size of the Floc
 Amount of Floc
 Volume of Floc

MIXING
The degree of mixing is measured by the velocity gradient, G, which is a function of the power input into the water:
𝑷
𝑮=√
𝝁𝑽
Where G = velocity gradient (s−1),
P = power input, J/s or (ft·lb/s)
V = volume of water, m3 or (ft3)
μ = absolute dynamic viscosity of water, Pa·s; kg/m·s or (lb·s/ft2)

 The purpose of rapid mixing is to achieve instantaneous, uniform dispersion of the chemicals through the water body.
Instantaneous flash mixing is not only sufficient, but is desirable because :
a. The production of effective coagulant species greatly depends on being able to achieve a uniform dispersion
of the added chemicals.
b. Rates for the formation of monohydroxocomplexes and other hydroxometal polymers are very rapid.
c. The adsorption rate for the various coagulant products is also very fast.
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  The efficiency of a rapid mix is based on the power imparted to the water, which is measured in terms of the velocity
gradient G and the contact time t.
 Recommended detention times range from less than 1 s up to 1 min and G values from 700 to 4000 s−1.

FLOCCULATION
 the flocculation process allows the colloidal particles to come together and build into larger flocs that are more
amenable to separation by settling, or filtration
 Slow mixing can be achieved mechanically or hydraulically.
 Mechanical flocculation devices may be paddle wheel flocculators, flat blade turbines, and axial flow propellers.
 Mixing by hydraulic means is most commonly used in horizontal flow flocculators.

COMMON COAGULATION & FLOCCULATION PROBLEMS

Problems Possible Causes
Poor floc formation Inadequate coagulant dose.
Improper detention time.
Flakey-feathery floc Excess lime. Lime has a low solubility;
formation of light floc
Inadequate coagulant dose.
Poor flocculation when optimum dose Improper mixing.
of coagulant is used
Poor floc formation under winter Not enough turbidity for an effective
conditions with low water turbidity flocculation.
Improper detention time. Low
temperature causes slower coagulation
which needs longer detention time.
Inadequate flocculation of yellowish Color of water is due to decomposition
water of natural organic substances like
leaves.
Possible Solutions
Run jar test; determine optimum dose
and increase coagulant as required.
Apply needed detention time, if
possible, by adjusting flocculators’
speed or changing flow rate.
Run jar test; lower lime dose as
required.
Check rapid mix and mixer speed;
adjust as needed.
Try some weighting coagulant aid like
clay or sodium silicate.
Determine optimum detention time
and apply it.
Provide low pH and high dose of
coagulant. Alum lowers pH.

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 Inadequate flocculation of summer
water with low turbidity
Floc settles in coagulation basins
Drought condition. A lack of proper
dilution factor and high concentration
of minerals cause poor flocculation
conditions.
Excessive coagulant dose forms heavy
floc.
Weighting coagulant aid dose is too
high.
Velocity in basin is too low.
Run jar test by using alum and a
weighting coagulant aid that will
increase floc density and rate of
coagulation by providing nuclei.
Run jar test to check coagulant dose
and lower as required.
Run jar test with and without coagulant
aid to determine if coagulant aid is
needed. Lower or stop feeding
coagulant aid.
Check velocity and flocculator’s speed.
Increase velocity as needed since too
low velocity allows sedimentation of
floc in basins.

Sample Problems
1. A rapid-mix tank is designed to treat 26 MGD of turbid water. If the detention time is 30 s and the water operating
temperature is 60°F, find a) The required volume of tank, b) The required mixing power in hp

GIVEN: Q = 26 Mgal/day t = 30 s μ = 2.359 × 10−5 lb·s/ft2 at T = 60°F

SOLUTION:
a) volume in ft3
26𝑥106 𝑔𝑎𝑙 1𝑑𝑎𝑦 1𝑓𝑡 3
𝑉 = 𝑄𝑡 = ∙ 30𝑠 ∙ ∙
𝑑𝑎𝑦 86400𝑠 7.481𝑔𝑎𝑙
𝑽 = 𝟏𝟐𝟎𝟔. 𝟕𝟔𝟎𝟖𝒇𝒕𝟑

b) mixing power in hp
G = 900 /s (from table)
900 2 𝑙𝑏 ∙ 𝑠 1ℎ𝑝
𝑃 = 𝐺 2 𝜇𝑉 = ( ) ∙ 2.359𝑥10−5 2
∙ 1206.7608𝑓𝑡 3 ∙
𝑠 𝑓𝑡 550𝑓𝑡 ∙ 𝑙𝑏 ∙ 𝑠 −1
𝑷 = 𝟒𝟏. 𝟗𝟐𝟒𝟖𝒉𝒑

For a given impeller and tank geometry, the impeller Reynolds number, ReI determines the flow pattern in the tank
𝑫𝟐 𝑵𝝆
𝑹𝒆𝑰 =
𝝁
Where D = impeller diameter
N = rotational speed
ρ = density
μ = viscosity
Typically, ReI > 104 is required for fully turbulent conditions throughout the tank.
The power, P drawn by the impeller is made dimensionless by the power number:
𝑷
𝑵𝑷 =
𝝆𝑵𝟑 𝑫𝟓

2. A first-stage flocculator uses a six-bladed Rushton turbine 2m in diameter rotating at 25 rev/min. What is the impeller
Reynolds number? How much power must be applied to the shaft to rotate it?

GIVEN: Rushton turbine NP=5 D=2m N=25rev/min

ρ = 998 kg/m3 μ = 1.31x10-3 kg/m·s
25 998𝑘𝑔
𝐷2 𝑁𝜌 (2𝑚)2 ∙ ∙
𝑚𝑖𝑛 𝑚3
𝑅𝑒𝐼 = =
𝜇 60𝑠
∙ 1.31𝑥10−3 𝑘𝑔/𝑚 ∙ 𝑠
𝑚𝑖𝑛
𝑹𝒆𝑰 = 𝟏. 𝟐𝟔𝟗𝟕𝒙𝟏𝟎𝟔

𝑘𝑔 25 𝑚𝑖𝑛 3
𝑃 = 𝑁𝑃 𝜌𝑁 3 𝐷5 = 5 ∙ 998
∙ ( ∙ ) ∙ (2𝑚)5
𝑚3 𝑚𝑖𝑛 60𝑠
𝑷 = 𝟏𝟏𝟓𝟓𝟎. 𝟗𝟐𝟓𝟗 𝑾𝒂𝒕𝒕𝒔
ChE 513: Industrial Waste Management & Control
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