Industrial Wastewater

Industrial Wastewater
The water or liquid carried

waste from an industrial process

These wastes may result from
any process or activity of
industry, manufacture, trade or
business, from the development
of any natural resource, or from
animal operations such as
feedlots, poultry houses, or
dairies
The term includes contaminated
storm water and leachate from
solid waste facilities
Waste material (solid, gas or
liquid) generated by a
commercial, industrial or
nonresidential activity

What is pollution?
Pollution means:
changes in the physical, chemical and biological characteristics of
air, land and water
harms for the human and other living species, and,
degradation of the ecosystems
...the undesirable state of the natural environment being
contaminated with harmful substances as a consequence of human
activities
For example, Water Pollution refers to contaminants in aquatic
ecosystems (streams, lakes, etc) which render them unfit for a
particular use.
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Pollutants can reach:

1.

Air

2.

Water

3.

Solid waste

Water standards:
Drinkable
Recreation: swimming, fishing.
Irrigation

Water impurities may or may not be harmful; it depends on:

The amounts and nature of these impurities,
The next use to which the water will be put, and
The tolerance of these impurities for the next use.

Types and characteristics of wastewaters:

Contaminants

Reason for importance

Physical suspended solids

They can lead to the development of

sludge deposits.

Chemical biodegradable
organics

When discharged untreated to the

environment, they lead to the depletion of
natural oxygen resources.

Nutrients

If discharged, they can lead to water

pollution.

Hazardous

Because of their characteristics

(e.g.,toxicity, flammability) are dangerous
for human health and the environment.

Heavy metals

They can negatively impact upon

biological waste treatment processes.

Dissolved inorganic solids

They are result of water use, and may

have to be removed if the wastewater is to
be reused.

Biological pathogens

Communicable diseases can be

transmitted by the pathogenic organism in
wastewater.

Water standards

Industrial effluent standards

Parameter
Total suspended
solids, (mg/l)

BOD5, (mg/l)

pH

Mexico

USA

Canada

150

27

15

20

56

15

5-10

6-9

6-10.5

What is BOD?
By definition, BOD is the quantity of oxygen required for the stabilization
of the oxidizable organic matter present over 5 days
of incubation at 20 oC; that can be explained as a measure of the
oxygen required by microbes to degrade a sample of effluent.
The organic content of the water can be estimated by the BOD.

Biochemical Oxygen Demand (BOD)

Definition: The amount of dissolved oxygen utilized by microbes for

the biochemical oxidation of organic (carbonaceous BOD) and

inorganic (autotrophic or nitrogenous BOD)

The BOD test was developed in 1930s. This is a five day test that
measures the amount of O2 consumed in a wastewater sample by
a mixed population of heterotrophic bacteria in the dark at 20oC

BOD of wastewater is typically 110-440 mg/L and must be

reduced to 20 mg/L for discharge

BOD = Di Df
P
where:
Di = initial dissolved O2 concentration
Df = final or 5-day dissolved O2 concentration
P = volumetric fraction of wastewater
Example: 5 ml wastewater is added to a 300 ml BOD flask
P=

5 = 0.0167
300

Di = 8 mg/L

Df = 2 mg/L

BOD = 8 2
= 359 mg/L
0.0167

Oxidation is usually 60-70% complete after 5 days

Total Organic Carbon (TOC)

TOC is measured using a TOC analyzer. The sample is combusted and

organic carbon quantified using infrared detection.

Chemical Oxygen Demand (COD)

COD is measured following digestion at high temperature with

strong oxidant such as chromic acid, or sulfuric acid/potassium
dichromate. The chromate ion reacts with the COD producing a
color that is measured.

If COD >> than BOD what does this mean?

Why should we minimize the use of water?

Water is such an important part of many manufacturing

processes that we must consider Effluent Treatment as a

part of the main process because of the great amount
always involved.
Water is abstracted from aquifers and rivers, treated and

supply to industries and homes for different uses; used

water is supposed to be treated and discharged again into
the rivers. Most of the times, this water returns to its
natural environment but unfortunately, with a greater
heat content or with some substances added.

Why should we minimize the use of

water?
It is also important to minimize use of water because of several reasons:
Fresh water is often scarce. High costs involved operating effluent
treatment plants.
Difficult to separate all the elements that pollute water.

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Industrial pollution problems

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Industrial pollution problems:

The main pollution problems are related to :
Increasing use of water for agriculture.
The increase of aqueous effluent to receiving water.
Population growth.
Industrial products and services.
The mental, technical, financial, regulatory and institutional barriers

to implement preventive modern technologies.

RESULTS:
Ecosystems decline.
Industrialization social costs.
The increase of human diseases.

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The petroleum industry

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The Petroleum Industry:

Crude oil refining operations involve extracting useful petroleum
products from crude oil. Crude oil contains fractions of napthas,
gasoline, gas oils, diesel fuel, asphalt, jet fuel and lubrication fuels.
Large quantities of production wastes are produced during
exploration and production:
Wastewater
Solid waste
Toxic pollutants

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The Petroleum Industry:

Production wastes in the petroleum industry can be grouped broadly
into 2 classes:

Wastes related to drilling including chemical additives: treatment

and disposal of oil drilling wastes takes place either on or off the
drilling site.

Wastes related to oil production, primarily produced water:

The volume of produced water exceeds the volume of drilled wastes.
If environmental quality standards are not exceeded the remainder
may be discharged to surface waters. The majority of produced
water is disposed of underground through injection wells and it is
permitted under U.S. EPA control programs.

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What is refinery effluent?

Petroleum refineries use large volumes of water in their processes.
The wastewater contains hazardous chemicals:

Refinery wastes:
Emissions from refineries include:
Sulphur oxides
Nitrogen oxides
Benzene, toluene and xylene
VOC
Wastewater containing BOD levels
Heavy metals

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Wastes generated:
Pollution
Cooling systems

Polluted wastewater

Solid waste and

sludge
VOC emissions

Others emissions

Approximate Quantities
3.5-5 m3 of wastewater generated per ton of crude.

BOD 150-250 mg/l

COD 300-600 mg/l
phenol 20-200 mg/l
oil 100-300 mg/l (desalted water)
oil 5000 mg/l in tank bottom
benzene 1-100 mg/l
heavy metals 0.1-100 mg/l

3 to 5 kg per ton of crude (80 % should be considered as hazardous waste

because of the heavy metals and toxic organic presence).
0.5 to 6 kg/ton of crude.

BTX (Benzene, Toluene and Xylene) 0.75 to 6 g/ton of crude

Sulphur oxides 0.2-0.6 kg/ton of crude
Nitrogen oxides 0.006-0.5 kg/ton of crude

(Pollution Prevention and Abatement Handbook World Bank Group)

Programs for reducing pollution

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Government programs for reducing

pollution:
For sustainable development, governmental pollution prevention
programs can best counteract the pressure to invest in end of
pipe pollution solutions by demonstrating the economic and
environmental benefits of a source reduction approach, making
technical information available and providing technical
assistance.

EPA has been working with industry and government representing

environmental, community and work force issues to prevent
pollution at the source prior to end of pipe treatment.
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Government programs for reducing

pollution:
Laws such as NEPA, TCSA, CAAA and PPA remain outside the scope of
most pollution control work. The following options were
suggested for USEPA for moving forward interaction in the US:
1.

Add multi-media provisions to the existing regulations.

2.

Correct laws in other policy sectors with environmental

measures.

3.

Make NEPA a stronger statute.

4.

Make TSCA a law which can use EPA programs to control and
reduce toxic substances.

5.

Establish pollution prevention approaches.

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Programs for reducing pollution:

Manufacturers could implement a variety of
improved management procedures
that would aid pollution reduction:

Environmental audits. Identify (inventory) and correct problems (strategies

to achieve reductions) that generate wastes.

Regular preventive maintenance. Inspection, maintenance and

replacement of equipment.

Material handling and storage. Emissions of hazardous material must be

avoided. There should be labels of all containers and first aid
recommendations.

Employee training. Well informed employees are better able to make

valuable waste reduction suggestion.

Operating manual and record keeping. Good facility documentation:

process procedures, control parameters, hazards and operator
responsibilities.

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Environmental programs:
Some industries may see no difference between end of pipe pollution control and
a front end pollution prevention control.
The importance is that those industries may not go beyond the first stage of waste
reduction.
As the environmental concern deepens, industries have to move further up the
production chain:

End of pipe solution to wastes

and pollutants; and later

Internal process modifications to reduce emissions and wastes, and

eventually

Redesign products to achieve a maximum level of recycling of raw

materials and minimization of wastes after the products are used.
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Some measurements to save water:

Keep water effluent streams separated.
Reuse water as close to source as possible.
Recycling whenever it is possible.
Better control of usage with automated systems.
Checking and control of leaks.
When buying new equipment, evaluate water-efficiency
models including accessories.

Reducing the quantities of chemicals so that the amount of

dilution water will be reduced.

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Reusing water:
It is not only possible but necessary to reuse wastewater of a process
stream before it leaves the plant accomplished by piping, diluting
or treating some of the effluents before using them again.
Some plants are now using closed systems, so that there are no
water discharges.
Zero discharges has been practiced in locations where water is
scarce, and may involve technologies for removing suspended and
dissolved solids.
Complete demineralization is relatively expensive, however, in some
cases wastewater discharges can be reduced significantly with
other less expensive technologies.

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Treatment processes

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Expectations of a water treatment program:

The expectations from a water treatment program should be
integrated to include all aspects of the program, from the proposal
through to the implementation stages.

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Treatment Program
As we will see in the next diagram, the expectations that a
good treatment program should give us are listed below:
Overview of a new or existent problem.
Lab study of all system and water composition.
Submit a proposal.
Program implementation.
Monitoring to optimize.
Use of modern treatment techniques.

Program under control

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Treatment Program

New or
Problem
System

Plant
Study

Proposal

Lab
Study

Implement
Program

System
under
control

Follow-up

New Product
Technology

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Wastewater treatment processes:

Wastes are generated by every industrial enterprise, and this wastes
can either be liquids or solids.
Wastewater treatment can be divided into three stages:
1.

Primary treatment that uses physical operations to remove free

oil and/or suspended solids.

2.

Secondary treatment to remove dissolved contaminants

through chemical or biological action, and

3.

Tertiary treatment for the removal of residual contaminants.

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Separation order
This list shows how separation is carried out:

Primary treatment
Sedimentation
Aeration

Secondary treatment
Tertiary treatment

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Treatments
Primary treatment prepares the wastewater for biological
treatment. Large solids are removed by screening, and grit.
Equalization in a mixing basin, levels out the flows variation and
concentrations. Neutralization, where required, follows
equalization. Oils, greases and suspended solids are removed by
flotation, sedimentation of filtration.
Secondary treatment is a biological degradation of soluble organic
compounds from input levels of 50- 1000 mg/l BOD or greater to
effluent levels under 15 mg/l. Aerobic treatment in an open vessel
is done. After biotreatment, the microorganisms and solids
suspended are allowed to settle.
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Treatments
The tertiary treatment remove specific residuals. By filtration,
suspended colloidal solids can be removed; adsorption removes
organics by granular activated carbon (GAC); and chemical
oxidation also removes organic compounds.
Tertiary systems have to treat great amounts of wastewater, so
they are expensive.
When streams rich in heavy metals, pesticides or other substances
that may pass through primary treatment and inhibit biological
treatment are present, in-plant treatments are necessary.
Precipitation, activated carbon adsorption, chemical oxidation, air or
steam stripping, wet air oxidation, ion exchange, reverse osmosis
are some of the methods useful when in-plant treatments are to be
used.
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The tertiary treatment

Tertiary treatment is a polishing step. Its importance is that rather
than have to find solutions at the end of pipe, where primary and
secondary treatments are used to, it is possible to minimize some
toxics or hazardous components in the process before they are
combined with other less hazardous.

Biological treatment usually produces a 30/20 effluent with no more

than 30 mg/l suspended solids and 20 mg/l BOD.

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Tertiary treatment
However, river flows have decreased owing to drought conditions. In these
circumstances, new limits are imposed on the quality of the final effluent.
The treatment processes beyond the secondary treatment to achieve the
required limits in the process are well known as tertiary treatments.

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In plant treatment
Before end of pipe wastewater treatment, a program of waste minimization
should be initiated.
1.

Recirculation. In the paper board industry, white water from a paper

machine can be put through a save all to remove the pulp and fiber
and recycled to various points in the process.

2.

Segregation. Clean streams are separated for direct discharge.

3.

Disposal. In many cases, the total discharge BOD and suspended

solids can be reduced by removal of residue in semidry state for
disposal.

4.

Reduction. The use of automatic cutoffs can reduce the wastewater

volume.

5.

Substitution. The substitution of chemical additives of a lower

pollutional effect in processing operations.

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Wastewater treatment processes:

Process selection

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Figure 1. Conceptual treatment program for

organic and toxic industrial wastewater
For wastewaters containing nontoxic organics, process design criteria can be obtained from lab
studies.
To define the wastewater treatment problems, a preliminary analysis should be carried out:
Organic
streams
Biodegradable

volatile

Streams containing
heavy metals

Mineral
streams

Toxic and/or
nonbiodegradable

Source control
Figure 3.

Equalization
Neutralization
Oil/grease removal
Suspended solids

Biological treatment

Final disposal
(Eckenfelder, 2000)

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Source treatment:

goal

Source reduction is any activity that reduces or eliminates the

generation of hazardous wastes at the source

The fundamental goal is to enact changes in consumption, use and

waste generation patterns associated with products

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Source treatment:
Source treatments involves different definitions of source reduction,
but the general consensus appears to be that include any in-plant
actions to reduce the quantity or the toxicity of the waste at the
source.
Examples include equipment modification, design and operations
changes of the process and products and substitution of raw
materials.

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Figure 2. Laboratory studies for heavy

metals/volatile organics
start
Equalized
sample

Priority
pollutants
scan and
bioassay

Fed
batch
reactor

VOC/NH3

Air or steam
stripping

Heavy metals

Chemical
oxidation
reduction

Precipitation

When toxic and nontoxic organics and

Nondegradable/ toxic
Source
treatment

Degradable

inorganics are present, it is necessary

to evaluate the existence of heavy
metals or volatile organics.

Long-term
biodegradation
Granular
activated
carbon
Priority
pollutants
scan and Priority pollutants/toxic
bioassay

Powder
activated
carbon

Reverse
osmosis

Ion
exchange

TDS/inorganics
(Eckenfelder, 2000)

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Figure 3. Treatment of toxic wastewater:

In-plant treatment
To discharge
recycle or
treatment

Reverse
osmosis

If the wastewater is
nonbiodegradable or
toxic, it should be

Ion
exchange

Polymeric
resins

Filtration

Granular
carbon
adsorption

Precipitation

Anaerobic
treatment

Oxidation
reduction

Wet air
oxidation

considered source
treatment or in-plant
modification.

Process
wastewater
(Eckenfelder, 2000)

Heavy
metals

Organic
chemicals

Chemical
oxidation

Air or steam
stripping

Volatile
organics
ammonia

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Methods for suspended solids removal

Sedimentation is the more common technique in wastewater
treatment because it involves little mechanical equipment and it is
very stable to operate. However, there are some situations where
flotation is a better choice.

Flotation is a good technique for solids removal when the

density difference between water and the solids is marginal, or the
solids have a high fat or oil content.

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Methods for suspended solids removal

Coagulation is employed for removal of waste materials in
suspended or colloidal form. Colloids are particles within the size
range of 1 nm to 0.1 nm, do not settle out on standing and can not
be removed by conventional physical treatment processes.

Precipitation. In the water treatment, the precipitation process

is used for softening (removal of the hardness caused by calcium
and magnesium) and removal of iron and manganese.

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Flotation:
Dissolved air flotation, which is a common technique. This technique
basically consists on injecting an aqueous stream containing
dissolved air into the wastewater . The dissolved air forms
bubbles when it comes out of solution and carries suspended
particles, which tend to concentrate at the bubble wastewater
interface, to the surface, where they form an emulsion.

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Flotation:
General diagram for flotation methods:

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Coagulation:
Paperboards wastes can be effectively coagulated with low dosages
of alum. Silica or polyelectrolyte will aid in the formation of a rapid
settling floc.
Wastes that contain emulsified oil can also be clarified by
coagulation.
For effective coagulation, alkalinity should first be added, . After
addition of alkali and coagulant, a rapid mixing is recommended.

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Heavy Metals Removal:

HEAVY METALS REMOVAL TECHNOLOGIES
Conventional precipitation
Hydroxide
Sulfide
carbonate
coprecipitation

Enhanced precipitation
Dimethyl thio carbamate
Diethyl thio carbamate
Trimercapto-s-triazine, trisodium salt

Other methods
Ion exchange
Adsorption

Recovery opportunities
Ion exchange
Membranes
Electrolytic techniques

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The Biological Treatment

When biological

Influent
wastewater

treatment is
needed, there
are several

Physical and
chemical treatment

No

Biodegradable

Yes

High
High
strength
strength

Yes

Anaerobic
treatment

options:
Yes
Discharge

Yes

PACT

Inhibitory
No
Nondegradable
fraction

Polished
effluent

No
Discharge

Complete mix
system

No

Readily
degradable

Yes

Plug
flow system

Selector
system

No

Nitrogen
removal
required

No

Dispersed
growth system

Fixed
Growth system

Yes

Intermittent
process

Nitrification/
Denitrification
system

Yes

Polished
effluent

No
Discharge

(Eckenfelder, 2000)

Discharge

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The biological treatment: typical operating

parameters and dimensions
Treatment
method

Mode of operation

Degree of
treatment

Land requirements

Lagoon

Intermittent or continuous
discharge; facultative or
anaerobic

Intermediate

Earth dug; 10-60 days

retention

Activated

Completely mixed or facultative

lagoons

continuous basins

High in summer;
less in winter

Earth basin, 8-16 ft

deep, 8-16 acres/
(million gal/d)

Pier-mounted or
floating surface
aerators or
subsurface diffusers

Solids separation in
lagoon; periodic
dewatering and sludge
removal

> 90% removal of

organics

Earth or concrete
basin; 12p20 ft deep;
75000-350000ft3/
(million gal/d)

Diffused or
mechanical
aerators; clarifier
for sludge
separation and
recycle

Excess sludge
dewatered and
disposed of

225-1400 ft /(million
gal/d)

Plastic packing 2040 ft deep

Pretreatment before
POTW or activated
sludge plant
Solids separation
required

Equipment

Odor control
frequently required

Activated

Completely mixed or plug flow;

sludge

sludge recycle

Trickling filter

Continuous application; may

employ effluent recycle

Intermediate or
high, depending on
loading

RBC

Multistage continuous

Intermediate or high

Plastic disks

Anaerobic

Complete mix with recycle;

upflow or downflow filter,
fluidized bed; upflow sludge
blanket

Intermediate

Gas collection
required;
pretreatment before
POTW or activated
sludge plant

Spray

Intermittent application of

irrigation

waste

(Eckenfelder, 2000)

Complete; water
percolation into
groundwater and
runoff to stream

40-300 gal/(min.acre)

Remarks

Aluminum irrigation
pipe and spray
nozzles; movable for
relocation

Solids separation
required; salt content
in waste limited

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Advanced wastewater treatments

Advanced wastewater treatment is defined as the processes that remove more
pollutants from wastewater than the conventional treatments. This term
may be applied usually as tertiary treatment, but most of their goals are to
remove nitrogen, phosphorus, and suspended solids.
Advanced treatments include:

Chemical coagulation of wastewater

Granular media filters

Ultrafiltration

Nanofiltration

Wedge-wire screens

Microscreening

Diatomaceous earth filters

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Volume and disposal reduction

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Volume reduction
Volume reduction can be used to reduce treatment cost and to
reduce handling and disposal costs for residues remaining after
treatment. Volume reduction can be accomplished by using a
variety of methods:
Reuse of treated wastewater and wastes
Treatment modifications to reduce solid residues
Segregated treatments to reduce hazardous waste mixtures
Incineration to reduce waste volume and to render a hazardous
waste nonhazardous.

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Reduction of waste production and disposal

volumes
Simple dewatering: the sludge is discharged into a series of tanks
and allowed to settle. Top water can then be decanted. This
method reduce the volume of sludge for disposal.

Composting: the material is mechanically turned at intervals, force

aerated and often contained in a building where heat losses, odor
and water content can be controlled.

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Reduction of waste production and disposal

volumes
Digestion: is the slow degeneration of the organic content of
sludge by obligate anaerobic bacteria to simpler compoundscarbon dioxide, water and anions (nitrate, sulphate, phosphate).
Digestion is one of the few sludge treatment processes in which a
significant reduction of pathogens is possible.
The digestor gas produced is 65-70% methane, 30-34% carbon
dioxide, and traces of sulphur compounds. The collected gas is
burnt in a boiler to keep the digestor warm and the excess put to
further heating or power generation purposes.

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Reduction of waste production and disposal

volumes
Incineration: its main advantages lie in the complete destruction of
organic compounds, the ash being inert and usually less than 25%
of the original sludge volume.
Most incinerators are of the fluidized bed variety.

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A waste management diagram

Upgrade
operation

Waste
recycle

Redesign
process

Waste
treatment

Increasing Effectiveness
of waste management
Substitute
raw material

Waste
disposal

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