CDB 3044: PROCESS PLANT DESIGN

Environmental Studies - Waste Water Treatment

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 Outcome

 To design a waster water treatment method

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 Introduction

A typical water and effluent treatment system.

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Water Reuse and Regeneration

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 Introduction
 The capital cost of aqueous waste treatment operations is
generally proportional to the total flow of wastewater.
 The operating cost generally increases with decreasing
concentration for a given mass of contaminant to be removed.
 If two streams require different treatment operations, it makes no
sense to mix them and treat the two streams in both treatment
operations.
 This will increase both capital and operating costs.

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Distributed Effluent Treatment

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 Introduction

 The concept of distributed effluent treatment is one that tends

to treat effluents before they are mixed together.
 Treatment is made specific to individual (or small numbers of)
contaminants while still concentrated.
 The benefit is that, by avoiding mixing, this increases the
potential to recover material, leading to less waste and lower
cost of raw materials.

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 Water Contamination

Aqueous contamination
There are two significant reasons why water contamination needs to be
considered.
 The first is that aqueous effluent must comply with environmental regulations
before discharge. The concentration, and perhaps load, of contamination of
various specified contaminants must be less than the regulatory requirements.

 The second reason is that contaminant levels will affect the feasibility of reuse
and recycling of water, as shown in Figure 26.2. If water is to be reused or
recycled, then the level of inlet contamination to the operation receiving
reused or recycled water must be acceptable.

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 Water contamination
What types of contamination need to be considered?
 Consider first aqueous emissions of organic waste material.

 When this is discharged to the receiving water, bacteria feed on

the organic material. This organic material will eventually be
oxidized to stable end products.

 Carbon in the molecules will be converted to CO2, hydrogen to

− 2−
H2O, nitrogen to NO3 , sulfur to SO4 and so on.

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 Water Contamination
For an example, consider the degradation of urea:
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CH 4 N 2O  O2  CO2  2 H 2O  2 NO3
2

 For every molecule of urea requires 9/2 molecules of oxygen for

complete oxidation.

 The oxygen required for the reactions depletes receiving water of

oxygen, causing the death of aquatic life.

 Standard tests have been developed to measure the amount of oxygen

required to degrade a sample of wastewater

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 Waste Contamination

Standard test:

• Biochemical oxygen demand (BOD)

• Chemical oxygen demand (COD)
• Total oxygen demand (TOD)
• Total organic carbon (TOC)

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 Testing Methods
Biochemical oxygen demand:
 A standard test has been devised to measure BOD in which the
oxygen utilized by microorganisms in contact with the wastewater
over a five-day period at 20◦C is measured (usually termed BOD5).
 The period of the test can be extended to a much longer period (in
excess of 20 days) to measure the ultimate demand.
 While the BOD5 test gives a good indication of the effect the effluent
will have on the environment, it requires five days to carry out (or
longer for the ultimate BOD).

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 Testing Methods

Chemical oxygen demand:

 In the COD test, oxidation with acidic potassium dichromate is used. A catalyst (silver
sulfate) is required to assist oxidation of certain classes of organic compounds.
 Chemical oxygen demand results are generally higher than BOD5, since the COD test
oxidizes materials that are only slowly biodegradable.
 Although the COD test provides a strong oxidizing environment, certain organic
compounds are oxidized only slowly, or not at all.
 The ratio of BOD5 to COD varies according to the contamination. The ratio can vary
between 0.05 and 0.8, depending on the chemical species.
 Domestic sewage has a value of typically around 0.374. An average value across all
types of contaminants is around 0.35.

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 Testing Methods
Total oxygen demand:

 The TOD test measures the oxygen consumed when a sample of

wastewater is oxidized in a stream of air at high temperature (900◦C) in a
furnace.
 Under these harsh conditions, all the carbon is oxidized to CO2.
 The oxygen demand is calculated from the difference in oxygen content
of the air before and after oxidation.
 The resulting value of TOD embraces oxygen required to oxidize both
organic and inorganic substances present.
 The relationship between BOD5, COD and TOD for the same organic
waste is in the order, BOD5 < COD < TOD
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 Testing Methods
Total organic carbon:

 The total organic carbon TOC test measures the carbon dioxide
produced when a sample of wastewater is subjected to a strongly
oxidizing environment.
 One option is to oxidize the sample in a stream of air at a high
temperature (800 to 900◦C) in a furnace, similar to the TOD test, but
measuring the change in CO2 rather than the change in O2.

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 Testing Methods
 Rather than using high temperature in a furnace, other strongly
oxidizing environments (e.g. chemical oxidation) can also be used.

 To obtain the TOC requires that inorganic carbon compounds must be

removed prior to test, or results corrected for their presence.

 The inorganic carbon can be removed prior to test by adding acid to

convert the inorganic carbon to carbon dioxide that must be stripped
from the sample by a sparge carrier gas.

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 Waste Contamination
 If the composition of the waste stream is known,
then the theoretical oxygen demand (ThOD) can be
calculated from the appropriate stoichiometric
equations.

 As a first level of approximation, it can be assumed

that the ThOD would be equal to the COD

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 Contaminants
 Specifically nominated contaminants (e.g. phenol, benzene, etc)
 Heavy metals (e.g. chromium, cobalt, vanadium, etc.),
 Halogenated organic compounds
 Organic nitrogen
 Organic sulfur
 Nitrates
 Phosphates
 Suspended solids
 pH, and so on

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 Specifications
 In addition to the levels of contamination, typically specified
as parts per million (ppm) or milligrams per liter (mg/l),

 There might be regulations for the total discharge of a

contaminant in kilograms per day (kg/d) or tons per year (t/y).

 There might also be a specification for the maximum effluent

temperature.

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 Water Treatment Processes

 Primary (or pretreatment)

 Secondary (or biological)
 Tertiary (or polishing)

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 Primary Treatment Processes

Primary or pretreatment of wastewater can involve either physical or

chemical treatment, depending on the nature of the contamination, and
serves three purposes:

• Allows reuse or recycling of water;

• Recovers useful material where possible;
• Prepares the aqueous waste for biological treatment by removing
excessive load or contaminants that will inhibit the biological
processes in biological treatment.

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 Primary Treatment Processes
Solids separation techniques:
• Sedimentation
• Centrifugal separation
• Filtration

Clarifiers:
• The effectiveness of clarifiers, in petroleum refinery
applications, they are capable of removing typically 50 to
80% of suspended solids, together with 60 to 95% of
dispersed hydrocarbon (which rises to the surface), 30 to 60%
of BOD5 and 20 to 50% of COD
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 Primary Treatment Processes

 Settling to remove solids from aqueous effluent can be enhanced

by the use of centrifugal forces in hydrocyclones

 Solids removal by centrifugation can typically be in the range 50 to

80%, increasing to typically 80 to 95% with chemical addition

 Filtration can be used to remove solid particles down to around 10

μm. Both cake filtration and depth filtration can be used

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 Primary Treatment Processes
Coalescence:

 Coalescence by gravity in simple settling devices can often be

used to separate immiscible liquid–liquid mixtures.
 The coalescence can be enhanced by the use of mesh pads and
centrifugal forces.
 In petroleum and petrochemical plants, a common device used for
the separation of dispersed hydrocarbon liquids from aqueous
effluent is the American Petroleum Institute (API) separator

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 Primary Treatment Processes
Membrane processes:

• Conventional filtration processes can separate particles down to a

size of around 10 μm. If smaller particles need to be separated, a
porous polymer membrane can be used.
• Microfiltration retains particles down to a size of around 0.05 μm.
• A pressure difference across the membrane of up to 4 bar is used.
• The two most commonly used arrangements are spiral wound and
hollow fiber

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 Primary Treatment Processes
Stripping:
• Volatile organic compounds and dissolved gases can be stripped
from wastewater.
• The usual arrangement would involve wastewater being fed down
through a column with packing or trays and the stripping agent
(usually steam or air) fed to the bottom of the column
Crystallization
• If contamination in wastewater has a solubility that varies
significantly with temperature, then cooling might allow
crystallization of a significant proportion of the contamination

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 Primary Treatment Processes
Evaporation
• An extreme case of the use of evaporative crystallization is to
use evaporation to simply concentrate the contamination as a
concentrated waste stream.
• This will generally only be useful if the wastewater is low in
volume and the waste contamination is nonvolatile
Liquid–liquid extraction
• With liquid–liquid extraction, wastewater containing organic
waste is contacted with a solvent in which the organic waste is
more soluble.
• The waste is then separated from the solvent by evaporation or
distillation and the solvent recycled
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 Primary Treatment Processes

 One common application of liquid–liquid extraction is the removal and

recovery of phenol and compounds of phenol from wastewaters.
Adsorption:
• Adsorption can be used for the removal of organic compounds (including
many toxic materials) and heavy metals (especially when complexed with
organic compounds).
• Activated carbon is primarily used as the adsorbent, although synthetic
resins are also used.
• Both fixed and moving beds can be used, but fixed beds are by far the
most commonly used arrangement.
• As an example, adsorption with activated carbon when applied to
petroleum refinery effluent can remove typically 70 to 95% BOD5 and 70
to 90% COD, depending on the effluent being treated.
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 Primary Treatment Processes
Ion exchange
• Ion exchange is used for selective ion removal and finds some
application in the recovery of specific materials from wastewater,
such as heavy metals.
Wet oxidation
• In wet oxidation, an aqueous mixture is heated in the liquid phase
under pressure in the presence of air or pure oxygen, which
oxidizes the organic material.
• The efficiency of the oxidation process depends on reaction time
and pressure.
• Temperatures of 150 to 300◦C are used, together with pressures
of 3 to 200 bar, depending on the process and the nature of the
waste being treated and whether a catalyst is used
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 Biological Treatment Processes (Secondary treatment)

 In secondary or biological treatment, a concentrated mass of

microorganisms is used to break down organic matter into stabilized
wastes.
 The degradable organic matter in the wastewater is used as food by the
microorganisms.
 Biological growth requires supplies of oxygen, carbon, nitrogen,
phosphorus and inorganic ions such as calcium, magnesium, and
potassium.

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 Secondary Treatment

 Domestic sewage satisfies the requirements, but industrial wastewaters

may lack nutrients and this can inhibit biological growth.

 In such circumstances, nutrients may need to be added. As the waste

treatment progresses, the microorganisms multiply producing an
excess of this sludge, which cannot be recycled

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 Biological Treatment Processes
There are three main types of biological process
• Aerobic
• Anaerobic
• Anoxic
Aerobic
• Aerobic reactions take place only in the presence of free oxygen
and produce stable, relatively inert end products such as carbon
dioxide and water.
• Aerobic reactions are by far the most widely used

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 Biological treatment processes

Anaerobic:
• Anaerobic reactions function without the presence of free
oxygen and derive their energy from organic compounds in
the waste.
• Anaerobic reactions proceed relatively slowly and lead to
end products that are unstable and contain considerable
amounts of energy, such as methane and hydrogen sulfide

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 Biological treatment processes
Anoxic:
• Anoxic reactions also function without the presence of free oxygen.

• However, the principal biochemical pathways are not the same as in

anaerobic reactions, but are a modification of aerobic pathways and
hence termed anoxic.

• Anoxic reactions are used for denitrification to convert nitrate to

nitrogen:

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Biological Treatment Processes

Suspended growth aerobic digestion

Attached growth aerobic digestion

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 Biological Treatment Processes

Suspended growth anaerobic digestion using an upward flow anaerobic sludge blanket

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Biological Treatment Processes

Attached growth anaerobic digestion using a fluidized anaerobic bed.

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Biological Treatment Processes

A reed bed.

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 Biological treatment processes

Flow rate Q[L/d] Q-Qw [L/d]

BOD S0 [mg/L] rx = growth rate of biomass [mg/L/d] S [mg/L]
Sedimen- X [mg/L]
Micro-organism rs = consumption rate of limited organic [mg/L/d] e
tation
conc.X0 [mg/L]
Influent Clarified
Aerobic digestion
A effluent
B
C
Aerating sludge
Settling
sludge
Aeration tank
Settling tank
V[L]

Recycle of concentrated sludge Excess sludge

D QW [L/d] E
S [mg/L]
Xr [mg/L]

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Comparison of Biological Wastewater Treatments

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Summary of Treatment Processes for Some Common Contaminants

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 Tertiary Treatment Processes

 Tertiary treatment or polishing treatment prepares the aqueous waste

for final discharge.

 The final quality of the effluent depends on the nature and flow of the
receiving water

 Table 3 gives an indication of the final quality required

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Typical Effluent Quality for Various Receiving Waters

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 Tertiary Treatment Processes

Tertiary processes used include

• Filtration
• Ultrafiltration
• Adsorption
• Nitrogen and phosphorous removal

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 Tertiary Treatment Processes
Filtration

• Examples of such processes are microstrainers (a

fine screen with openings) and sand filters.
• They are designed to improve effluents from
biological treatment processes by removing
suspended material, and with it, some of the
remaining BOD5.
• Sand filtration can remove effectively all of the
remaining BOD5 in many circumstances
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 Tertiary Treatment Processes
Ultrafiltration
• It is used to remove finely divided suspended solids and when
used as a tertiary treatment can in many circumstances remove
virtually all the BOD5 remaining after biological treatment
Adsorption
• Some organic materials are not removed in biological systems
operating under normal conditions.
• Removal of residual organic material can be achieved by
adsorption.
• Both activated carbon and synthetic resins are used.

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 Tertiary Treatment Processes
Nitrogen and phosphorous removal

• Since nitrogen and phosphorous are essential for growth of the

microorganisms, the effluent from secondary treatment will contain
some nitrogen and phosphorous.
• The amount that is discharged to receiving waters can have a
considerable effect on the growth of algae.
• If discharge is to a high-quality receiving water and/or dilution rates
are low, then removal may be necessary.

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 Water Use
Water is used for a wide variety of purposes in process operations:

• reaction medium (vapor or liquid)

• extraction processes
• steam stripping
• steam ejectors for production of vacuum
• equipment washing
• hosing operations, and so on.

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 Water Use
 The reduction in the water usage will be limited by either the operation
requiring some minimum flowrate, below which it cannot operate, or
the outlet concentration from the operation goes to a maximum value.

 The maximum outlet concentration might be set by a number of

considerations:
• maximum solubility
• corrosion limitations
• fouling limitations
• minimum of mass transfer driving force
• minimum flowrate requirements
• maximum inlet concentration for downstream treatment
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Waste Water Treatment Process

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 References

1. Smith, R. Chemical Process: Design and Integration. Wiley, 2005.

2. Sinnott R. K. Chemical Engineering Design, Coulson & Richardson’s Chemical

Engineering Volume 6. 4th Ed. Oxford, UK: Elsevier, 2006.

3. Peters M. S. and Timmerhaus K. D. Plant Design and Economics for Chemical

Engineers. 5th Ed. New York: McGraw-Hill, 2003.

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