Chemical Process

Industries [1]
LESSON 3B:
WATER CONDITIONING AND ENVIRONMENTAL PROTECTION
 Part B

•Environmental
Protection
Environmental Protection

 The protection of the environment is requiring more attention for

chemical engineers every year.
 Environmental factors affect almost every sector of the CPIs, as well
as industries and business in general.
 Expenditures for pollution control for 1981 and those planned for
1982 to 1985 are shown in Table 3.2.
Environmental Protection

 The current large expenditures for pollution control in the U.S. reflect
mainly the intervention of the federal government with strict laws.
 These laws are enforced by the Environmental Protection Agency (EPA).
 Federal water pollution laws were enacted in 1948, 1956, 1961, 1965,
1966, and 1970, but they were primarily involved in aiding states in
establishing limitations for interstate waters.
 The nation’s initial program covering all navigable waterways was
passed and is known as the Water Pollution Control Act of 1972.
 This law established effluent guidelines for both private industry and
municipal sewage treatment plants on a national level.
 In addition, the law set the ambitious goal of prohibiting the discharge
of any type of pollutant into U.S. waters by 1985.
Environmental Protection

 A focal point of the 1972 law is the National Pollutant Discharge

Elimination System (NPDES), which regulates point sources of water
pollution.
 The law states that a NPDES permit is required for the discharge of
any type of pollutant.
 A permit does not condone pollution, but rather controls the type
and amount of effluent from each source.
 Target dates for reducing the amount of discharge in accordance
with a goal of zero discharge are arranged with the recipient of the
permit, who is legally bound to obey the conditions under threat of
possible still penalty.
Environmental Protection

 Federal legislation on air pollution control in the U.S. followed a

pattern somewhat similar to that enacted for water.
 It was 1955 before the first federal law was enacted as the 1955 Air
Pollution Act.
 This provided for research on air pollution effects by the Public
Health Service, some technical assistance to the states, and the
training of personnel in the area of pollution control.
 In 1963, the Clean Air Act provided federal financial assistance but
left the control problem to the states.
 The 1965 Amended Clean Air Act established the first federal
emission standards for cars.
Environmental Protection
 The 1967 Air Quality Act covered the first requirement for ambient air
standards, but these were to be set by the states.
 Finally, in 1970, the 1967 act was amended into strong legislation ,
which has become known as the Clean Air Act.
 This Act provided for:
1. Additional research efforts and funds
2. Additional state and regional grant programs
3. National ambient air quality standards *to be set by the federal gov’t.
4. Complete designation of air quality control regions
5. Implementation plans to meet the standards (item 3)
6. Standards of performance for new stationary sources *
7. National emission standards for hazardous air pollutants
Environmental Protection

 The 1970 Act required that industry monitor air pollutants, maintain
emission records, and make them available to federal officials.
 It also covered automobile emission standards, the development of
low-emission vehicles, and aircraft emission standards.
 On Dec. 23, 1971, the first new source performance standards were
set by the EPA.
 These standards covered 5 types of sources:

Fossil fuel-fired
steam generators Sulfuric acid Portland cement
Incinerators Nitric acid plants
(≥265x10³ MJ/h plants plants
input)
Environmental Protection

 Periodically, additional such standards are set for other sources.

 In general, the standards are strict and are based on the best
pollution control technology available at the time they are set.
 These are revised frequently.

 In 1977, additional Clean Air Act Amendments were enacted, which

further strengthened the role of the government in controlling air
quality throughout the US.
 EPA has established regulation for several identified air pollutants
called criteria pollutants.
Criteria Air Pollutants[1]

Carbon Ground-
Lead
monoxide level ozone

Particulate Nitrogen Sulfur

matter dioxide dioxide
Environmental Protection

 The 1977 Act requires each state to classify areas that are presently
cleaner than the national ambient air quality standard, and allows
for a permissible increase in pollution, provided that the air will still
meet the air quality standard.
 The goal is to ensure that the air in clean air areas does not
significantly deteriorate while allowing industrial growth.
Municipal Wastewaters

 Efficient sewage disposal is important to the health of any Image source:

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 The easy method of disposal in the past was by dilution; the waste
was dumped into an available body of water such as a river or lake,
where the already present oxygen would in time destroy the
organic sewage.
 However, dilution is no longer tolerated even in places where it is
satisfactory.
 There is simply not enough water to dilute the large amount of
wastes from our increasing population and industry.
Municipal Wastewaters

 Pollution controls restrict the dumping of sewage into the sea or the
barging out to sea of sewage solids, which become much more
concentrated in sewage treatment plants.
 The federal Water Pollution Control Act Amendments of1972
required that by 1983, the best practicable waste treatment
technology be used, and that by 1985, the goal of zero discharge is
met.
Municipal Wastewaters

 The impurity in a particular sewage, i.e. the amount of treatment

required, is usually measured on one of two bases:
1) The amount of suspended solids, and
2) The biochemical oxygen demand (BOD), which is the amount of
molecular oxygen required by a microbial population to stabilize
biodegradable organic material.
 Methods of sewage treatment are usually divided into:

Primary (physical) Secondary

Tertiary treatment
treatment (biochemical) treatment
Primary (Physical) Treatment

 Primary treatment in a simple primary plant is design to

 remove 30-60% of the suspended solids in the sewage
 reduce BOD by a like amount
 The effluent is usually chlorinated to destroy bacteria and viruses
 In the primary plant, the influent is screened to allow the passage of
solids not larger than 2.5 to 5 cm.
 “Settleable” solids are then removed.
 Fine particles may be agglomerated to increase their size and
permit settling, so that coagulation of fine particles makes larger
ones by flocculation, and these are then removed by
sedimentation.
The total process is a clarification
operation (Fig. 3.8).
Primary (Physical) Treatment

 Coagulants are added to assist in these operations.

 The chemical additives include inorganic salts, usually of iron or
aluminum (ferric sulfate or aluminum sulfate with lime) which, under
alkaline conditions, form hydrated colloidal flocs of their hydroxides.
 Polyelectrolytes (organic polymers) are also used.

 Primary treatment alone is considered inadequate, since it leaves

much of the fine particles, as well as all of the material in solution.
Secondary (Biochemical)
Treatment
 With secondary treatment, dissolved organic materials are oxidized
to reduce the BOD by 85-90%.
 This imitates nature’s conversion by animal microorganisms, which
feed on them.
 Gases are formed, and a much smaller mass of solids remains.
 Biochemical oxidation may be accelerated in the secondary
treatment by a trickling filter or an activated sludge system (Fig. 3.8).
Activated-sludge Process

 Activated sludge contains aerobic microorganisms that digest raw

sewage.
 Some activated sludge from the previous run is introduced into the
raw sewage, and air is blown in, not in excess but only in the amount
needed.
 Disposal of the solids removed by any of these processes depends
upon local conditions.
 In some cases, they are buried, burned, or sold as fertilizer after
filtering and drying.
 The liquids remaining after the removal of the solids are usually
chlorinated to destroy harmful microorganisms and then discharged
into nearby streams.
Secondary (Biochemical)
Treatment
 Oxygen-producing companies have developed processes using
oxygen rather than air to speed up t he aerobic treatment of
sewage.
 Union Carbide with its UNOX System (Fig. 3.9) is active in this field.
 This is a multistage operation utilizing the highest purity oxygen in the
first stage where the requirements of the sludge being treated are
highest.
 The oxygen is dissolved using low-speed surface aerators or, in large
installations, with a submerged spurge turbine.
Secondary (Biochemical)
Treatment
 Another system of oxygenation of sewage is the PROST System,
which utilizes pressure digestion with air and/or oxygen.
 The influent sewage liquid is mixed with air, oxygen, or a mixture of
the two in a centrifugal pump and passed to a pressure vessel at
pressures of 200 to 500 kPa.
 As the oxygen is dissolved rapidly in the pump, it is almost
completely dissolved by the time the mix reaches the pressurized
digestor, and oxidation takes place so calmly that the digestor may
be simultaneously used as a clarifier to settle out the sludge.
 The liquid then overflows the top with a BOD reduction of 80-90%
and a near absence of turbidity.
Secondary (Biochemical)
Treatment
 High-purity oxygen enjoys a basic economic advantage over air
because of energy considerations.
 The volume of oxygen dissolved per unit of electrical power
consumed is at least 4 times that of oxygen in air, but the amount of
energy need to separate oxygen from air is relatively low.
 Oxygenation systems have other cost advantages, e.g., with regard
to treatment capacity.
 With oxygen systems, the size of the plant may be reduced from
one-half to one-third the size of one operating on air.
 Also, there is a lower rate of sludge generation, and the new systems
can adjust quickly to sudden overloads of waste, a frequent
problem in secondary treatment plants.
Secondary (Biochemical)
Treatment
 Another side
benefit is that odors
are virtually
eliminated
because covered
aeration tanks are
used.
 Table 3.3 shows a
comparison of air
vs. oxygen for
secondary
treatment.
Secondary (Biochemical)
Treatment
 Another development for secondary treatment is the use of fluidized
beds, which combine the best features of trickling filters and
activated sludge systems.
 This system consists of a bioreactor partially filled with sand.
 Wastewater passing upward through the bottom of the reactor
imparts motion to the sand and “fluidizes” it.
 This expanded sand presents a vast surface to support a biological
population.
Secondary (Biochemical)
Treatment
 The surface of the sand eventually becomes covered with a firmly
attached biomass which then consumes the waste materials in the
wastewater.
 The concentration of the biomass is an order of magnitude greater
than conventional activated sludge systems.
 Thus, the bioreactor’s volume may be as little as 10% of that of the
conventional reactor.
Secondary (Biochemical)
Treatment
 When compared with the usual aerobic process,
 Anaerobic fermentation is an energy-saving, biological method of
removing organic matter from wastewater.
 This process has the advantage of being able to treat wastewater
high in organic material (>1000 mg/L BOD) and to convert >90% of
the biodegradable material into methane.
Secondary (Biochemical)
Treatment
 A combination of primary and secondary treatments of municipal
wastewater into one process utilizes a novel approach.
 The water hyacinth, long regarded as a weed, appears to thrive on
sewage.
 It floats on the surface, and its roots adsorb the waste materials
including toxic materials and heavy metals.
 The process is efficient and economical.
Tertiary Treatment

 Tertiary sewage treatment involves further processing steps after

secondary treatment, usually for the removal of pollutants with no
BOD.
 After secondary treatment, water still contains phosphorous,
nitrogen, and carbon compounds in solution, which can serve as
nutrients for the overabundant growth of algae and other aquatic
plants.
 The enrichment of waters with nutrients is referred to as
eutrophication (derived from the Greek words eu, meaning “well”,
and trophein, “to nourish”).
Tertiary Treatment

 Since phosphorous, a major ingredient required for growth, is used in

detergents, excess growth of algae in natural waters receiving
domestic waste discharges is generally blamed on the high
phosphorous content of the water.
 Since complete removal of phosphorous from domestic waste
cannot be accomplished by only limiting the use of phosphorous
compounds in detergents, considerable work has been done in
developing processes for removing phosphates from municipal
wastewater.
 The most common types of chemical treatment are precipitation
with lime and/or metallic hydroxides such as aluminum.
 It is about 90-95% effective and the cost is <$1.32/100 m³.
Tertiary Treatment

 Under some conditions, microorganisms can absorb quantities of

phosphates greatly in excess of their usual needs, a so-called luxury
uptake.
 This uptake is reversible, as decay of the cells can release the
phosphate.
 A treatment plant, such as the one used in the District of Columbia,
has a process that removes the sludge from the final clarifier rapidly
and feeds it into a phosphorous stripper operated in the fashion of
an anaerobic digester.
 ~2/3 of the phosphate in the sludge is released in the digester and
can be removed by chemical means.
 ~90% removal of phosphorous can be accomplished.
Tertiary Treatment

 In 1980, more than 500 plants in the U.S.A. and Canada used
chemical treatment methods to remove phosphorous and nitrogen
compounds.
 In 1972, only 10 such plants were operating.
Industrial Wastewaters

 The problem of adequately handling industrial wastewater is more

complex and much more difficult than that involving sewage.
 Increasing stringent national and local regulations have been
enacted, prohibiting or limiting the pollution of streams, lakes, and
rivers.
 U.S.A.’s federal Water Pollution Control Act of 1972 set the following
goals:
 July 1, 1977 – the utilization of the best practicable control technology
currently available;
 July 1, 1983 – the utilization of the best available technology
economically achievable;
 July 1, 1985 – the discharge of pollutants into the nation’s water to be
eliminated.
Industrial Wastewaters

 Economic and technical studies are necessary to determine the

least expensive way to comply with legal requirements and to
reduce expenses or to show a profit through the recovery of salable
materials.
 Other factors, such as reduction in real estate values, danger to
inhabitants, and destruction to wildlife, are also involved.
 The great variety of chemical wastes produced in the nation’s
factories forces specific treatment in many instances.
 A few general practices are in use in many fields.
Industrial Wastewaters

 One is that of storing, or lagooning, wastes.

 This may serve many different purposes.
 In factories having both acidic and basic wastes, it reduces the cost
of neutralization.
 In plants having wastewater containing large amounts of organic
material (e.g., some paper mills), this results in a decrease in
suspended matter and a reduction in the BOD.
 The use of flocculating agents (alum, FeSO₄) to remove suspended
solids, and aeration to reduce the BOD, are also common to many
industries.
Industrial Wastewaters

 A general problem in all industries is the disposal of wastes obtained as

a result of water softening treatment.
 Lime sludges may be lagooned and settled, or they may be dewatered
and calcined for reuse.
 This sludge also finds some application in absorbing oil from other
wastes.
 Brine used in regenerating ion-exchange plants is best stored and then
added to streams by controlled dilution at high water.
 When the industry uses raw materials of complicated organic nature,
an activated-sludge process may be used to treat the wastes.
 This process can be adapted to wastes from canneries, meat-packing
plants, milk-processing plants, rendering plants, and others.
Industrial Wastewaters

 Many organic compounds are toxic, resistant to natural

degradation, and require special handling before they can be
safely discharged.
 One technique for removing this toxic materials from wastewater is
by absorption onto activated carbon or a porous polymeric resin.
 Often, the organic material may be removed from the resin with a
suitable solvent and recycled.
 The process has been particularly useful for treating wastewater
containing chlorinated pesticides.
Industrial Wastewaters

 Tannery wastes may be treated by flocculation and sedimentation

or filtration.
 Brewery wastes are subjected to trickling filters to reduce the BOD
and remove most of the suspended solids.
 Paper mills have a serious problem, especially in treating sulfite
wastes.
 The processing of wastes from large chemical plants is exceedingly
complex because of the variety of chemicals produced.
 Ex. The Dow Chemical Co. at Midland, Michigan manufactures 400
chemicals in 500 processing plants and laboratories, resulting in a
total of 757,000 m³/day of wastewater.
Industrial Wastewaters

 Equalization of acid and basic wastes and other general practices

are followed, but many of the wastes are given treatment at the
source, with an eye to recovery of valuable materials and by-
products.
 Kodak ensures limited pollution of the Genesee River by the use of
clariflocculation basins, sludge filtration, and cake disposal, and is
employing ion exchange to regenerate phosphoric acid used as
the electrolyte in anodizing aluminum sheet.
Industrial Wastewaters

 Anaerobic treatment is useful for a wide range of organic wastes, and

as a bonus, produces methane-rich fuel gas that can be burned in the
power plant.
 Increasing emphasis in industrial-waste treatment is being placed on
the recovery of useful materials.
 Fermentation wastes (slop), after evaporation and drying, are being
sold as animal food.
 The use of ion exchangers promises the recovery of chromium and
other metals from plating procedures.
 Ferrous sulfate is being obtained from pickling operations to a limited
extent.
 The cost of energy is also an important consideration in any method of
waste disposal.
Industrial Wastewaters

 In the past, the waste streams or sludges containing hazardous

chemicals have been injected into deep wells, dumped into the
ocean, or stored in a landfill.
 All of these methods are objectionable for one reason or another,
and new regulations are demanding alternative methods of
disposal.
Industrial Wastewaters

 Wet air oxidation is one such method and offers an opportunity to

recover inorganic chemicals.
 The oxidation takes place in an aqueous medium at temperatures
ranging from 177-315°C.
 Preheated wastewater is reacted with a stoichiometric quantity of
compressed air.
 The exothermic heat of reaction of the organic components with
oxygen raises the temperature of the reactor.
 Temperature and oxidation times can be varied depending upon
the waste to be treated.
Industrial Solid Wastes

 Most solid wastes are separated as sludge from process of

wastewaters and must be treated to render them comparatively
harmless before they can be disposed of.
 Hazardous materials range from inorganic salts to organic
compounds to radioactive materials.
 Each type of material may require a different treatment.
 The sludge is usually dewatered by centrifugation, filtration, and/or
heat treatment.
 Aerobic or anaerobic digestion can remove some organic
compounds from organic, petrochemical, and paper processes,
and thus reduce the BOD of the resultant sludge.
Industrial Solid Wastes

 However, many inorganic compounds and some organic materials

must be chemically fixed.
 Neutralization of acids and bases is an obvious method.
 Oxidation of many compounds can convert them into harmless
products, but the toxicity of many other compounds cannot be
destroyed so readily.
 Binding into a chemical matrix that is impervious to water penetration is
another method of inactivating hazardous materials.
 Incineration, both dry and wet, has many variations designed to
detoxify waste materials.
 Pyrolysis (breakdown without oxidation) is now a common technique
used to convert plastic waste into energy, in the form of solid, liquid and
gaseous fuels.[2]
Industrial Solid Wastes

 Both high- and low-level radioactive wastes have posed difficult

disposal problems.
 Vitrification and granulation are being used to eliminate the need
for storing liquid radioactive materials, and thus the possibility of
seepage of waste through a deteriorating container.
 Landfill and storage in deep geologic formations have been the
usual method of disposal.
 However, ecological questions continue to be raised and much
research is being conducted into more adequate, safe methods for
disposal of this type of waste.
Industrial Solid Wastes

 Waste exchanges serve a useful function in finding customers for

wastes.
 They publish listings of wastes available for reuse and of companies
seeking particular waste materials, and act as the go-between for
both parties.
 Waste disposal firms are becoming more active in the chemical
waste disposal business.
 They are particularly useful for small companies which do not have
the facilities to dispose of their own wastes.
Air Pollution

 Air pollution, or atmospheric contamination, is an acute problem

throughout the country.
 Among the many causes of air pollution are industrial operations,
transportation vehicles, and incineration of rubbish and waste by
individuals.
 Many contaminants may be eliminated at the point of production, for
instance, at the exhaust pipe of an automobile, before smog is formed.
 For this, catalytic afterburners have been developed.
 Catalytic exhaust systems were installed on 1975 model cars in the
U.S.A. to meet the tough emission guidelines of the EPA for
hydrocarbons and carbon monoxide.
 The use of catalytic exhaust systems requires the use of lead-free
gasoline, so that the catalyst will not be poisoned by the lead.
Air Pollution

 Air pollutants leaving chemical processes and other industrial

installations may be gases, mists (liquid particles <10µm in diameter),
spray particles (liquid particles >10µm), dusts, fumes, or
combinations of these.
 Electrostatic precipitators are widely used for dust collection, along
with baghouses, cyclones, and scrubbers.
 Mist eliminators have been developed and applied widely in the
chemical process industries for the collection of liquid particles.
Air Pollution

 Of the various gaseous pollutants from industrial processes, sulfur

dioxide has probably received the most attention.
 Sulfur dioxide has been discharged into the atmosphere in large
quantities from electric power plants that burn coal and oil
containing sulfur.
 Other sources have included ore-roasting processes for the
production of lead, copper, and zinc, and sulfuric acid plants.
 Of these various sources, the electrical power industry problem has
been studied the most extensively because of the amount of sulfur
dioxide discharged.
Air Pollution

 One approach has been the desulfurization of fuel prior to its use in
a boiler.
 This approach has been used for years by the petroleum industry to
produce low-sulfur oil; however, it has not been developed to date
for the large-scale desulfurization of coal.
Air Pollution

 A number of stack gas sulfur dioxide removal processes have been

worked out for large boilers.
 The chemical processes for air pollutants include scrubbing with a
magnesium oxide slurry, limestone slurry scrubbing, catalytic
conversion of sulfur dioxide to sulfur trioxide, spray dryer-type
scrubbing in which the slurries are reduced to a dry powder product
of the process, dry scrubbing with nahcolite or similar alkaline
agents, reaction of SO₂ with sodium sulfite to form sodium bisulfite at
relatively low temperature (Well-man Lord process), and the
absorption of SO₂ by sodium citrate solution (Flakt-Boliden process).
Air Pollution

 The removal of SO₂ and also NOₓ from the flue gases of coal and oil
burning is becoming a very important ecological issue.
 Smokestacks have been built higher and higher to discharge the
pollutants high into the atmosphere so that they would not
contaminate the surrounding air.
 However, these noxious gases now are caught by the prevailing
winds, changed into nitric and sulfuric acids by contact with
moisture in the air, and deposited as “acid rain” perhaps hundreds
of miles away from the source.
 This acid rain may have a pH as low as 1.5, but more often it is about
pH 3.5.
 The effect of this on plant and marine life is disastrous and is certainly
not desirable for humans.
Air Pollution

 Forests are rendered quite unhealthy, primarily because of the

decrease in soil microorganisms that fix nitrogen.
 The fish in the lakes that the rain falls upon become stunted or dying.
 The cost of reducing sulfur emissions by 3% (10⁶ t/y) by the electric
utilities (which produce 65% of the SO₂ emissions) has been
estimated at $2,000M in 1981.
 To reduce emissions 15-30% (6 to 10⨯10⁶ t/y) would cost $5,000M to
$7,000M.
 Weighed against these figures, the U.S.A. National Academy of
Science has estimated the cost of the damage in the eastern third
of the country to be $5,000M in 1978.
Other References

[1] https://www.epa.gov/sites/default/files/2015-
10/documents/ace3_criteria_air_pollutants.pdf
[2] https://www.frontiersin.org/articles/10.3389/fenrg.2019.00027/full
end