Chemical Methods of Wastewater Treatment

Organized as Waste Technology Assignment C-E Class submitted to

Irnia Nurika, STP, MP, PhD

Organized By:

Dwi Suryo Harini (155100300111048)

Putri Fitriani Sita (155100301111047)
Puspamega Yulisnaiani E. (155100300111053)

AGROINDUSTRIAL TECHNOLOGY
AGRICULTURE TECHNOLOGY FACULTY
BRAWIJAYA UNIVERSITY
MALANG
2017
 PREFACE

This assignment is part of course contract that has to be fulfil the

requirement subject of Waste Technology of Agricultural Technology Faculty,
major of Agroindustrial Technology, University of Brawijaya, year of 2017. The
topic is relevant to the term of Waste Technology about the method of industrial
waste treatment and its process. The aim of this assignment is to get more
knowledge in the terms of Waste Technology in specific purpose of Chemical
Methods of Wastewater Treatment. Thanks and appreciation to our respect lecturer
Venerable: Ma'am Irnia Nurika, STP, MP, PhD who is advising us about this
subject.
 CHAPTER 1

INTRODUCTION

1.1 Background

Nowadays, production of waste increase continously with the increasing of

population, so that it become a pressing problem. As we know, there are three
types of waste: solid waste, waste water, and air pollution. But, in this paper just
focus on the wastewater discussing. Wastewater or sewage is the byproduct of
many uses of water from household or industry. Therefore, wastewater treatment
is important to manage water dischareged from home and industries to reduce the
threat of water pollution. In general, these processes are divided into three stages:
preliminary (physical), primary (physical) treatment and secondary (biological)
treatment. Minimally, wastewater should receive primary (physical
removal/settling) and secondary (biological) treatment, which can be followed by
disinfection before discharge. More advanced processes (tertiary treatment) may
be required for special wastes.
Selection of the proper process was preceded by classifying characteristics
of contaminants in wastewater using the indicator parameters. It is because the
technology that will be used for wastewater treatment should be appropriate with
the characteristics of wastewater, so that can consistently meet the standard as
required. After contaminants were characterized, held a detailed consideration of
the economics, technical aspects, security, reliability, and ease of operation. In the
economic factors, it means that the process should allow optimum utilization of
capital, the require of land should be minimized, and the process design (operation
and maintenance) should be conducive to attaining lower running cost. Beside
that, the technology should be easy to understand and deliver the desired quality
on consistent basis. After consideration detail, it is also necessary doing the
feasibility studies or laboratory scale experiments that aim to ensure that the
chosen technology consists of processes that is appropriate to the characteristics of
the waste that would be treated, develop and collect the necessary data to
determine the expected processing efficiency, and provide technical and economic
information necessary for the application of the actual scale.

Chemical wastewater treatment is usually performed to remove particles

that are not easy to settle, heavy metals, phosphorus compounds, and toxic
substances, by neutralization and coagulation. Several factors can affect the
chemical method (coagulation) such as the quality of water (dissolved gases,
color, turbidity, taste, odor, and hardness); the number and characteristics of
colloid; the degree of acidity (pH); the temperature of the water; the alkalinity of
water; and the characteristics of ions in water.
1.2 Formulation Problem
How is the processing of wastewater treatment using chemical method?
How does the chemical process can be used to remove substances from
wastewater?
How is the procedure that can be used to develop an effective and efficient
treatment technology?

1.3 Purpose
Knowing the processing of wastewater treatment using chemical method
Knowing the chemical process can be used to remove substances from
wastewater
Knowing the procedure that can be used to develop an effective and
efficient treatment technology

CHAPTER II
 DISCUSSION

Wastewater treatment using chemical method depend on the chemical

characteristics of the pollutants, their tendency to react with chemical compound,
and the chemical characteristics of reaction between pollutants and chemical
compound, their solubilities, volatilities, and the other properties. In general, there
are six chemical processes can be used to remove substances from wastewater:

1. Reaction to Produce an Insoluble Solid

The industry standard procedure for removing metals from wastewaters is
alkaline precipitation. Alternative methods include precipitation of the metal as
the sulfide, precipitation as the phosphate, precipitation as the carbonate, or co-
precipitation with another metal hydroxide, sulfide, phosphate, or carbonate. All
of these technologies use the law of mass action, illustrated as follows:
When a chemical system is in equilibrium as expressed by

A+B C+D
it must obey the equation

[C][D]
[A][B] = K ; where K is a constant

For a given system of chemical substances that have reacted to the point of
equilibrium, the mathematical result of multiplying the products, each expressed
as moles per liter, divided by the mathematical product of the reactants, is always
the same number. Consequently, in order to not change the value of K, an increase
in either A or B will shift the equilibrium to the right, causing a corresponding
decrease in B or A, respectively. Likewise, removal of some or all of either C or D
will shift the equilibrium to the right, causing decreases in both A and B. It
follows, then, that if substance A is a pollutant, substance B will react with A to
produce an insoluble precipitate (C or D), and because precipitation constitutes
removal from solution, then substance B can be added until substance A has
essentially disappeared.
The procedure that can be used to develop an effective and efficient
treatment technology is as follows: First, identify one or more insoluble
compounds of the target pollutant. The second step, identify one or more soluble
compounds that are inexpensive sources of the remaining substances in the
insoluble compound. After that, perform experiments in the laboratory to confirm
the technical and financial feasibility of each treatment.

Table 1. Solubility of Lead Compound in Water

COMPOUND SOLUBILITY IN WATER (mg/L)
 Lead hydroxide (Pb(OH)2) 2.1
Lead carbonate (Pb(CO3)) 7.0 10-3
Lead phosphate (Pb3(PO4)2) 20 10-3
Lead sulfide (PbS) 3.8 10-9

As an example of the foregoing procedure, consider that lead is the target

pollutant. And of these three compounds, lead carbonate and lead sulfide are seen
to be essentially insoluble in water. Table 1. shows that the following compounds
of lead are highly insoluble. Executing the second step, it is determined that an
inexpensive source of carbonate ions is common soda ash, Na2CO3. And then add
soda ash and precipitate the lead as the insoluble carbonate. When an insoluble
precipitate is formed, individual atoms share electrons to build a crystal lattice
structure that results in particles that grow to a size that will settle in a clarifier
under the influence of gravity. Often, two distinct processes take place. The first is
the formation of small crystals of the substance being precipitated. The second is
coagulation of the small crystalline particles, which is the clumping together of
many small particles to form larger particles that settle well. Sometimes a
coagulant or a coagulant aid can assist with this process. It is common practice to
include a deep bed granular filter, or, in some cases, ultrafiltration, as the final
step in removing substances by forming an insoluble solid. Typically, chemical
precipitation followed by sedimentation results in 10 mg/L or less of the target
substance remaining in the treated effluent. Polishing this effluent normally
reduces the residual to 1 to 3 mg/L. It is always necessary to confirm a chemical
treatment process by laboratory experimentation. Even though there are
voluminous books and research papers that describe how various substances, such
as heavy metals are removed, the presence of interfering substances such as
chelating agents, complexing substances, and substances that will compete for the
proposed treatment chemical can sometimes render a given method ineffective in
any given application.
 A suggested procedure for determining, in the laboratory, optimum doses
of reagent chemicals and ranges of pH is as follows using jar apparatus:
1. Place wastewater, pretreated by sedimentation or otherwise, as anticipated
for a fullscale treatment plant, in jars of about 1200 ml volume. 1000-ml
beakers can be used, but jars of square cross-section produce better mixing
action.
2. Determine reagent doses to bracket the anticipated optima, depend on pH,
Precipitant, Coagulant (if any).
3. With all stirrers in the rapid mix mode, add the decided-on doses to each
jar as nearly simultaneously as possible. One method is to place each dose
in a small beaker and have several people, each with a beaker in each
hand, dose each jar at the same time.
4. Rapid mix for 30 seconds.
5. Slow mix to achieve good coagulation. Observe the coagulation process
(appearance of particles in the test solutions) and the flocculation process
(building of particles into large, flocculent solids with attendant decrease
in the turbidity of the test solution). Record observations. Carry on for up
to 30 minutes.
6. Allow to settle. Observe flocculation and settling characteristics. Record
observations.
7. Measure results of the following target substance concentration, pH,
turbidity, TSS, and residual reagents, if desired.
 Figure 1. Jar Test Apparatus

The Use of Carbamate

Carbamates is an organic compounds that was developed for use as
pesticides, have been found to function extremely well as precipitants for certain
metals. In some cases, one or more carbamates have been found to be capable of
precipitating metals in the presence of chelating agents and other substances that
interfered with removal of the metals using more conventional methods such as
pH adjustment.

Disadvantages of Treatment by Production of an Insoluble Compound

One method of avoiding the expense and future liability of disposing of
sludge as hazardous
waste is to dewater, dry, then store the dried material for later recycle and reuse.
Even though this would require licensing as a hazardous material storage facility,
it might prove to be the most cost-effective option.
The aim of precipitation is to precipitate the chemical from dissolved substances
in the wastewater by adding a reagent, which forms an insoluble compound with
the to-be-separated matter. Positive ions such as (heavy) metals, but also negative
ions like phosphates and sulphates, can be removed via precipitation.
disadvantage is the large quantity of silt that is produced. Few problems are
encountered if the silt can be precipitated as a useful by-product; if, for example,
the silt contains heavy metals, it will be regarded as dangerous waste and will be
accompanied by high processing costs.

Suggested Approach for Treatment of Industrial Wastewater by Formation of

an Insoluble Substance
as in all industrial wastewater treatment applications, the cost effectiveness
of primary treatment, including plain sedimentation, should be evaluated. The
second step should be pH adjustment to that range required for optimum
effectiveness of the third step, which should include whatever conditioning steps
are to take place before the principal treatment process. Next, a second pH
adjustment step may be required for optimum performance of the principal
treatment process, to be chemical precipitant addition, mixing, flocculation,
sedimentation, and finally, filtration.
2. Reaction to Produce an Insoluble Gas
Considering, again, equations 8-5 and 8-6, it can be seen that if product C
or D is a gas that is very poorly soluble in the wastewater being treated, it will
remove itself from solution as it is formed, thus forcing the equilibrium to the
right until the target substance (A or B) has essentially disappeared. An example
of thistreatment technology is the removal of nitrite ion by chlorination. As
chlorine is added in the form of chlorine gas or hypochlorite, or another chlorine
compound that dissolves in water to yield free available chlorine, the nitrite ions
are oxidized to nitrogen gas and water. Nitrogen gas, being only sparingly soluble
in water, automatically removes itself from the chemical system, driving the
equilibrium to the right until all of the nitrite ion has been removed.

Breakpoint Chlorination to Remove Ammonia

Breakpoint chlorination has been used to produce a free chlorination residual in
drinking water. The basic process of breakpoint chlorination is that chlorine reacts
with ammonia in four different stages to ultimately produce nitrogen gas,
hydrogen ions, chloride ions, and possibly some nitrous oxide, and some nitrate.
First, chlorine reacts with water to yield hypochlorous and hydrochloric acids:

Then, hypochlorous acid reacts with ammonia:

When an organic macromolecular solid is placed in a given liquid, one of three
possible states of solute-solvent interaction results (solubility in this instance is
defined as a limited parameter indicating compatibility with the solvent but not
true solubility in the strict sense of the definition):
1. The macromolecular solid is insoluble in the liquid.
2. The solid swells but has a limited solubility.
3. The substance is soluble in the liquid.
In cases 1 and 2, the systems are always lyophobic, whereas in case 3, the only
possibility is that of a lyophillic sol.

3. Reduction of Surface Charge to Producen Coagulation of a Colloidal

Suspension
A colloidal suspension consists of one substance in a fine state of
aggregation evenly dispersed throughout a second. The first phase, which may
consist of single polymers or aggregates of smaller molecules, is called the
dispersed or discontinuous phase, and the second phase is called the dispersing
medium or continuous phase. The distinguishing characteristics of a colloid
system are the size of the dispersed particles and the behavior of the system,
which is governed by surface phenomena rather than the chemical properties of
the components.

Coagulation of Colloidal Waste Systems Lyophobic Colloids

Coagulation, or agglomeration of the particles in a lyophobic colloidal system,
can be brought about by neutralization of the surface charge on each particle to
the point where the repulsive forces will be less than the London van der Waal
forces of attraction.

Lyophillic Colloids
The principal stabilizing factor in the case of lyophillic sols is the
solvating force exerted on the particles (not on the ions in the diffuse double
layer) by the suspending medium. Two methods can be employed to desolvate
lyophillic colloids. In the first method, a liquid can be added to the system that is
both a poor solvent for the suspended particle and highly miscible with the
suspending medium. When this is done the colloid is no longer able to form bonds
with the medium that are stronger than the internal bonds between elements of the
medium, and the principal stabilizing factor is removed. This process is called
coacervation. The other method is to add a substance, such as a sulfate salt,
which can form stronger solvation bonds with the solvent than the solvent can
with the suspended colloids. When this is done, the added salt effectively pulls the
hydrated water layer from the surface of the colloid, again, destroying the
principal stabilizing factor. This process is known as salting out.

4. Reaction to Produce a Biologically Degradable Substance from a

Nonbiodegradable Substance

Hydrolysis, under either acidic or alkaline conditions, can be used to break

up many large organic molecules into smaller segments that are amenable to
biological treatment. Heat may be required for effective hydrolytic action, and
consideration of proper reaction time is very important. Hydrolysis of these water-
soluble fats and oils can break them into small segments that are still soluble in
water and readily degradable by anaerobic microorganisms, aerobic
microorganisms, or both. Laboratory experimentation is required to determine the
technological feasibility for a given industrial waste, as well as a cost-effective
process.

Patented process that is based on the principles described earlier uses

hydrolysis to alter the structures of refractive organics that remain in wasted
biological treatment sludge after aerobic or anaerobic digestion has been carried
out to essential completion. As an alternative to dewatering and disposing of this
digested sludge, which, by definition, is not biodegradable, it can be broken into
smaller organic units by hydrolysis, then sent back through the industrys
biological treatment process from whence it came. Advantage can be taken of
periods of low loading, such as weekends, holidays, periods of plant shutdown for
maintenance, or during shifts when loadings to the treatment plant are low.

5. Reaction to Destroy, or Otherwise Deactivate, a Chelating Agent

Removal of metals from an industrial wastewater by simple pH
adjustment, with or without addition of sulfide, carbonate, phosphate,or a
carbamate, is ineffective because of the presence of chelating agents. A chelating
agent is a substance whose molecules can form several bonds to a single metal
ion. In other words, a chelating agent is a multidentate ligand. There are two kind
of chelating agent, organic and inorganic chelating agent. and these are method to
solving type of wastewater treatment problem

Organic Chelating Agents

1. Destroy the chelating agent by acid hydrolysis.
 2. Destroy the chelating agent by hydroxyl free radical oxidation, by using
one of the following technologies
3. Destroy the chelating agent by adding potassium permanganate and
heating.
4. Pass the wastewater through granular activated carbon. In some cases, the
chelating agent will adsorb to the carbon.

Inorganic Chelating Agents

1. Add a stronger chelating agent, such as heptonic acid, or EDTA, both of
which are organic
2. after add heptonic acid or EDTA, then it is sometimes possible to remove
the metals by passing the wastewater through a strong cationic exchange
resin generated on the hydrogen (acid) cycle.
3. If the chelating agent is polyphosphate, it may be feasible to hydrolyze it
with acid and heat.

6. Oxidation or Reduction to Produce a Nonobjectionable Substance

Some highly objectionable substances can be chemically oxidized and
some can be reduced to produce nonobjectionable substances such as carbon
dioxide and water. Ex : the destruction of warafin by potassium dichromate, acid,
and heat, as shoen in the picture the high toxic of warafin oxidized to harmless
CO2 and H2O, and the presence of Cr+++ in the effluent, which may have to be
removed in a subsequent step.

The removal of chromium from industrial wastewaters by chemically reducing

hexavalent chrome ions, which are soluble in water and highly toxic, to the
trivalent state, which is neither soluble (in the correct pH range) nor toxic, is
another example of treatment by chemical oxidation or reduction to produce
nonobjectionable substances.

Oxidation of (soluble) Ferrous Ions to (insoluble) Ferric Ions by Oxygen

Iron soluble in water in the +2 (ferrous) valence state. Ferrous ions are very easily
oxidized to the +3 (ferric) valence state, soluble only in strongly acidic aqueous
solutions. The oxygen content of air is a sufficiently strong oxidizing agent to
effect this oxidation. During aeration step following by sedimentation is
successfull to remove iron from industrial wastewater. the aeration step already
conversion of the dissolved ferrous ions to the insoluble ferric state. Then the
ferric ions quickly and readily sedimented from solution as ferric oxide (Fe2O3),
which forms a crystal that builds to particle sizes that settle well under the
influence of gravity.

Oxidative Destruction of Organics by Free Radicals

A free radical is an atom, or group of atoms, possessing an odd (unpaired) electron
(has no partner of opposite spin). Free radicals are powerful oxidizers that can
convert many organics all the way to carbon dioxide, water, and fully oxidized
states of other atoms that were part of the original organic pollutants, including
sulfates and nitrates. Free radicals can be produce by the following methods:
1. Adding hydrogen peroxide.
2. Adding hydrogen peroxide to a solution that contains ferrous ions, either
present in the wastewater or added along with the hydrogen peroxide
(Fentons reagent).
3. Adding hydrogen peroxide, then irradiating with ultraviolet light.
4. Adding ozone and hydrogen peroxide.
5. Adding ozone and irradiating with ultra violet light.

Oxidation with Hydrogen Peroxide

Hydrogen peroxide has the ability to oxidize some compounds directly; for
instance, alkenes, as shown following. Peroxidic oxygen adds to the double bond,
producing a hydroperoxide, then autooxidizes to alcohols and ketones

Hydrogen Peroxide Plus Ferrous Ion (Fentons Reagent)

Hydrogen peroxide will react with ferrous ions to produce ferric ions, hydroxide
ions, and hydroxyl free radicals, The hydrogen peroxide thus dissociates into one
hydroxide ion [OH] and one hydroxyl free radical (nine protons and nine
electrons [OH]),

Oxidation with Ozone

Ozone (O3) is a gas at ambient temperatures, and have similar characteristic with
oxygen, Ozone reacts with organic compounds similar with oxygen, adding across
double bonds and oxidizing alcohols, aldehydes, and ketones to acids. Ozone
requires less assistance than does oxygen, as from heat, catalysts, enzymes, or
direct microbial action.

Ozone Plus Hydrogen Peroxide

Addition of both ozone and hydrogen peroxide has stronger and effective effect of
oxidizing to destruction many organics than by just adding either ozone or
hydrogen peroxide. When both ozone and hydrogen peroxide are present in water
containing organics, OH free radicals are formed through a complex set of
reactions

Ozone Plus UV Light

Ozone combine with UV in some cases can produce more rapid complete
oxidation of undesirable organic matter than with just either ozone or ultraviolet
light

Chlorination of Hydrogen Sulfide to Produce Elemental Sulfur

Hydrogen sulfide can be oxidized to elemental sulfur

It may then be necessary to neutralize the hydrochloric acid by one of the usual
methods. Additional methods of oxidizing hydrogen sulfide to either sulfate ion or
elemental sulfur (both odor free) include the following:
1. Raising the level of dissolved oxygen (beyond the level of saturation at
atmospheric pressure) by adding oxygen under pressure.
2. Adding hydrogen peroxide.
3. Adding potassium permanganate

Co-Precipitation
co-precipitation often brought about as a result of chemical treatment to produce
an insoluble substance of another target pollutant. For the example is both arsenic
and cadmium are effectively co-precipitated with aluminum or iron. If there is
dissolved iron and arsenic and/or cadmium in an industrial wastewater, oxygen
can be added to form insoluble ferric oxide, which then builds a rather loose
crystal lattice structure. This precipitate exists in the wastewater medium as a
suspension of particulate matter. As these particles are building, arsenic and/or
cadmium ions, which are relatively hydrophobic, adsorb to them, effectively
removing them from solution. As the particles settle to the bottom of the reaction
vessel, and the resulting sludge is removed, the treatment process is completed

Solvent Extraction
Solvent extraction operates on the principle of differential solubilities. When a
solute substance is dissolved in one solvent, and a solvent in which that substance
is more soluble than it is in the first solvent is added, and the two solvents that are
not miscible with each other (not soluble in one another) are mixed vigorously
together, the dissolved substance will pass from the first solvent into the second.

Thermal Oxidation
Thermal oxidation has often been used to remediate contaminated soil. The
mechanism and products of thermal oxidation are the same as for chemical
oxidation with oxygen. The mechanism is electrophyllic attack, and the products
are carbon dioxide, water, and oxidized ions and molecules such as sulfate, sulfur
oxides, and nitrogen oxides

Catalytic Oxidation
There are two way to overcome the defiency when the energy of activation
required for oxygen, or another oxidizing agent, to react with a certain organic
substance is too great for the reaction to proceed under normal conditions (1) to
add heat to supply the energy of activation (thermal oxidation), and (2) to add a
catalyst, which reduces the energy of activation (catalytic oxidation).

CHAPTER III

CONCLUSION

3.1 Conclusion
 Wastewater treatment using chemical method depend on the
chemical characteristics of the pollutants, their tendency to react with
chemical compound, and the chemical characteristics of reaction between
pollutants and chemical compound, their solubilities, volatilities, and the
other properties. In general, there are six chemical processes can be used
to remove substances from wastewater, they are Reaction to produce an
insoluble solid, reaction to produce an insoluble gas, reduction of surface
change to produce coagulation of a colloidal suspension, reaction to
produce a biologically degradable substance from a nonbiodegradable
substance, reaction to destroy or otherwise deastive a chelating agent, and
then oxidation or reduction to produce a non-objectinable substance or a
substance that canbe removed more easily by one of the prvious method.

3.2 Suggestion
There are may chemical method to applied in wastewater treatment
technology, so we need to choose the best method to minimize cost and to
get effectively and efficiency.

REFERENCE
Woodard, Frank. 2001. Industrial Waste Treatment Handbook. Butterworth
Heinemann : USA.