JEFCOR LABORATORIES, INC.

“Quality Service is Our Business”

WASTEWATER TREATMENT PROCESS

IMPROVEMENT PROJECT

FOR

BAYER CROPSCIENCE

TECHNICAL REPORT
Introduction:

The services of JEFCOR Laboratories, Inc. were requested by Bayer Cropscience for the
Wastewater Treatment Process Improvement. Treatment of wastewater can either be an
expensive and effective process or expensive yet not effective or it can be cheaper yet effective
or cheaper but not effective. The reduction of COD to comply with effluent standards is the basic
objective of the project by establishing the most effective yet cheaper treatment process through
the bench tests. The basic chemistry of the process will describe the mechanism by which the
treatment undergoes.

Bench test procedure:

Materials:
One (1) gallon of wastewater
500 ml of FeCl3
One (1) kg of activated carbon powder
1) Take the initial pH of the wastewater.
2) Analyse the COD.
3) Prepare FeCl3 stock solution of 1,000 mg/L concentration. Add FeCl 3 to the sample to
bring pH to 4.0-4.5. Stir the solution for at least 5 min.
4) Add 30% NaOH and bring up the pH to 5.5-6.0. Stir the solution until precipitation
occurs or the solution separates into two layers.
5) Separate the precipitate in a separating funnel.
6) Analyse COD of supernatant liquid.
7) Mix activated carbon powder in the supernatant solution equivalent to 8-10 gms/liter.
8) Stir the mixture for 2 to 3 hours (120-180 min) with a magnetic stirrer to effect thorough
adsorption.
9) Filter the mixture to separate the saturated activated carbon from the solution.
10) Analyse the COD of the supernatant liquid.

Present Treatment Process:

Air
AC
FeCl3

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 FeCl3
NaOH
NaOH

Final effluent

Filter cake
Wastewater Coagulation Tanks Plate and Frame
Activated Carbon
Pails Adsorption Vessel Filter Press

The treatment process at present is composed of five stages namely,

First stage: Coagulation with FeCl3 solution

Second stage: Neutralization with NaOH solution

Third stage: Decantation

Fourth stage: Adsorption with activated carbon powder

Fifth stage: Filtration and Dewatering

I. Discussion of Bench Test Results and Recommended Treatment Process

Discussion of Results

The second stage presently is neutralization with NaOH solution after coagulation with
FeCl3 solution. Coagulants normally are low pH or acidic substances that react readily with the
alkalinity of the liquid with considerable suspended solids content being coagulated.

In as much as Bayer’s wastewater is alkaline in nature, the FeCl 3 effectively coagulated

the suspended solids which readily separated and precipitated at the bottom of the vessel. The
color removal is also quite good.

Effect of pH

The neutralization stage can be eliminated from the treatment process because the
increase in pH of the wastewater interferes in the adsorption process. In many literatures
concerning adsorption such as: Mall ID, Mishra N, Mishra IM (1994). Removal of organic
matters from sugar mill effluent using bagasse fly ash activated carbon. Res. Ind. 39: 115-119
and Mohan S, Karthikeyan J (1997). Removal of lignin and tannin colour from aqueous solution
by adsorption onto activated charcoal. Environ. Pollut. 97: 183-187, it has been shown that the
activated carbon adsorption for COD reduction is quite effective at pH below 5 and not higher
than 6. Better adsorption is achieved because of the prevalence of H + ions in the wastewater

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being treated which neutralizes the negatively charged adsorbent surface, thus reducing the
interference to the diffusion of organics at higher pH. The increase in OH - ions present causes a
hindrance in the diffusion of organics which compose the COD content of the wastewater.

After adsorption the pH of the wastewater increased to 7.22 – 8.10 because of the
prevalence of H+ ions in the wastewater at pH 4.0 – 4.5, the activated carbon reacted with the
acidity of the wastewater. On the other hand, after neutralization and increasing the pH to 8.0 -
9.0 the COD reduction was only 30 – 67 % which agrees with the findings of Mohan and
Karthikeyan (1997).

It should also be noted that every activated carbon adsorbent depending on the
carbonaceous raw material source such as coconut shell, wood charcoal or animal bone char has
different properties. In the case of Bayer CropScience, the activated carbon has better adsorbent
property at pH 4.0 – 5.0 which decreases at pH 5.0 and higher.

Eliminating the neutralization stage of the treatment process will entail substantial
savings in chemical usage. This translates to the following:

NaOH (30% solution) consumption to increase pH to 8.0 – 9.0 = (0.35 ml NaOH / 250 ml
wastewater) x (5.0 x 106 ml wastewater treated/batch) x 1liter/ 1,000 ml

NaOH (30% solution) consumption = 7.0 liters / batch

Effect of Reaction/Contact Time

The adsorption reaction/contact time with agitation was from 120-180 minutes per batch.
This is a very important aspect in the treatment process to allow the organics in the wastewater to
get adsorbed in the activated carbon powder. A longer period may be desired but the increase in
reduction efficiency is not commensurate to the increase in power consumption to facilitate
mixing.

Effect of Dosage of Activated Carbon Adsorbent

The dosage or quantity of activated carbon used in the bench test averaged from 10-11
g/L of wastewater in order to minimize the usage so that there will enough for all the tests that
were conducted. The dosage was increased to 15 g/L wastewater to determine whether the
increase in dosage will further lower the final COD concentration of the effluent. A more
suitable dosage would have been 50 - 60 g/L. An optimum dosage of up to 90 g/L in many
adsorption treatment processes. This would have been equivalent to 250 – 300 kilograms of
activated carbon in 5,000 liters of wastewater that will be treated per batch compared to 50 – 75
kilograms only per batch.

An average dosage activated carbon of 15 g/L of wastewater showed a COD reduction

efficiency of 88% for the dilute sample and 92 % for the raw wastewater sample or an average of
90% at pH range of 4.25 – 4.46. But this reduction efficiency was attained by increasing the
adsorbent dosage from 10-11 g/L to 13-17 g/L (15 g/L average) wastewater after the adsorption

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process at pH 4.25 – 4.46 and filtration through filter paper. The reduction efficiency would have
been higher if the activated carbon dosage of 15 g/L average were used during the adsorption
process and not after.

Depending on the COD concentration, the amount of activated carbon adsorbent has to be
adjusted as follows:

COD, mg/L Activated Carbon, g/L Wastewter

<15,000 10
15,000 – 25,000 15
>25,000 20

Effect of NaOH in the Treatment Process

The effect on the addition of NaOH solution with the hope not only to increase the pH of
the wastewater but also to improve coagulation with the reaction with FeCl 3 is apparently
counterproductive. This could be due to the following reaction:

3NaOH + FeCl3 3NaCl + Fe(OH)3

The resulting redox solution is in effect ionic in nature, with the formation Fe(OH) 3
brown precipitate but also forms NaCl in the solution. The solution becomes saline but alkaline
and the presence of Cl- ions may interfere with the COD analysis. Aside from this, the presence
of OH- ions interfere with the dispersion of organics which in effect hinders adsorption.

The NaOH will also react only with the remaining ferric ions as shown by the succeeding
discussion.

Effect of Ferric Chloride

Ferric chloride in solution by itself has the following chemistry where it ionizes into iron
(ferric) and chloride ions:

FeCl3 Fe+3 + 3Cl-

On the other, the water in the solution ionizes into hydrogen and hydroxyl ions,

H2O H+ + OH-

Since there are ferric ions and hydroxyl ions present, some of these ions will combine to
form ferric hydroxide which slightly soluble in water and precipitates from solution as a brown
solid. This explains the reason why NaOH is not needed in the process anymore because the
coagulation will proceed anyway.

Fe+3 + 3OH- Fe(OH)3

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 The precipitation of Fe(OH)3 removes the hydroxyl ions from the solution thus leaving an
excess of hydrogen ions (H+) which makes the solution acidic.

Due to the above mentioned, the addition of NaOH results to an excess of OH - which
makes the solution (wastewater) alkaline causing a hindrance in the adsorption process.

Effect on Effluent Color

The color of the raw wastewater is too high and thus cannot be measured directly but the
final effluent color after coagulation treatment with FeCl 3 alone, decanting and adsorption
attained a color range 60 – 80 pcu while compared with NaOH neutralization, the color ranges
from 90 – 600 pcu.

Sludge Formation

The coagulation process results to the formation of sludge with an average volume of 112
ml which is equivalent to 22% of the total volume of wastewater or 220 liters per cubic meter of
wastewater. The sludge has average density of 0.9897 g/ml.

In every batch of 5,000 liters, total weight of sludge that will be formed is shown in the
following:

Total amount of Fe(OH)3 sludge/batch = 5,000 liters x 0.22

= 1,100 liters x 0.9897 kg/L
= 1,089 kgs

The quantity is quite substantial that the sludge may have to be mixed with the spent
activated carbon sludge and passed through the filter press to remove the water and reduce the
volume. Coagulated sludge normally has a concentration of 10,000 mg/L or 1% solids.

Amount of solids in the sludge = 1,100 liters x 10,000 mg/L x 1 kg/106 mg

= 11 kgs/batch

Net volume of wastewater (supernatant liquid) = 5,000 liters – 1,100 liters

= 3,900 liters

Spent Activated Carbon Filter Cake

The estimated amount of filter cake that will be produced can be shown by the following:

Activated carbon used = 10 g/L x 5,000 Liters wastewater x 1 kg/1,000 g

= 50 kgs/batch

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Concentration of activated carbon in the adsorption vessel = 50 kgs / 5,000 liters/batch

= 0.01 kg/L or 10 g/L

Assume 60% water content:

Amount of spent activated carbon cake = 10 g/L x 5,000 Liters wastewater x 1 kg/1,000 g

= 50 kgs/batch/0.40

= 125 kgs/batch

Total sludge generated/batch = Sludge + carbon cake

= 1,089 kgs + 125 kgs

= 1,214 say 1,200 kgs/batch

Total solids in the combined sludge = Fe(OH)3 sludge + Activated carbon sludge

= 11 kgs + 50 kgs

= 61 kgs

Assume 60% moisture content of cake after the plate and frame filter press:
Total amount of filter press cake = 61 kgs/(1.0 – 0.60)

= 152.5 kgs/batch

II. Concerns on the Disposal of the Solid Waste by Thermal Destruction

The presence of chlorides in the solid waste can be a cause of concern if it is disposed by
thermal destruction or in simple terms pyrolysis, combustion or incineration. The thermal
destruction process may cause the formation of dioxins and furans in the flue gas if the following
operating conditions are not met:

1. Complete destruction of dioxins and furans and their chemical "building blocks" in
waste material during combustion. This is achieved through the "3-T Rule":

 High combustion Temperature to maximize waste destruction;

 Adequate combustion Time (usually two seconds) to maximize waste destruction;
and
 High combustion Turbulence to distribute heat evenly and ensure complete waste
destruction.

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 2. Prevention of conditions that favor formation of dioxins and furans immediately
following combustion. This is achieved by the following design specifications:

 Use a "fast-quench" of post-combustion gases by cooling them quickly from higher

temperatures through the temperature range of approximately 400 oC down to 250
o
C, to avoid prolonged exposure in the temperature range known to favor dioxin
and furan formation; and
 Minimize the presence of certain metals, such as copper, on particulate matter, that
are known to facilitate dioxin and furan formation.

III. Description of Recommended Wastewater Treatment Process

Recommended Treatment Process

Air
FeCl3 AC

Coagulation Tank

Final effluent

Filter cake
Wastewater Activated Carbon Plate and Frame
Pails Adsorption Vessel Filter Press
Sludge Collecting
Tank

The recommended treatment process will be composed of four stages only which are,

First stage: Coagulation with FeCl3 solution

Second stage: Decantation

Third stage: Adsorption with activated carbon powder

Fourth stage: Filtration and Dewatering

Stage 1: Coagulation

a) Determine the COD and pH of the wastewater.

b) Add ferric chloride (FeCl3) coagulant with continuous stirring and bring
down the pH to 4.0 – 4.5. Care should be observed when handling FeCl 3
because of its oxidizing property and acidity.
c) As soon as the pH stabilizes, stand the mixture for several minutes to
allow the sludge to settle. The liquid will have two layers, the clear
supernatant liquid and the reddish-brown Fe(OH)3 sludge. The sludge will
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 occupy at least 22% of the total operating volume in the coagulation
vessel.

Stage 2: Decantation

a) Drain the sludge from the coagulation vessel into a container.

b) Let the sludge stand in the container for several hours to let it settle some
more.
c) Decant the supernatant liquid that will still separate from the sludge.
Dewater the sludge in the plate and frame filter press. This may not be
possible though because the solid particle size might be too small and will
just pass through the filter.
d) Add the collected liquid to the main supernatant liquid that will undergo
adsorption.

Stage 3: Adsorption with Activated Carbon Powder

a) Transfer 5,000 liters (5 cubic meters) of decanted wastewater from the

coagulation tank and add 10 – 20 g/L activated carbon powder adsorbent
depending on the COD content of the wastewater.
b) Thoroughly mix with constant agitation the mixture. Allow a contact time
of 120 – 180 minutes. In the case of Bayer, agitating air is used.

Stage 4: Filtration

a) If the present process directly pumps the wastewater with the activated
carbon in suspension (slurry) to the plate and frame filter press to separate
the liquid from the activated carbon powder, continue the pressure-driven
process.
b) An alternative process can be used. After sufficient contact time had
elapsed, stop the adsorption process and allow the activated carbon to
settle. If it is possible, put the adsorption vessel under 3-5 psig of pressure
to facilitate the settling of the activated carbon sludge. Pump out the
supernatant liquid and remove the settled carbon sludge to undergo
filtration to dewater the sludge. Mix the reddish-brown Fe(OH)3 sludge
with the spent activated carbon sludge for dewatering in the plate and
frame filter press.
c) Determine the COD concentration of the filtrate or final effluent.
d) The final effluent may be already discharged.

Recommended Process Equipment Dimensioning

Equipment No. of Material Capacity, Dimensions

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 Units
Cubic meters
*Coagulation Stainless Steel Top Cylinder:
Tank 1 type 304, 6mm 1.5 V=1.0 cu.m.
thickness d= 1.0 m
h= 1.3 m
Bottom cone:
V = 0.35 m
d=1.0 m
h=1.4 m
Sludge Collecting IBC Plastic Cube: Existing
Tank 1 Container 1.0 1 m x 1 m x 1m
(Existing)
Adsorption 1
Vessel Existing 5.0 Existing
Plate and Frame
Filter Press 1 Existing Existing

*New equipment

COAGULATION TANK

1m

1.3 m Draw-off Pipes

3.7 m 12 inches

1.4 m

1m

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SLUDGE
COLLECTING
TANK
Description of Coagulation Tank

The Coagulation Tank is cylindrical tank with conical bottom and an operating volume of 1.5
cubic meters. It is made of stainless steel type 304 to make it corrosion resistant because of the
acidic nature of the FeCl3 coagulant. The sludge/slurry composed mainly of Fe(OH) 3 a reddish
brown precipitate collects at the conical bottom where it is decanted out. Two draw-off pipes, 2-
inches in diameter with 2-inch diameter ball valves placed 12 inches vertically apart from each
other draws off the clear liquid from the tank.

The sludge/slurry is drained off at the bottom through a 2-inch diameter ball valve-pipe set-up.
With the sludge composing about 22-25% of the total volume of tank, around 0.33-0.375 cubic
meter of sludge/slurry will settle at the conical bottom. The sludge will collected in an IBC
plastic cube container. The system is a batch process handling 1.5 cubic meters of wastewater
per batch.

The Coagulation Tank is a new process equipment recommended for installation.

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Report prepared by:

JEFFREY G. MIJARES
Vice-President Operations

Approved by:

EDNA C. MIJARES
President and CEO

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