SEAISI 2017 CONFERENCE, 22-25 MEI 2017, SINGAPORE

WASTE PICKLE LIQUOR UTILIZATION AS A COAGULANT FOR

WATER TREATMENT PROCESS IN PT. Krakatau Steel (Persero), Tbk.

BY

AGY YOGHA PRADANA*

AHMAD FAISAL**
DZAKY ABDUL HANIF***

SYNOPSIS:

Waste Pickle Liquor (WPL) is waste of pickling process in Continuous Pickling Line (CPL)
at Cold Rolling Mill (CRM). CPL produce 35 m3/shift WPL which contains 80-150 g/L
ferrous ion and 4 – 7% HCl. WPL is processed in Acid Regeneration Plant (ARP) to
regenerate HCl and also produce Fe2O3 as by product. Currently, ARP only processed 20 –
25 m3/shift WPL and around 10-15 m3/shift excess WPL need to be taken by third parties,
since it cannot disposed directly to the environment. Fortunately, ferrous ion in WPL can be
oxidized into ferric ion and used as coagulant in water treatment process. This study aim to
produce coagulant from WPL by using two methods: (1) WPL oxidation by H2O2 and (2)
WPL oxidation by HOCl generated from electrolysis.

Based on the jar test result using raw water with specification pH 7 – 8; DHL 200 – 250
µS/cm; Turbidity = 40 - 75 NTU; Color = 300 – 700 Pt.Co, coagulant produced by first
method can purify the water into pH 5.5 – 4; DHL 240 - 300 µS/cm; Turbidity = 1 - 2 NTU;
Color = 20 – 30 Pt.Co, meanwhile coagulant produced by second method can purify the
water into pH 3 – 3.5; DHL 500 - 600 µS/cm; Turbidity = 1 - 2 NTU; Color = 10 – 20 Pt.Co.

The result from coagulant produced by first and second method has already meet the target of
desirable water specification which Turbidity ≤ 3 NTU, Color ≤ 30 Pt.Co, but the water
production cost, compared with water production cost in one of water treatment company in
Cilegon, first coagulant is 143% and second coagulant is 63.8%. Due to excess HCl in WPL,
indicated by low pH in purified water, sufficient amount of iron scrap can be added into WPL
before oxidation, so the ferric content will increase after oxidation and decrease coagulant
consumption / m3 raw water, which reduce coagulant conversion cost. With this result, this
study not only able to solve waste handling problem at Krakatau Steel but also create
additional value to WPL and effectively help to increase innovation sense of Krakatau Steel
Personnel.

Keywords: Coagulant, Electrolysis, Oxidation, Wasted Pickle Liquor, Water Treatment

* Senior Technology Engineer. Division of Technology & Energy Development. PT

Krakatau Steel (Persero) Tbk. Cigading Plant Site, Cilegon, Indonesia.
** Technology Engineer. Division of Technology & Energy Development. PT Krakatau
Steel (Persero) Tbk. Cigading Plant Site, Cilegon, Indonesia.
*** Production Engineer. Division of Cold Rolling Mill. PT Krakatau Steel (Persero) Tbk.
Cigading Plant Site, Cilegon, Indonesia.

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 SEAISI 2017 CONFERENCE, 22-25 MEI 2017, SINGAPORE

I. INTRODUCTION

The large volume of the iron and steel production has brought problem in the utilization and
disposal of material such as slag, flue dust, mill scale, scrap iron, waste pickle liquor, and
other waste from coal processing. Appropriate process for the utilization of waste from iron
and steel industry have been in operation for years, but steel need improvement, especially to
utilize waste into by-product that have economic value

Steel pickling in PT. Krakatau Steel, as part of the process in the production of Cold Rolled
Coil (CRC) from Hot Rolled Coil (HRC) which oxide and scale are removed from the surface
of strip steel by dissolution in acid use Hydrogen Chloride (HCl). Pickling process produce
waste called Waste Pickle Liquor (WPL), which contains iron chloride and residual HCl
solution that can be recycled by Acid Regeneration Plant (ARP) into regenerated acid for
pickling operation.

Currently, ARP experiencing a significant performance loss. ARP only able to process about
25 m3 WPL/shift from about 35 m3 WPL/shift produce by CPL which caused excess 10 m3
WPL/shift, even though ARP designed to process 48 m3 WPL/shift. Execss WPL is processed
in Reject Treatment Plant (RTP), however RTP only able to process 4 m3 WPL/shift and
others 6 m3 WPL/shift taken by 3rd party.

Figure 1. ARP Performance Profile 2015

WPL processing in RTP was not efficient because there is no added value after process and
need a lot of lime milk. PT. Krakatau Steel also cannot depend on 3rd party to take over WPL
because some 3rd party do not take WPL consistently. This paper will explain the alternative
WPL processing from waste into valuable material.

II. OVERVIEW WPL EXISTING PROCESS FACILITIES AND PROBLEM

A. CPL and ARP Process Overview

CPL remove scale from HRC by mechanical and chemical process. Mechanical process
happen in scale breaker, and chemical process happen in pickling tank that filled with HCl at
certain temperature (about 80oC). HCl reaction with scale produce FeCl2 (WPL) which then
processed in ARP to produce regenerated acid from combustion reaction. FeCl2 oxidized in

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fluidized bed reactor at 800-850oC produce iron dust (Fe2O3) and acid vapor (HCl) which
separate by cyclone. Acid vapor then contacted with reactor input stream by HE to reduce
acid vapor temperature and increase reactor input stream temperature, after that, acid vapor
traped by water in absorber to produce regenerated acid.

Figure 2. Continuous Pickling Line

Figure 3. Acid Regeneration Plan

B. RTP Process Overview
RTP is liquid waste processing unit in PT. Krakatau Steel. RTP processed acid effluent (AE)
and waste industrial effluent (WIE). AE such as rinse water and WPL from CPL also acid
condensate from ARP. AE is neutralized by lime milk until reach pH 8 – 10, after that AE
oxidized by air to convert disolved ion into their maximum oxidation state. AE then mixed
with WIE so the coagulation reacion will occurs, to accelerate sludge formation, floculant is
added before sedimentation process. Sedimentation process happened at sedifloat to separate

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 SEAISI 2017 CONFERENCE, 22-25 MEI 2017, SINGAPORE

clear water from sludge, the clear water can be disposed directly to environment if the
temperature, pH, TDS and TSS already meet the waste disposal standard.

WIE AE

OXIDATION TANK

Figure 4. Reject Treatment Plant

C. Coagulant
Coagulants is chemical substance that have function to neutralize the negative electrical
charge on particles, which destabilizes the forces keeping colloids apart. Water treatment
coagulants are comprised of positively charged molecules that, when added to the water and
mixed, accomplish this charge neutralization. Inorganic coagulants, organic coagulants or a
combination of both are typically used to treat water for suspended solids removal.

When an inorganic coagulant is added to water containing a colloidal suspension, the cationic
metal ion from the coagulant neutralizes the negatively charged electric double layer of the
colloid. Much the same occurs with an organic coagulant, except the positive charge most
commonly comes from an amine (NH4+) group attached to the coagulant molecule. Examples
of coagulants are aluminum salts, iron salts, and polyelectrolytes. Ferric salt (especially ferric
chloride) is good at attracting inorganic SS. Gives more compact sludge. pH sensitivity is
somewhat less than alum. Suitable for usage in the lime-softening process (pH 9).

III. METHOD FOR PROCESSING WPL INTO COAGULANT

Process converting WPL into coagulant consist of Fe enrichment process and oxidation
process as shown in the figure 5.

FE
OXIDATION
ENHANCHEMTN CHARACTERIZATION
PROCESS
PROCESS

Raw Material Coagulant

(Waste Pickle Liquor) (FeCl3)
H2O2
Electrolysis
Oxidation

Figure 5. WPL Processing Method

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A. Fe Enhancement Process
Prior to oxidation process, Fe content of WPL need to be enhanced. So, the final product will
have higher ferric ion (Fe3+). Ferric ion content is the main key to determine the quality of the
coagulant since the ferric. First, scrap is added into WPL at 80oC for two hours. The product
is then treated at the filter press for separating unreacted scrap with the solution. So the final
result will not contain solid particle.

B. Oxidation Process
The process is to oxidize ferrous ion into ferric ion by using two different method; (1)
Oxidation using Hydrogen Peroxide (H2O2) and (2) Oxidation by using HOCl generated from
electrolysis of WPL. Coagulant is produced as a solution from the oxidation of ferrous.

 Oxidation using Hydrogen Peroxide (H2O2)

The first method is using strong oxidation agent hydrogen peroxide (H2O2) to convert ferrous
ion (Fe2+) into ferric ion (Fe3+). WPL which already enhanced on the first process is then
oxidize by addition of Hydrogen Peroxide (H2O2). Addition ratio of H2O2 is maintained at 1:5
by volume.

 Oxidation by using HOCl generated from electrolysis of WPL

The second method is utilizing residual HCl at WPL to be reacted into HOCl by using
electrolysis. HOCl is basically strong oxidation process which can be used to oxidize ferrous
ion into Ferric ion. The principle of electrolysis process is using electron supplied by from
electrolysis to promote reaction on cathode and anode to form HOCl as follow:
1. Hydrogen Evolution on Cathode:
2 H2O + 2e-  H2 (g) + 2OH-
2. Chlorine Generation on Anode:
2 Cl-  Cl2 (g)
3. Reaction on the solution:
Cl2 (g) + 2OH- Cl-+ ClO- + H2O
2 FeCl2 + HOCl + 2HCl  2FeCl3 + H2O + HCl
2 FeCl2 + Cl2  2FeCl3
So the process of HOCl generation and oxidation of ferrous ion in WPL will be done
simultaneously.

Electricity Supply

WPL Chamber

Cathode

WPL
Anode

Figure 6. Process Flow Diagram of WPL Electrolysis

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In this method, the reaction is performed in the 1000 cc electrolysis batch reactor integrated
with electricity supply and WPL chamber. The material of cathode and anode is using inert
material (Pt | Pt) to make sure Cl- and hydrogen ion at solution will be reacted. WPL as raw
material is fed into 1L WPL chamber. After the preparation is done, electricity is turned on to
start supplying electron into cathode and anode. The reaction will take time for 20 minutes.
The voltage is maintain at 6V while the pressure and temperature is being kept at room
condition.

C. Characterization of coagulant

The final result of oxidation process on H2O2 oxidation method as well as Electrolysis
method is analyzed to determine the performance as coagulant by using jar test. As the basis
of benchmarking data, raw water as well as requirement for processed water is referred to
standard from one of established water treatment company in Cilegon, Indonesia. The
performance of coagulant parameter tested on jar test consist; (1) Dosage Coagulant
Consumption, (2) pH of processed water, (3) Conductivity of process water, (4) Turbidity of
Process Water and (5) Color of process water.

IV. RESULT AND DISCUSSION

A. Dosage for Jar Test Result

(a) (b)
Figure 7. (a) Coagulant from H2O2 Oxidation (b) Coagulant from HOCl Oxidation

The dosage needed to clean raw water is related to ferric ion (Fe3+) content on the coagulant.
Raymond (2009), on his study shows that Fe3+ has the ability to destabilize the particle on
raw water and form denser flock to clean water. So, higher Fe3+ will give better coagulant
performance to clean water.

Based on jar test result, coagulant produced by first method have higher Fe3+ conversion than
coagulant produced from second method. Moreover, residual Fe2+ on coagulant is not as good
as Fe3+ in term of coagulant performance. The optimum dosage for each sample are shown on
the following table.
Coagulant Dosage
Al2SO4 (Existing Coagulant) 80 ppm
FeCl3 (H2O2 Oxidation Method) 155 ppm
FeCl3 (Electrolysis Method) 300 ppm

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Dosage of Coagulant produced by first method need less dosage to clean raw water into clean
water than Coagulant produced by second method, 155 ppm and 300 ppm respectively.
Lesser dosage will reduce water treatment cost since it consumes less coagulant.

B. Jar Test Parameter Result

 Oxidation using Hydrogen Peroxide (H2O2)

TDS Turbidity Color

Sample pH
(μS/cm) (Ntu) (Pt.Co)
Raw Water 7-8 200 - 250 40 – 75 300 - 700
Processed Water 5,9 – 5 240 – 300 1–2 20 - 30
Clean Water Standard* 6–7 N/A <3 < 30

Based on the jar test result using raw water with specification pH 7 – 8; DHL 200 – 250
µS/cm; Turbidity = 40 - 75 NTU; Color = 300 – 700 Pt.Co, coagulant produced by first
method can purify the water into pH 5.5 – 4; DHL 240 - 300 µS/cm; Turbidity = 1 - 2 NTU;
Color = 20 – 30 Pt.Co.

All the parameter, TDS, Turbidity and Color met the minimum requirement except pH. Final
pH water is 5 – 5,9 which is slightly lower than standard required. It indicated that coagulant
still have unreacted HCl on the solution during oxidation process.

 Oxidation by using HOCl generated from electrolysis of WPL

TDS Turbidity Color

Sample pH
(μS/cm) (Ntu) (Pt.Co)
Raw Water 7-8 200 - 250 40 – 75 300 - 700
Processed Water 3 – 3.5 500 – 600 1–2 10 – 20
Clean Water Standard* 6–7 N/A <3 < 30

Based on the jar test result using raw water with specification pH 7 – 8; DHL 200 – 250
µS/cm; Turbidity = 40 - 75 NTU; Color = 300 – 700 Pt.Co coagulant produced by second
method can purify the water into pH 3 – 3.5; DHL 500 - 600 µS/cm; Turbidity = 1 - 2 NTU;
Color = 10 – 20 Pt.Co.

All the parameter, TDS, Turbidity and Color met the minimum requirement except pH of
water. Final pH of water is 3 – 3,5 which is still far from standard required due to high
dosage of coagulant added into water. It also indicated that there are still residual HCl left on
the solution. However, pH can still adjusted on the neutralization process on water treatment
process even though it will cost higher to neutralize water.

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C. Economic Analysis

Economic analysis is performed with the assumption where production price is only consider
conversion cost in the pilot scale. The following is summary of economical calculation

Production Water
Coagulant Dosage
Cost Treatment Cost
Al2SO4 (Existing Coagulant) IDR 100% / kg 80 PPM IDR 100% / m3
FeCl3 (H2O2 Oxidation Method)* IDR 76.5% / kg 155 PPM IDR 143% / m3
FeCl3 (Electrolysis Method)* IDR 14.6% / kg 300 PPM IDR 63.8% / m3
* Pilot Scale

Based on economic analysis, production cost of FeCl3 of the second method is only 14.6%
from existing coagulant production cost since it only need electricity to convert WPL into
coagulant. Meanwhile, production cost of FeCl3 by first method is higher than second
method, 76.5% from existing coagulant production cost. The use of H2O2 as oxidation agent
is very expensive (USD 580/m3) even though give the best conversion.

In term of water treatment cost, coagulant produced by electrolysis method is lower than the
H2O2 oxidation method and also lower than commercial coagulant conversion cost, only
63.8% from existing water treatment cost.

V. CONCLUSION

1. Waste Pickle Liquor (WPL) can be processed into coagulant by using H2O2 Oxidation
Method and HOCl generated from electrolysis of WPL.
2. Based on the Jar test result,
a. The optimum dosage for coagulant produced by first method and second method is
155 ppm and 300 ppm respectively.
b. Both coagulant from first and second method can purify raw water into clean water as
per minimum standard requirement (refer to clean water standard from one of water
treatment company in cilegon) which Turbidity ≤ 3 NTU, Color ≤ 30 Pt.Co.
3. Based on the economic analysis, Production cost and water treatment cost of second
method is 14.6% and 63.8% from existing respectively , while for the first method is
76.5% and IDR 143% from existing respectively.

VI. RECOMMENDATION

Due to excess HCl in WPL, indicated by low pH in purified water, sufficient amount of iron
scrap can be added into WPL before oxidation, so the ferric content will increase after
oxidation and decrease coagulant consumption / m3 raw water, which reduce coagulant
conversion cost.

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