Presented at National Institute of Technology Goa, India

Online Faculty Development Program on

ENVIRONMENTAL GEOTECHNOLOGY

Production of composite clay bricks: A value-added solution

to hazardous sludge through effective heavy metal fixation

Vihangraj V. Kulkarni, PhD

Assistant Professor
Department of Civil Engineering
National Institute of Technology Silchar
Assam – 788010

kulkarni@civil.nits.ac.in
 Subject motivation

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 Subject motivation

1997

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 Subject motivation

Lead-solder coated PV ribbons are Lead-sheathed sub-sea cables are vital

used globally in energy storage projects for offshore wind farms

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 Relatable Sustainable Development Goals

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 Introduction and Literature Review

 Rapid industrialization - effect on water quality Agricultural sources

 Careless handling of waste Domestic sources

Air-borne sources
Metal
plating
Industrial or
Lead-
Waste acid
anthropogenic sources
disposal battery
(LAB)
Industrial • Fe, Cu, Zn
sources Essential
• Cr(III), Co

Fly ash Mining

Beneficial • Si, B, V, Ni

smelting • Pb, Cd, As

Detrimental
• Hg, Cr(VI)

6/25/2021 Presented at National Institute of Technology Goa, India

 LAB industry and heavy metal pollution

Lead
• 18th century Consumption • Groundwater
• By Plante • 1966 (28%) contamination
• 1999 (27%) • Pb poisoning
• 2015 (85%)
LAB Industry
Pollution
Commencement

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 Instances of ULAB industry HM pollution
Figure: Crude, unhealthy,
and illegal practices of ULAB
recycling through breaking of
batteries for lead recovery,
spillage of acid, and lead
fumes in trolley filing
(source: self captured at
Amingaon, Assam)

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 Future of LAB industry in India
• Use of LABs and growth rate of 8% (2017 – 2022)
• Automobiles demand

• Expansion of telecommunication infrastructure

• Increasing number of solar power projects

• IT industry

• Explosion in production of battery-driven e-bikes/cars

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 Waste generation in LAB industry
• Pb loss during mining and concentrating, primary smelting, recycling, and battery
manufacturing process - 16.2, 7.2, 13.6, and 4.4%, respectively [7]

• Wastewater: Pb (2-50 mg/L), high TDS (up to 10000 mg/L), Ni (up to 2 mg/L), Cu
(up to 2 mg/L) with pH between 1-2

• Manufacturing of 7.5 to 8 lacs batteries used in two-wheeler motorbikes generates 35

tons solid sludge

• Sludge: pH 6-9, Pb 500-10000 mg/L, Fe 1000-20000 mg/L, Cu 50-600 mg/L, Cd

upto 200 mg/L, Ni 150-20000 mg/L, and Ca upto 60000 mg/L.
6/25/2021 11
Presented at National Institute of Technology Goa, India
 Sludge in brick production
• Bricks - two types:
• Conventional bricks prepared with clay followed by kiln firing
• Cemented bricks using ordinary Portland cement (OPC)
concrete or other appropriate binder

• Production of fired and cemented bricks leaves large carbon

footprints through emission of gases and other wastes generated in
manufacturing [8]

• Developed countries started using sludge for production of bricks

to conserve limited resources.

• Developing countries still exploring possible utilization of wastes

in bricks production [9]
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 Production of fired bricks

Source: Brick Industry Association TN9, 2006

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 Production of fired bricks
• Global annual production -1391 billion units [9]
• India: second largest producer (>100,000 kilns: 150-200 billion units)

Firing Bricks (hard, non or less water

Clay minerals Clay
+ Silt + Sand absorbing, porous and thermally depletion
insulated)

• Advantages of sludge bricks: saving fertile clay, metal fixation, value addition to
sludge, and manufacturing of thermal resistant bricks
• Researchers utilized waste products from industries for purpose including mine
tailings, fly ash, blast furnace slag, processed waste tea, textile laundry sludge,
gypsum sludge and Pb/Zn smelting slag, degraded municipal solid waste, arsenic–
iron sludge, and calamine processing wastes
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 Lacunae in literature

Best available sludge disposal/management technique even suffers from

potential heavy metal leaching/contamination. Lead-acid battery sludge
(LABS) laden with heavy metals including Pb and Cd.

Understanding the nature of LABS and its potential treatment with an effective
heavy metals fixation are prudent areas of research.

Implication of LABS for the production of fired clay brick production could
provide an effective solution to get rid of the problems associated with LABS
disposal

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 Objectives of the talk

Toxicity assessment and valorization potential of LABS

• Characterizations, toxicity and risk assessment, speciation, and valorization of

LABS
• Pertinence of heavy metallic sludge for the production of fired clay bricks and
effective heavy metal fixation
• Testing of manufactured fired clay bricks for its suitability as construction material
through compressive strength, water absorption test, and toxicity characteristics
leaching procedure

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 Toxicity Abstract of LABS
Collection
Characterization
 Total metal, TCLP
 Spectroscopy analysis
 BCR extraction
 Particle size & metals
 Risk assessment

Utilization
 Brick casting & firing
 Effect of firing temp.
 Engineering properties 7.5–8 lacs batteries (two-wheeler) generates 35 tons
 Color changes and
standard compliance
 Environmental Inefficient disposal practices leading to heavy metal
considerations (TCLP) uptake/leaching
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 Characterization of LABS
Metal Disposal LABS, total TCLP TCLP of
Collection limita metal limitb LABS
Characterization (mg/kg) (mg/kg) (mg/L) (mg/L)
 Total metal, TCLP Pb 500 8322 5 20.45
c 15721 c 16.57
 Spectroscopy analysis Fe
c
 BCR extraction Cu 400 175 0.114
c
 Particle size & metals Cd 1215 1 3.78
 Risk assessment Ni 200 155 5 1.520
c 4324 c 8.6
Mg
c c
Utilization Mn 300 0.82
 Brick casting & firing Cr 300-400 ND 5 ND
 Effect of firing temp. Al c 4800 c 13.24
 Engineering properties Co c 425 c 1.26
 Color changes and Ca c 65712 c 36.75
standard compliance Zn 500 310 5 1.16
 Environmental a NationalStandard of the People’s Republic of China GB 15618–1995:
environmental quality standard for soils
considerations (TCLP) b Maximum allowable concentration for TCLP by USEPA
c Element not enlisted & ND: Not Detected.

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 Spectroscopic characteristics of LABS
XRD pattern of LABS
Collection  Basanite (56%)
Characterization  Manitobaite (9%)
 Total metal, TCLP  Fe(PO4) (8%)
 Spectroscopy analysis  Calcite (6%)
 BCR extraction  Mn(MoO4) (5%)
 Particle size & metals FESEM of LABS
 Risk assessment  Irregular and angular
particles - metals ppt
Utilization  Crystals of calcite
 Brick casting & firing
 Effect of firing temp. EDX image mapping
 Engineering properties  High concentrations -
 Color changes and Fe, Pb, Ca, and Cd
standard compliance with traces of Cu & Zn
 Environmental  Oxygen - uniformly
considerations (TCLP) distributed over LABS
having oxide forms of
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 BCR Extraction scheme
Collection  Exchangeable metals
fraction (F1)
Characterization
 Total metal, TCLP  Metals bound to iron
 Spectroscopy analysis and manganese oxides
 BCR extraction (Reducible fraction) (F2)
 Particle size & metals  Metals bound to organic
 Risk assessment matter and sulphides
(oxidizable fraction) (F3)
Utilization
 Brick casting & firing  Residual fraction (F4)
 Effect of firing temp.
 Engineering properties
 Color changes and Sol A: 0.11 M acetic acid
standard compliance Sol B: 0.1 M NH2OH.HCl
 Environmental Sol C: 30% H2O2
considerations (TCLP) Sol D: 1 M CH3COONH4

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 BCR Extraction scheme
Collection  Al and Ca - associated
Characterization with sulphates and
 Total metal, TCLP carbonates (F1)
 Spectroscopy analysis
 BCR extraction  Mn, Fe, Zn, and Mg -
 Particle size & metals 56, 49, 44, and 42%
 Risk assessment and predominant in F2

Utilization
 Brick casting & firing  Pb and Cu - showed
 Effect of firing temp. higher affinity for
 Engineering properties organic fraction with
 Color changes and 67 and 55%
standard compliance abundance
 Environmental
considerations (TCLP)  Cd was mostly in F4
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 Particle size distribution and metal content
 Heterogeneous in nature
(1-100 microns)
Collection
Characterization  Two major fractions of
particles 1-10 and 10-100
 Total metal, TCLP micron
 Spectroscopy analysis
 BCR extraction  Most particles (>75%) in
 Particle size & metals range of 5 to 50 µm with
 Risk assessment an average particle size
of 15 µm

Utilization  Metals concentrated in <

 Brick casting & firing 10 µm size: Pb, Cd, Fe,
 Effect of firing temp. and Ni were 53, 45, 59,
and 53%
 Engineering properties
 Color changes and
 Coarse fraction (>75 µm)
standard compliance contained inorganics <5%
 Environmental of total heavy metals
 considerations (TCLP)
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 Risk assessment indices
Risk Estimation of risk levels Metal of interest
Collection Index Pb Cd Ni Cu Zn
Contamination Low (<1), moderate (1-3), 16 14 0.7 0.4 0.06
Characterization factor (Cf)a considerable (3-6), very high (>6)
 Total metal, TCLP Contamination Low (<5), moderate (5-10), 15.58
 Spectroscopy analysis degree (Cd)b considerable (10-20); very high (>20)
 BCR extraction Pollution load No risk (0), baseline (1), progressive 1.38
 Particle size & metals index (PLI)b deterioration (>1)
 Risk assessment Low (<40), moderate (40-80), 83 429 4 2 0.06
considerable (80-160), high (160-
Utilization 320), very high (>320)
 Brick casting & firing Potential Low (<65), moderate (65-130), 435
environment considerable (130-260), very high
 Effect of firing temp.
risk (PER)b (>260)
 Engineering properties
a risk index estimated for individual metal; b risk index estimated for LABS
 Color changes and
standard compliance  Pb and Cd - highest risk of LABS with Cf 16 and 14 respectively
 Environmental
 Ni, Cu, and Zn - low risk to environment
considerations (TCLP)
 Cumulatively PER for LABS (435) - risky for direct land disposal
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 Pictorial abstract of LABS valorization
Collection
Characterization
 Total metal, TCLP
 Spectroscopy analysis
 BCR extraction
 Particle size & metals
 Risk assessment

Utilization
 Brick casting & firing
 Effect of firing temp.
 Engineering properties
 Color changes and
standard compliance
 Environmental
considerations (TCLP)
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 Brick casting & firing
Blending: Bricking materials i.e. pulverized clay soil (PCS)
Collection
and pulverized LABS (PBS) blended varying PBS (5 - 50%
Characterization w/w) with 35−40% tap water (w/w)
 Total metal, TCLP
 Spectroscopy analysis Casting: Cuboid bricks cast manually as per IS 2117: 1991
 BCR extraction (size 60 mm × 30 mm × 20 mm)
 Particle size & metals
 Risk assessment Drying: Air dried (24 h) and oven dried at 105°C (24 h)
Firing: Fired in muffle furnace at 500−1250°C at 2°C/min
Utilization
increment (2 h hold time)
 Brick casting & firing
 Effect of firing temp. Cooling: Cooled naturally
 Engineering properties
 Color changes and Terminology followed: Bricks termed as B5 for 5% (w/w)
standard compliance PBS content in PCS
 Environmental Testing: Fired clay bricks tested following BIS procedure
considerations (TCLP) (IS:3495 1992)
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 Effect of firing temperature on brick composition
Collection  PCS and PBS: fine particles
Characterization  B0 bricks @ 875°C: partial
 Total metal, TCLP vitrification of clay
 Spectroscopy analysis minerals
 BCR extraction
 Particle size & metals  B0 bricks @ ≥1000°C: high
 Risk assessment degree of vitrification

Utilization  B0 bricks @ 1250°C:

 Brick casting & firing complete dissolution of clay
 Effect of firing temp. minerals and soil started
 Engineering properties boiling and highest pore
 Color changes and volume expansion
standard compliance
 Environmental
considerations (TCLP)
Figure: FESEM images of (a) PCS, (b) PBS, (c) B0 bricks at 875°C, (d) B0 bricks at 1000°C, and
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(e) B0 bricks at 1250°C.
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 Engineering properties: Water absorption & Strength
Collection
Characterization
 Total metal, TCLP
 Spectroscopy analysis
 BCR extraction
 Particle size & metals
 Risk assessment

Utilization
 Brick casting & firing
 Effect of firing temp.  Water absorption - indicator of  Firing temp and compressive strength
 Engineering properties durability of brick formation of new crystalline phases
 Color changes and  Water absorption increased with and minerals e.g. moganite, hematite,
standard compliance increase in PBS content mullite
 Environmental  Water absorption decreased with  PBS addition and firing temperature
considerations (TCLP) increase in firing temperature  PBS addition improved at higher
firing temperatures
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 Engineering properties: Failure patterns
• 500-875°C: plastic
Collection failure and low
Characterization compressive strength
 Total metal, TCLP
 Spectroscopy analysis • 950−1000°C:
 BCR extraction Improved compressive
 Particle size & metals strength and sudden or
 Risk assessment brittle failure, lack of
ductility and a high
Utilization stiffness causing
 Brick casting & firing catastrophic failure
 Effect of firing temp.
 Engineering properties • PBS added bricks:
 Color changes and Figure: Stress-strain curves for bricks a) for brick B0 at significant
standard compliance different firing temperatures, b) for bricks B5−B30 at 1000°C compressive strength
firing temperature, and c) for bricks B5−B30 at 1050°C to comply with
 Environmental
firing temperature. standards along with
considerations (TCLP)
plastic failure
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 Engineering properties: Compressive Strength
Collection
Characterization
 Total metal, TCLP
 Spectroscopy analysis
 BCR extraction
 Particle size & metals
 Risk assessment

Utilization
 Brick casting & firing
 Effect of firing temp. Figure: a) Compressive strength of B0 bricks at different firing temperature and b)
 Engineering properties Compressive strength of bricks B5−B50 at different firing temperature
 Color changes and
standard compliance • Imparted by formation of new crystalline phases and minerals e.g. moganite,
 Environmental hematite, and mullite
• Compressive strength improved from 7.3 to 54.8 N/mm2 when firing temperature
considerations (TCLP)
increased from 500 to 1000°C
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 Color changes & compliance with standards
 Bricks color- due to
Collection conversion of Fe2O3 to
Fe3O4
Characterization  Color of bricks added
 Total metal, TCLP with PBS light red and
 Spectroscopy analysis faded with increasing
 BCR extraction PBS amount when fired
until 1000°C
 Particle size & metals
 Risk assessment  At firing temperature
1050°C, bricks became
Utilization yellow due to higher
content of CaO
 Brick casting & firing
 Effect of firing temp.  Coloring property used
 Engineering properties for manufacturing
bricks for decorative
 Color changes and
work
standard compliance
 BIS and ASTM international criteria: compressive strength and water absorption
 Environmental
considerations (TCLP)  Bricks B0−B40 at all temperatures complied compressive strength requirements
 Water absorption higher than 20% at 950°C
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 Environmental considerations (TCLP)
Sample 950°C 1000°C 1050°C
Collection Pb Cd Ni Zn Pb Cd Ni Zn Pb Cd Ni Zn
Characterization B0 ND ND ND ND ND ND ND ND ND ND ND ND
B5 0.41 ND ND ND 0.38 ND ND ND ND ND ND ND
 Total metal, TCLP
B10 0.87 0.06 ND ND 0.65 ND ND ND ND ND ND ND
 Spectroscopy analysis B15 0.84 0.11 0.05 0.56 0.72 0.06 0.08 0.48 0.52 0.08 ND 0.32
 BCR extraction
 Particle size & metals B20 0.93 0.17 0.13 0.81 1.21 0.12 0.15 0.76 0.76 0.12 0.06 0.48

 Risk assessment B30 1.26 0.23 0.14 0.96 0.98 0.16 0.18 0.81 0.81 0.16 ND 0.65

PCS ND ND ND ND TCLP 5 1 5 5
Utilization Limits
 Brick casting & firing PBS 20.42 3.78 1.5 1.16
 Effect of firing temp.
 Engineering properties  PCS did not leached any metal but PBS did leached
 Color changes and  Fired bricks added with PBS tested for heavy metal leaching through TCLP
standard compliance  Test on fired bricks revealed leaching of Pb and Cd within prescribed limits
 Environmental
 Thermal treatments changed metals from exchangeable fraction to non-
considerations (TCLP)
exchangeable forms.
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 Major Findings from the work
TCLP test and toxicity indices qualitatively as well as quantitatively categorized
LABS as hazardous waste for the land disposal

Heavy metals found to be concentrated in the finer fractions and, only 5% in

coarse fraction

The present study is the first to propose a viable sludge management practice for
LABS by utilizing in manufacturing of fired clay bricks complying IS:1077:1992 class
12.5

Win-Win situation for industries

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6/25/2021 Presented at National Institute of Technology Goa, India