ARTICLE IN PRESS

Building and Environment 42 (2007) 196–202

www.elsevier.com/locate/buildenv

Trials on sludge of lime treated spent liquor of pickling unit for use in
the cement concrete and its leaching characteristics
Anupam Singhal, Satya Prakash, V.K. Tewari
a
Department of Metallurgical and Materials Engineering, Indian Institute of Technology Roorkee, Roorkee 247667, India
Received 3 August 2005; received in revised form 23 August 2005; accepted 29 August 2005

Abstract

Disposal of sludge of lime treated spent liquor pickling unit, as per the Act of Hazardous Waste (Management and Handling) Rules,
1989 is not easy. Its transportation and construction of lined disposal sites pose very severe problem. In the normal practice, sludge is
being disposed off on sides of roads and railway tracks to generally fill the low-lying areas. This may cause severe health hazards. An
attempt has therefore been made to utilize the treated spent liquor sludge in cement concrete. Design mix M20 has been prepared with
varying concentration of sludge in the laboratory. Toxicity characteristics leaching procedure (TCLP) test as per USEPA has been
carried out on cement concrete cubes.
r 2005 Elsevier Ltd. All rights reserved.

Keywords: Hazardous waste; Spent liquor; Sludge; Cement concrete; Leaching

1. Introduction [3–8]. Cement based on solidification/stabilization has been

Waste is classified by United States Environmental
Protection Agency (USEPA) as hazardous waste, if it
exhibits any of the following-corrosivity, ignitability,
reactivity and toxicity. Other characteristics, such as
carcinogenicity, bioaccumulation or photo toxicity, etc.,
are also classified as hazardous [1].
One of the major environmental problems for the steel
industries comes from pickling plant waste. Steel finishing
operations, such as pickling, galvanizing, plating, etc.,
involve a surface cleaning process to eliminate the scale,
rust and dust. This process is carried out by immersion of
steel into hot acidic solution. Pickling solutions are
specifically listed in hazardous waste (management and
handling), amendment rules 2002 [2] (Table 1).
2. Literature review
Most commonly used technology for disposal of metal
sludge is solidification/stabilization by cementitious binder
Corresponding author. Tel.: +91 1332 285733, fax: +91 1332 285243.
E-mail addresses: ansindmt@iitr.ernet.in (A. Singhal),
truthfmt@iitr.ernet.in (S. Prakash), vinayfmt@iitr.ernet.in (V.K. Tewari).
effectively demonstrated as treatment technique to isolate
hazardous wastes from the environment [9]. Conversion of
metal containing solid waste into building material by
using solidification/stabilization has been recommended by
various researchers [10]. Leaching of heavy metal in the
solidification/stabilization can be considered as a pH
dependent and corresponding metal hydroxide solubility
controlled process [11]. The leachability of Cr (+6) during
the toxicity characteristics leaching procedures (TCLP) test
is dependent on the initial Cr (+6) concentration and the
leaching time [12].
In past, attempts have been made to solidify/stabilize the
metal sludge for disposal sites. An attempt has therefore
been made in this study to utilize the treated spent liquor
sludge in cement concrete in the laboratory and to study its
leaching characteristics.
3. Experimental procedure
The pickling spent acid has been collected from
an industry in Wazirpur Industrial area, Delhi, India.
In this industry, stainless-steel components and sheets
are pickled using sulphuric acid. Spent acid is being

0360-1323/$ - see front matter r 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.buildenv.2005.08.029
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A. Singhal et al. / Building and Environment 42 (2007) 196–202 197

treated with sodium metabisulphite and lime. The 3.4. Fine aggregate (sand) analysis
XRD analysis of treated sludge has been carried out
(Figs. 1 and 2). Fine aggregate is analysed as per IS-383-1970 [14], and
results are shown in Table 5.
3.1. Characterization of spent acid
3.5. Coarse aggregate analysis
Spent liquor is being characterized as per the standard
methods on Atomic Absorption Spectrometer (AAS) [13], Coarse aggregate is analysed as per IS-383-1970 [14], and
and results are shown in Table 2. values are given in Table 6.

3.6. Sieve analysis of treated spent liquor sludge

3.2. Characterization of treated spent liquor sludge
Treated spent liquor sludge is being characterized as per
the standard methods [13], and values are presented in
Table 3.
3.3. Chemical composition and physical properties of cement
Chemical and physical properties of the cement are given
in Table 4.
Table 1
List of hazardous waste
Sieve analysis results are given in Table 7.
3.7. Preparation, casting and curing of cement/sludge
concrete cubes
Cement/ sludge concrete cubes are prepared by adding
different percentage of sludge in cement using standard
design mix. The cube of standard size 15
15
15 cm3 are
prepared in the laboratory. For each set, 14 cubes are
casted and dipped in water at 2772 1C. Compressive
strength has been measured by taking average of reading of
3 cubes of each test at 7, 21 and 28 days of curing.

S. no. Process Hazardous waste
12 Metal surface 12.1 Acid residues
Treatment, such as 12.2 Alkali residues
etching, staining, 12.3 Spent bath/sludge containing
polishing, galvanizing, sulphide, cyanide and toxic metals
cleaning, degreasing, 12.4 Sludge from bath containing
plating, etc. organic solvents.
12.5 Phosphate sludge
12.6 Sludge from staining bath
12.7 Copper etching residues
12.8 Plating metal sludge
12.9 Chemical sludge from
wastewater treatment.
3.8. Toxicity characteristic leaching procedure (TCLP) test
(18 h) [16]
I. TCLP test for treated sludge:
Sludge sample is treated with a solution of buffered
0.1 N acetic acid (pH ¼ 2.88) at a liquid-to-solid ratio
of 20:1 for a period of 18 h. The leachate was filtered
and analysed for Cr and Ni.
II. TCLP test for cement/sludge concrete cubes:
After 28 days of curing, a slice has been cut from the
mid height, weighing approximately 10 g. It is crushed
carefully using a hammer. Each crushed sample is

Fig. 1. Treated spent liquor sludge.

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198 A. Singhal et al. / Building and Environment 42 (2007) 196–202

Fig. 2. XRD analysis of treated spent liquor sludge.

Table 2 Table 3
Characterization of spent liquor (pickling waste) Characterization of treated spent liquor sludge

S. no. Parameters Value S. no. Parameters Value

1 pH 0.85 1 pH 9.26
2 Suspended solids 162 mg/l 2 Calcium oxide (CaO) 62.62%
3 Total dissolved solids 19.21 g/l 3 Silica (SiO2) 31.32%
4 BOD5,20 192 mg/l 4 Iron (Fe) 0.57%
5 COD 6120 mg/l 5 Chromium (Cr) 0.038%
6 Dissolved oxygen Nil 6 Nickel (Ni) 0.002%
7 Chromium (Cr) 652.3 mg/l 7 LOI 9.21%
8 Nickel (Ni) 30.2 mg/l 8 Bulk density 2020 kg/m3

treated with an acetic acid solution of pH 2.88 at a liquid-

to-solid ratio of 20:1 for a period of 18 h. The leachate
has been filtered and analysed for pH, Cr and Ni.
3.9. Mix proportion of concrete
Concrete mix is designed as per IS: 10262 [17], and values
are given in Table 8.
4. Results and conclusions
Compressive strengths and leachate characteristics of
different cubes are given in Tables 9–11. The XRD analysis
of the cubes of mix samples MT0, MT3 and MT6 have
been carried out (Figs. 3–5). The XRD analysis of the
treated spent liquor sludge (Fig. 2) reveals that gypsum,
dicalcium silicate and tricalcium silicate are present in the
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A. Singhal et al. / Building and Environment 42 (2007) 196–202 199

Table 4 Table 7
Chemical and physical properties of cement Sieve analysis results [15]

S. no. Parameter Value Sieve size (mm) Percent retained

Chemical analysis +178 35.4

1 Lime (CaO) 63.5% 178+152 8.3
2 Silica (SiO2) 19.05% 152+124 12.6
3 Alumina (Al2O3) 4.2% 124+104 8.2
4 Iron oxide (Fe2O3) 3.1% 104+89 11.2
5 Magnesia (MgO) 2.9% 89+76 5.9
6 Sulphur tri oxide (SO3) 2.5% 76+66 11.7
7 Soda and/or potash (Na2O+K2O) 0.9% 66+53 4.4
8 Loss on ignition 2.1% 53 2.3
Physical tests
1 Consistency of standard cement paste 28%
2 Soundness of cement 3.5 mm
3 Initial setting time of cement 125 min
4 Final setting time of cement 182 min Table 8
5 Fineness by air permeability (cm2/g) 2698 cm2/g Mixture proportions of concrete

Compressive strength of 50 cm2 cubes, Mpa Mix no. TSLS % Water/ kg/m3
I 3 days ¼ 24.8 Mpa by weight C+TSLS
II 7 days ¼ 34.4 MPa Water C (kg) TPS FA (kg) CA (kg)
III 28 days ¼ 45.9 MPa (l) (kg)

MT0 0 0.5 191.6 383 0 546 1187

MT1 2.5 0.5 191.6 373.4 9.6 546 1187
MT2 5.0 0.5 191.6 363.8 19.2 546 1187
MT3 7.5 0.5 191.6 354.3 28.7 546 1187
MT4 10 0.5 191.6 344.7 38.3 546 1187
MT5 15 0.5 191.6 325.6 57.4 546 1187
Table 5 MT6 20 0.5 191.6 306.4 76.6 546 1187
Sieve analysis results of fine aggregate
Note: TSLS ¼ Treated spent liquor sludge, C ¼ Cement, FA ¼ Fine
IS sieve size Fine aggregate (percent Remarks aggregate, CA ¼ Coarse aggregate.
passing)

4.75 mm 100 Conforming to grading

2.36 mm 100 zone (3) of Table 4 of
1.18 mm 93 IS: 383-1970
600 mm 62 Table 9
300 mm 13 Compressive strength of different cubes
150 mm 3
Mix no. TPS % by weight (TPS/C) Compressive strength (MPa)

7 days 21 days 28 days

MT0 0 19.2 23.0 26.9

MT1 2.5 19.6 23.7 27.8
Table 6 MT2 5.0 18.3 23.3 27.9
Sieve analysis results of coarse aggregate MT3 7.5 18.1 23.9 27.1
MT4 10 16.7 18.0 20.3
IS sieve size (mm) Fine aggregate (percent Remarks MT5 15 13.5 15.6 17.3
passing) MT6 20 9.3 13.8 14.8
20 100 Conforming to Table 2
10 10.2 of IS: 383-1970
4.75 3.7
2.36 —
compressive strength has increased at lower concentration
of sludge in cement but at higher concentration of sludge,
the strength is reduced. At lower concentration of sludge in
cement, compressive strength is increased due to gypsum
sludge. These components have resulted in gain of and C–S–H gel formation. Cr and Ni is absent in leachate
compressive strength of the cubes. up to 5% addition of sludge in the cement. Hence, it is safe
In Figs. 3 and 4, it is evident that peaks of gypsum, to use 5% sludge in concrete mix of M20 grade. The TSLS
dicalcium silicate and tricalcium silicate are well developed may be used in cement concrete and this will solve its
but in Fig. 5 peaks are reduced. Due to this, initially disposal problem.
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Table 10
TCLP (18 h) test results for treated sludge

Name of the sample Chromium in leachate (mg/l) % leaching of chromium Nickel in leachate (mg/l) % leaching of nickel

Treated sludge 4.6 24.2 0.27 27.0

Table 11
TCLP (18 h) test results for cement/sludge concrete cube after 28 days of curing

Mix no. Chromium (mg/l) Nickel (mg/l) pH

MT0 — — —
MT1 BDL BDL 6.5
MT2 BDL BDL 5.9
MT3 0.021 BDL 6.3
MT4 0.028 BDL 6.4
MT5 0.052 BDL 5.8
MT6 0.063 BDL 5.8

Fig. 3. XRD analysis of MT0 sample.

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Fig. 4. XRD analysis of MT3 sample.

Fig. 5. XRD analysis of MT6 sample.

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