Process Safety and Environmental Protection 167 (2022) 434–442

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Process Safety and Environmental Protection

journal homepage: www.journals.elsevier.com/process-safety-and-environmental-protection

Single pot low float chromium tanning: Cleaner pathway approach to

environment friendly leather manufacturing
Naisini Ariram a, c, Srinivasan Pradeep a, c, Sundarapandiyan Sundaramoorthy b,
Balaraman Madhan a, c, *
a
Centre for Academic and Research Excellence, CSIR-Central Leather Research Institute, Chennai 600020, India
b
Regional Center for Extension and Development of CSIR-CLRI, Ahmedabad 382445, India
c
Department of Leather Technology, A.C.Tech, Anna University, Housed at CSIR-CLRI, Chennai 600020, India

A R T I C L E I N F O A B S T R A C T

Keywords: Chromium tanning is the most essential and extensively used tanning process in leather manufacture that re­
Low-float chromium tanning quires pre and post-treatment steps such as pickling and basification to stabilize the collagen in the skin matrix.
Pickle free The conventional chromium tanning process results in low chromium uptake. The unabsorbed chemicals end up
Basification free
in the effluent, directly affecting the environment. Stringent norms have been stipulated for the disposal of ef­
Cleaner tanning technology
fluents containing chromium, total dissolved solids and chlorides, forcing tanners to explore low-waste and
cleaner chromium tanning processes. A chemical mixture was formulated to overcome the issues associated with
chromium tanning process, which leads to pickle and basification free single pot chromium tanning. The
designed process reduces effluent load generation exhibiting nearly 99% chromium uptake, while the conven­
tional chromium uptake is only about 69%. The experimental process results in more than 99% reduction in TDS,
chlorides, and COD load compared to the conventional tanning process. Also, the experimental leather possesses
good thermal stability and physical strength comparable to the conventional leathers. Thus, the present research
work provides an option for cleaner tanning technology to reduce water and chemical load, and the system is
environmentally friendly.

1. Introduction 2019).
Chromium tanning is the key stage in leather processing that con­
Industrial effluent has very variable quality, quantity, and toxicity verts putrescible skin/hide into non-putrescible form as leather. Annu­
levels depending on the type of industry producing it. Complex and ally more than 40,000 tonnes of basic chromium sulphate (BCS) are
expensive treatment technologies are required to remove harmful sub­ discharged globally from the tanning process by the leather industry (Liu
stances from wastewater. In that aspect, the leather tanning industry et al., 2016). Furthermore, tannery effluent contains a high pollutant
generates wastewater with unused chemicals and unwanted components load due to the use of sodium chloride, sulphate, and a mixture of
from the skin matrix, leading to about 30 m3 of wastewater generation organic and inorganic pollutants (Akan et al., 2009). If the tannery ef­
while processing one ton of raw hide/skin (United Nations Industrial fluents are poorly treated, it damages the receiving water bodies and
Development Organization (UNIDO), 2000). The leather process gen­ land surface (Cooman et al., 2003; Hedberg, 2020). Discharged chro­
erates wastewater containing a high load of COD, suspended particles, mium clings tightly to the soil and adheres to the silt layer surrounding
BOD, sulphide, chromium, and dyes at levels 1470 ppm, 920 ppm, 619 or within the groundwater reservoir, which has deleterious effects on
ppm, 60 ppm, 30 ppm, and 50 ppm, respectively (Kanagaraj et al., groundwater and soil fertility (Zhang and Chen, 2020; Zhang et al.,
2015). The effluent outflow would vary with varied chemical pollutant 2020).
loads depending on the unit process. Because of its high pollutant con­ To avoid the usage of chromium and to reduce the effluent load in the
centration, the treatment of leather industry wastewater has been a key tanning process, many research works have focused on the chromium-
issue for pollution control in leather-producing countries, severely free tanning process, viz., mixed metal tanning system (Madhan et al.,
impacting the local environment and human health (Sawalha et al., 2001), zirconium (Sundarrajan et al., 2003), Al-Zr-oligosaccharides

* Corresponding author at: Centre for Academic and Research Excellence, CSIR-Central Leather Research Institute, Chennai 600020, India.
E-mail addresses: [email protected], [email protected] (B. Madhan).

https://doi.org/10.1016/j.psep.2022.09.024
Received 16 June 2022; Received in revised form 12 September 2022; Accepted 12 September 2022
Available online 14 September 2022
0957-5820/© 2022 Institution of Chemical Engineers. Published by Elsevier Ltd. All rights reserved.
N. Ariram et al. Process Safety and Environmental Protection 167 (2022) 434–442

tanning agent (Gao et al., 2022b, 2022a), selective degradation of Table 1

hemicellulose into oligosaccharides assisted by ZrOCl2 as tanning agent Description of Conventional Chromium Tanning Process (% chemical offer is
(Gao et al., 2022b, 2022a), sulfonated tetraphenyl Calix (4) resorci­ based on pelt weight).
narene (Zhou et al., 2018), D-Lysine aldehyde (Krishnamoorthy et al., Process Chemicals % Duration Remarks
2013), P(POSS-MAA)-aluminium tanning (Gao et al., 2020), and dia­ Pickling Salt 10% After the
ldehyde cellulose (Ariram and Madhan, 2020), as an alternative for Water 100% addition, run the
chromium in tanning process. Though these studies produced a drum for 20 min
chromium-free effluent, using chromium (III) salts for tanning is un­ Formic acid 0.5% Add diluted acid
(1:10 dilution in 3 feeds @
avoidable to attain superior leather properties such as high shrinkage
with water) intervals of 10
temperature, water resistance, softness, improved coloring, and light min (3 *10)
fastness. Sulphuric acid 0.5% Add diluted acid pH was noted to
Thus, BCS is still the first choice of tanning agent in the leather (1:10 dilution in 3 feeds @ be 2.8–3.0; 50%
process. Therefore, many research works have focused on the methods with water) intervals of 10 of pickled water
min (3 *10) and was drained
to enhance chromium uptake, thereby reducing effluent pollutant load, after reaching
viz., development of melamine based multisite chromium crosslinker the required pH
(Pradeep et al., 2021), enhancement of chromium uptake by nano­ run the drum for
composite (Liu et al., 2016), oxazolidine (Sundarapandiyan et al., 2011), another 30 min
Tanning Basic 4% After the
ultrasound technology (Mengistie et al., 2016), pickle-free chromium
Chromium 50% addition, run the
tanning using polymeric synthetic tanning agent (Rao et al., 2004), Sulphate drum for 45 min
pre-treatment of pelts to enhance chromium uptake using polyoxy­ Pickled water
ethylene diepoxy ether and urotropine (Jia et al., 2020), influence of Basic 4% After the Penetration of
microwave on chromium complex composition in tanning liquor (Zhang Chromium addition, run the Chromium was
Sulphate drum for 60 min checked
and Tian, 2020), and alternate medium like supercritical fluids, cyclic
Basification Sodium 1% After the
carbonates have been attempted. In most of these studies, an additional formate addition, run the
pre-treatment process was carried out to enhance chromium uptake. As drum for 30 min
a result, the cost of chromium tanning could be higher. Therefore, these Sodium 0.5% Add in 3 feeds @ Final pH
bicarbonate intervals of 10 determined to be
methods were not commercially exploited in leather industries.
(1:10 dilution min (3 *10) and 3.8–4 & tanned
Although significant progress has been achieved in cleaner leather with water) after reaching leathers were
production, water consumption for the leather process remains an issue the required pH piled overnight.
for practical application. As a result, the wastewater load discharge from run the drum for
leather manufacture remains high. And some of the cleaner chromium another 60 min

tanning process developed earlier requires an additional pre-treatment

step. Integrating processes and water reduction without pre-treatment to prepare chromium tan liquor varied from 5% to 40% while main­
will be a strategy for economic and environmental benefits. This is taining the optimized acid mixture and BCS (6%) constant. In the third
particularly important for the long-term sustainability of leather set of experiments, the offer of BCS was varied from 2% to 6% with an
industries. increment of 2% BCS; other parameters such as optimized acid mixture
The cleaner leather process system could boost the production of and amount of water were kept constant.
leather industries, which benefits both developed and developing In all the above experiments, sodium formate was used to prepare the
countries economically. Our group at CSIR-CLRI has recently steered the chromium liquor at 1%. Further duration (120 min) and temperature
implementation of waterless chromium tanning technology at various (25 ◦ C) were kept constant throughout the process. Chromium pene­
tanneries in India. The process involved the pre-treatment of the tration, pH of leather and their characteristics were determined to
delimed pelt and carrying out chromium tanning without water. optimize the chromium liquor suitable for single pot chromium tanning
Herein, we report a single pot low float and low chemical chromium system.
tanning process directly from the delimed pelt. The developed process
averts unit processes viz., pickling and basification. The process flow has 2.1.2. Single pot low float chromium tanning Vs. conventional chromium
been redesigned to achieve a cleaner leather processing system and tanning
produce finer leather in less time than the conventional chromium The wet salted goat skins were subjected to the conventional soaking,
tanning process. liming, and deliming process. The delimed pelt was cut into the left and
right half, while the left halves were kept as a control (conventional
2. Materials process), which was subjected to conventional pickling, chromium
tanning, and basification as per the process given in Table 1. The right
Wet salted goat skins were used for the study. The chemicals used for halves of the delimed pelt were taken for the experimental tanning
the leather processing were of commercial grade. The chemicals used for process. The experimental chromium tanning process was carried out by
characterization were of analytical grade. adding chromium tan liquor to the delimed pelt in the conventional
leather processing drum. The optimized chromium liquor mixture was
2.1. Methods added slowly into the drum, where the delimed pelt was placed without
any water while the drum was kept under rotation (rpm 10). Following
2.1.1. Optimization of chromium liquor formulation the continuous addition of chromium liquor for about 10 min, the
The effect of various parameters such as the amount of water, con­ chromium tanning process was carried out in the drum for 120 min. The
centration of acid mixture (formic:sulphuric acid - 1:1), and offer of BCS complete penetration of chromium was observed in 30 min (through
used for the preparation of chromium liquor for single pot process had cross-section) after adding liquor. After 2 h, the pH of the chromium
been optimized. In the first set of experiments, chromium liquor was tanned leather (wet-blue) reached 4. Therefore, the basification process
prepared with a varied amount of acid mixture viz., 0.1%, 0.15%, and was not carried out.
0.2% (% offered based on the pelt weight of the goat skins) while After the tanning process, the wet blue leathers were piled overnight.
maintaining the amount of water and BCS constant at 20% (v/w) and 6% Further, the tanned leathers were shaved for uniform thickness (~1
respectively. In the second set of experiments, the amount of water used

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Table 2
Process formulation of crust leather (Post tanning process) (% chemical offered based on the weight of the chromium tanned leather (wet blue) after shaving).
Process Chemicals % Duration (minutes) Remarks

Wetting Water 100% After the addition, run the drum for 10 min
Retanning and Synthetic tanning agents 16% After the addition of synthetic tanning agent and dye, run the Dye penetration checked
fatliquoring Dye 3% drum for 60 min
Fatliquors (1:10 dilution with warm 12% After dye penetration, add fatliquor and run the drum for
water) another 60 min
Fixing Formic acid (1:10 dilution with 2% Add diluted acid in 3 feeds @ interval of 10 min (3 *10) pH was noted to be ~3.5
water)
Washing Water 100% Allow the drum to run for 10 min Drain water and pile the post tanned
leather

Note: After ageing, mechanical operations such as setting and stacking were done for leathers.

mm), and a conventional post-tanning process was carried out to obtain

Table 3
crust leather. The process flow for the post tanning process is provided in
Optimization of Chromium liquor formulation.
Table 2.
Experiment Observations

2.2. Analysis of spent tanning liquor Chromium Wet Blue pH of the Colour
Penetration characteristics wetblue

The conventional chrome tanning composite liquor was made by A. Amount of Acid mixture (Water – 20% &BCS – 6% - Kept Constant)
0.1% Penetration at No swelling, ~4.0 Dark
mixing pickling and chrome tanning liquor. The collected control and
about 45 min Smooth grain blue
experimental process effluents were analysed, viz., chemical oxygen 0.15% Penetration Mild swelling ~3.8 Blue
demand (COD), total dissolved solids (TDS), and chloride content as per within 30 min
the standard procedure (Clesceri et al., 1989). The chromium content 0.2% Penetration Swelling & Coarse ~3.6 Blue
was quantified for the effluent discharged from the conventional and within 30 min Grain
B. Amount of Water (Acid mixture – 0.1% &BCS – 6% - Kept Constant)
experimental chromium tanning processes as decribed below.
5% Penetrated Mild swelling ~3.8 Dark
To determine the amount of chromium content in the effluent (both within 30 min blue
control and experiment), the known quantity (5 mL) of effluent was 10% Penetrated No swelling ~3.9 Blue
taken in a 100 mL conical flask. Then acid mixture (5 mL nitric acid, 3.5 within 30 min
20% Penetration at No swelling ~4.0 Blue
mL sulphuric acid and 11.5 mL perchloric acid) was added to it. The
about 45 min
mixture was allowed to be heated in a heating mantle, until the change 40% Penetration at No swelling ~4.0 Blue
in colour from green (Cr3+) to yellow (Cr6+) was observed. The mixture about 45 min
was then allowed to cool for five minutes, and later 10 mL of water was C. Amount of BCS (Acid mixture – 0.1% &Water – 10% - Kept Constant)
added to the mixture and allowed to boil. The permanent change in 2% Not fully Inadequate ~4.0 Light
penetrated chromium blue
yellow colour confirms chromium’s oxidation to its hexavalent state.
4% Complete Good ~4.0 Blue
The mixture was allowed to cool and diluted to a known volume. The pH penetration
was adjusted to 12 using sodium hydroxide before measuring the 6% Complete Good ~4.0 Dark
absorbance. The absorbance at 372 nm was measured for the samples penetration blue
using a UV-Visible spectrophotometer. Cr2O3 content was calculated
using the Beer- Lambert’s law, A = ℇcl, where ℇ value is 4830 mol− 1
rpm for 5 h. The sample was filtered using Whatman filter paper to
cm− 1, c is the concentration, and l is the thickness of the absorbing
remove wet blue pieces. The filtered solutions were analysed for the
medium. Triplicates were carried out for each sample, and the average
leached chromium per the procedure mentioned in Section 2.3.
values were reported.
2.3.3. Analysis of thermal stability
2.3. Characterization The thermal stability of the conventional and experimental chro­
mium tanned leather samples was determined using a differential
The processed wet blue leather (after chromium tanning process) and scanning calorimeter (DSC, Model No. Q200, Make: TA Instruments,
crust leather (after post-tanning process) were subjected to the following Waters Austria). The thermograms were obtained by heating the sample
characterization. from room temperature to 150 ℃ at a heating rate of 10 ℃ per minute.
The denaturation transition of the tanned leathers was obtained from the
2.3.1. Analysis of chromium content in wet blue leather enthalpy changes measured by DSC.
To determine the amount of chromium content in wet blue leather
(conventional and experimental), the known weight of wet blue was 2.3.4. Physical strength and organoleptic properties of leather
sliced into small pieces and placed into the 100 mL beaker. To the 0.5 g The functional attributes of the conventional and experimental crust
of wet blue (dry weight), an acid mixture (5 mL nitric acid, 3.5 mL leathers were tested for fullness, grain smoothness, softness, and general
sulphuric acid, and 11.5 mL perchloric acid) was added to the conical appearance. The specimens for physical strength testing were prepared
flask. After the wet blue digestion, chromium was determined as per the using the standard method and conditioned for 24 h at 25 ℃ and 65%
procedure mentioned in Section 2.2. relative humidity. The conditioned samples were analysed for physical
strength attributes IUP6 and IUP8 (International Union for Physical
2.3.2. Analysis of leachable chromium wet blue leather Testing (IUP6), 2000a; International Union for Physical Testing (IUP8),
A chromium leachability study was carried out to determine the 2000b). The control and experimental crust leathers were assessed for
unfixed chromium in wet blue leathers. The sample known weight (wet the functional properties such as fullness, grain smoothness, softness,
blue – conventional and experiment) was taken, sliced into small pieces, and general appearance and rated on a scale of 0–10 points by visual and
and placed into the beaker. To the weight of 1 g of wet blue, 25 mL of hand evaluation technique, where a higher value indicates better
water was added and allowed to agitate using an orbital shaker at low

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Fig. 1. Schematic representation of Conventional and Experimental Chromium Tanning Process.

property. 4% BCS was noted to be adequate to achieve wet blue leathers as per
requirement (Table 3). Thus, 0.1% acid mixture, 10% water, and 4%
2.3.5. Morphological analysis BCS were the optimum conditions, and 1% sodium formate for the
The surface morphology and cross-section of the crust leather sam­ chromium liquor used for the single pot low float chromium tanning
ples of control and experimental leather were analyzed using a Scanning process. The characteristics of the optimised low float pickle and basi­
Electron Microscope (SEM) (Phenom World, Phenompro). All sampling fication free experimental and conventional chromium tanning process
specimens were coated with gold using a JEOL JFC_1100E ion sputtering were compared and presented in the following section.
device.

3. Results and discussion 3.1. Comparison of experimental and conventional chromium tanning
process
Resource management has gained much attention for leather
manufacturing in recent decades due to economic and ecological rea­ As indicated in section 2.2.2, the delimed pelt was treated with the
sons. From a practical standpoint, reducing the use of chemicals and optimized chemical mixture in the experimental chromium tanning
process steps without affecting leather quality is necessary. A series of process: 10% water, 4% basic chromium sulphate, 0.1% acid mixture
experiments were conducted to optimize water, acid mixture, and BCS (0.05% formic acid, 0.05% sulphuric acid) and 1% sodium formate (to
for a single pot chromium tanning system directly from the delimed pelt the weight of the delimed pelt). The delimed pelt and chemical mixture’s
without any pickling/pre-treatment. Table 3 shows the results of trials to pH was 8–8.5 and 1.5, respectively.
optimize the chromium tanning liquor formulation. The delimed pelt was placed in a leather processing drum to avoid
The acid mixture of 0.1% resulted in wet blue leathers without grain damage, and the chemical mixture was progressively added into
swelling, and the penetration of chromium across the cross section was the drum dropwise. The formulated chromium liquor resulted in a pickle
achieved within 45 min. In contrast, using 0.15% and 0.2% acid mixture free and basification free chromium tanning procedure because the pH
resulted in mild swelling of the wet blue leathers. Hence 0.1% of the acid was decreased to 4 at the end of tanning. As a result, chromium ab­
mixture was considered for the subsequent optimization process. With sorption in the delimed pelt is influenced positively, resulting in an
reference to the amount of water used for the preparation of chromium increased chromium uptake of 99%. With 4% BCS given for delimed
liquor, in comparison with 5% water use, 10%, 15%, and 20% of water pelt, the experimental chromium tanning process resulted in a shrinkage
used for the tanning chemical mixture had resulted in good and uniform temperature exceeding 100 ◦ C. With an 8% BCS provided for pickled
penetration of BCS. Usage of 10% water is the lowest amount of water pelt, the conventional chromium tanning process has a chromium ab­
required to obtain good wet blue leathers. The same had been used as an sorption of 67%, resulting in a shrinkage temperature above 100 ◦ C. The
optimal water requirement for preparing the chromium liquor used for schematic representation flow of conventional and experimental chro­
experimental tanning. mium tanning process flow is depicted in Fig. 1. Further chromium input
and uptake details of the conventional and experimental process are

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Table 4 Table 5
Conventional and Experimental Chromium Tanning Process Comparison. Pollution load analysis of Conventional and Experimental Effluent.
S. Parameters Conventional Experimental S. Characteristics Conventional Composite Experiment
No Process Process No Liquor (Pickling Liquor
þChromium Tanningþ
1 Basic Chromium Sulphate 8% 4%
Basification)
Input
2 Chromium Uptake in Wet 67 ± 2 99 ± 0.02 1 Volume of effluent 2000 L 100 L
Blue generated (L/ton of
3 Cr2O3 Content in Wet Blue 4.3 ± 0.2 3.2 ± 0.05 * delimed pelt)
(dry weight basis) 2 Total Dissolved mg/L 39500 7500
Solids Load 79 0.75
Minimum chromium oxide (Cr2O3) content requirement in chrome tanned (in Kg)
leather – 2.5% (BASF, 4th Edition). 3 COD mg/L 12000 mg/L 5600 mg/L
Load 24 0.56
(in Kg)
4 Chloride mg/L 15600 mg/L 16 mg/L
Load 31 0.016
(in kg)
5 Chromium (as mg/L 3340 mg/L 1450 mg/L
Cr2O3) in Load 6.68 0.145
Effluent (in Kg)

tanning agent interacts only with the ionized carboxyl group of collagen.
Thus, in the pickling process, salt was used to prevent swelling of the
skin matrix. Further pH of the delimed pelt was reduced to 2.8–3 from 8
Fig. 2. Simplified representation of Collagen-Chromium crosslinked complex. to 8.5 by adding acid. Thus collagen carboxyl group gets protonated.
Furthermore, higher pH cannot be used for chromium tanning,
provided in Table 4. which prevents chromium from penetrating the skin matrix (Covington,
2009). Further, the gradual rise of pH to 4 using diluted sodium formate
3.1.1. Experimental chromium tanning process mechanism and sodium bicarbonate solution (basification process), fix the pene­
During the tanning process, tanning agents stabilize the collagen trated chromium into the skin substrate. This finally results in the for­
matrix and render it into a putrefaction resistant material. The delimed mation of coordinate covalent crosslinks between chromium salts and
pelt was treated with the formulated chemical mixture in the experi­ carboxyl groups of collagen. The chromium collagen crosslink image
mental chromium tanning process. Le Chatelier’s principle governs the was provided in Fig. 2.
penetration of tanning agents into the skin matrix. A very low amount of
water leaves the tanning chemical mixture at a high concentration. 3.2. Pollution load analysis
Applying this equilibrium principle, the higher concentration results in
high concentration gradience, which act as a driving force for the higher The conventional and experimental composite liquor was collected
rate of transfer of chemicals into the skin matrix. This also leads to for pollution load analysis and extrapolated per ton of raw material. In
higher uptake of tanning chemicals in the delimed pelt, resulting in wet processing per ton of pelt, the conventional and experimental tanning
blue leather production. Earlier it was established that a water-saturated process results in the effluent volume of 2000 L and 100 L, respectively.
delimed matrix is adequate as a medium for the diffusion of chromium The collected composite liquors were analyzed for COD, TDS, chloride,
salts into the delimed collagenous matrix (Selvaraj et al., 2015). How­ and chromium content, and the values are presented in Table 5.
ever, a lower load of water was used in the chemical mixture preparation The TDS load was determined from the collected effluent, and the
to act as a diluent to the acid to avert any deleterious effect it may cause TDS levels in the conventional and experimental processes were
to the delimed matrix. 39500 mg/L and 7500 mg/L, respectively. This developed single pot
And, despite the presence of concentrated acid in the formulated chromium tanning process is carried out without using salts such as
mixture, the inclusion of sodium formate creates a buffering effect that
prevents the swelling of the matrix during tanning. Here an attempt has
been made to technologically exploit the transfer of reagents into skin
substrate at very minimal water use. Here, the pre-masking (a modifi­
cation or replacement of chromium aquo ligands with carboxylate li­
gands) reduces chromium reactivity to collagen reaction sites. Though
fixation and penetration happen in parallel, the masking salts averts
heavy surface fixation to an extent.
Furthermore, the percentage of acid used in the experimental tan­
ning process was ten times lower than conventional chromium tanning
process acid usage. The inclusion of formic and sulphuric acid acidifies
the delimed pelt, initially at a pH of 8–8.5. The weak acid initiates the
penetration without any hindrance as an electrically neutral molecule,
and the later fully charged hydronium ion from the strong acid pene­
trates gradually into the substrate. Finally, the pelt pH drops to 4, and
chromium crosslinks with the ionized carboxyl sites of collagen through
a coordinate covalent bond.

3.1.2. Conventional chromium tanning process mechanism

Pior to the tanning process, pickling was carried out because the BCS
Fig. 3. Comparison Image of Conventional and Experimental Tanning Process.

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N. Ariram et al. Process Safety and Environmental Protection 167 (2022) 434–442

sodium chloride, sodium formate and sodium bicarbonate, resulting in a

TDS reduction of more than 90%. Also, the chloride load in the con­
ventional and experimental process was 15600 mg/L and 16 mg/L,
respectively, resulting in a chloride reduction of 99.9%. The salinity of
groundwater near tannery clusters is very high due to the uncontrollable
release of tanning effluent with chloride and TDS load. The drastic
reduction of chloride and TDS load observed in the experimental single
pot tanning process aids in future groundwater contamination. Further,
the COD load in conventional and experimental processes was
12000 mg/L and 5600 mg/L, respectively, with the experimental pro­
cess achieving a 98% reduction in COD load.
To determine the chromium content in the effluent, chromium
analysis was performed in the collected effluent from the tanning pro­
cess. The chromium concentration in conventional and experimental
effluent was 31% and 1%, respectively. Thus, the experimental process
reduced chromium discharge in the effluent to about 99%. Near com­
plete exhaustion of chromium was observed in the experimental process.
Fig. 3 illustrates a comparison image of the conventional and experi­
mental tanning processes in the leather processing drum, which clearly
Fig. 4. DSC Thermogram – Thermal stability of chromium tanned leathers.
shows that the drum was free of water content at the end of the exper­
imental tanning process compared to the conventional process. The
conventional process took more than 5 h to produce wet blue, whereas
the experimental process took 2 h.
Compared to the conventional process, the experimental single pot
low float chromium tanning process resulted in 99% absorption of
chromium salts. The experimental process enhances chromium pene­
tration into the skin matrix, releasing less chromium load into the
effluent. A sustainable chromium tanning process was obtained due to
the devised experimental process for minimizing effluent discharge and
increasing chromium uptake.

3.3. Characterization of wet blue and crust leather

The processed conventional and experimental chromium tanned

leathers (wet blue) were carried out for the following characterization.

3.3.1. Analysis of chromium content in wet blue leather

The chromium content in the wet blue was measured for both con­
ventional and experimental samples. As stated earlier in the procedure,
the wet blue was subjected to acid digestion, and Cr3+ was oxidized to
Cr6+. Based on the chromium content in the leather, the experimental
sample was observed to have an uptake of chromium above 99%,
whereas the conventional sample uptake was about 67%. As discussed
earlier in the Section 3.1.1, the higher concentration resulted in high
concentration gradience, which acted as a driving force for the higher
rate of transfer of chromium into the skin matrix. This led to higher
uptake of chromium in the delimed pelt. Thus, the experimental sample
had a higher chromium concentration in wet blue than the conventional Fig. 5. Grain and cross-sectional view of control and experimental leathers.
wet blue. Although only 4% chromium tanning salt was used in the
experiment, the amount of Cr2O3 in the leathers is noted to be about 3.3.3. Analysis of thermal stability
3.2%, which meets the minimum chromium content requirement for wet The thermal stability of the leather samples reflects the tanning ef­
blue leathers. ficiency. The higher thermal stability was achieved by strong cross­
linking between the tanning chemical and collagen functional groups in
3.3.2. Analysis of leachable chromium the skin matrix. The chromium tanning agent forms a coordinate co­
To determine the effect of single pot low float chromium tanning on valent crosslink with the protein’s carboxyl group, resulting in a higher
the binding affinity of chromium with a collagen matrix, chromium shrinkage temperature than any other tanning agent. A differential
leaching was assessed for both experimental and control leathers using scanning calorimeter (DSC) was used to determine the thermal stability
water as the leaching medium. After leaching, the collected solution was of the chromium-tanned leather samples. The thermal temperature
analyzed for chromium concentration, and only a negligible amount of measures the breakdown of stabilizing linkages in the collagen matrix
chromium is noted to be leached out from the experimental wet blue (Gustavson, 1956). Fig. 4 shows the thermal stability values of the
leathers. This concludes that chromium penetrated in the low float conventional and experimental chromium-tanned leather.
process is crosslinked with the collagen matrix more than the conven­ According to the results, experimental chromium tanned leather
tionally tanned leather. Additionally, the experimental process paves shrunk at a higher temperature than conventional chromium tanned
the way for the elimination of exhaustion. leather. Though the % BCS (Conventional– 8%, and Experiment – 4%)
offered for the experimental sample was lower than the conventional,

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Table 6 the experimental sample exhibited a slight higher shrinkage tempera­

Physical strength properties of crust leathers. ture. However, the obtained experimental thermal stability value is not
S.No Properties Conventional Experiment very significant, and the temperature value satisfies the important
requirement for shoe molding.
1 Tensile Strength (MPa) 24.3 ± 1.2 23.26 ± 0.9
2 Tear Strength (N/mm) 78.1 ± 1.9 68.77 ± 0.9
3 Elongation at Break (%) 59.73 ± 1.6 72.61 ± 1.2 3.3.4. Physical and organoleptic properties of leather
Fig. 5 shows the image of the grain surface and cross-section of
control and experimental wet blue leathers. Based on the observation,
both experimental and control leather is comparable. The wet blue

Fig. 6. Grain and Cross-sectional view of Control and Experimental Crust Leathers.

Table 7
Cost analysis of conventional and experimental process (US$ per ton of delimed pelt).
Chemical Cost analysis of conventional and experimental process

S. No Chemical Conventional Cost Experiment Cost

1 Salt 10% 7$ Nil –

2 Formic acid 0.5% 2$ 0.05% 0.2 $
3 Sulphuric acid 0.5% 5.5 $ 0.05% 0.55$
4 BCS 8% 86 $ 4% 43 $
5 Sodium formate 1% 5.5 $ 1% 5.5 $
6 Sodium bicarbonate 0.5% 2$ Nil –
Power consumption Cost analysis of conventional and experimental process
S. No Process Conventional (Time) Cost* Experiment (Time) Cost*
1 Pickling 60 mins 1.18 $ Nil –
2 Chrome tanning 120 mins 2.36 $ 120 mins 2.36 $
3 Basification 60 mins 1.18 $ – –
Total cost 112.72 $ 51.61$
(Chemical&Power consumption)

Note:Processing one ton load, per hour consumes 11 kWh; 1kWh = 1 unit = 0.11$

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leathers were further post tanned, and the crust leathers were compared formulation/process has good potential for commercialization that
for their physical and organoleptic properties. could pave the way for cleaner and sustainable leather production.
The physical strength characteristics of crust leathers from the
experimental and conventional processes are given in Table 6. From the
results, the strength characteristics of both conventional and experi­ Declaration of Competing Interest
mental leathers are comparable and meet the standard norms.
The organoleptic properties of the control and experimental crust The authors declare that they have no known competing financial
leathers were evaluated. It is found that the tanning directly from the interests or personal relationships that could have appeared to influence
delimed pelt with the low water chromium liquor formulation does not the work reported in this paper.
affect any organoleptic properties and is comparable with control crust
leathers, viz., grain smoothness, softness, roundness, and general Acknowledgement
appearance.
It is evident from the physical and organoleptic results that the The authors thank the funding support from DST (DST/TM/WTI/
leather is processed via. low float, pickle, and basification free tanning WR/2K17/89). CSIR-CLRI Communication number A/2022/CRE/
process has well penetrated through the inner layers of the skin matrix GAP1814/1668.
and satisfies the commercial requirements of leather manufacturing.
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