Accepted Manuscript

Chromium recovery from tannery sludge by bioleaching and its reuse in tanning
process

Hongrui Ma, Jianjun Zhou, Li Hua, Fengxia Cheng, Lixiang Zhou, Xianrong Qiao

PII: S0959-6526(16)31824-8
DOI: 10.1016/j.jclepro.2016.10.193
Reference: JCLP 8384

To appear in: Journal of Cleaner Production

Received Date: 16 March 2016

Revised Date: 29 October 2016

Accepted Date: 31 October 2016

Please cite this article as: Ma H, Zhou J, Hua L, Cheng F, Zhou L, Qiao X, Chromium recovery from tannery
sludge by bioleaching and its reuse in tanning process, Journal of Cleaner Production (2016), doi:
10.1016/j.jclepro.2016.10.193.

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 ACCEPTED MANUSCRIPT

Chromium recovery from tannery sludge by bioleaching and its reuse

in tanning process

Hongrui Maa, *, Jianjun Zhoua, Li Huaa, Fengxia Chengb, Lixiang Zhouc, Xianrong Qiaod
a
College of Environmental Science and Engineering, Shaanxi University of Science & Technology,

Xian 710021, P. R. China

b
College of Biological and Chemical Engineering, Jiaxing University, Jiaxing 314001, P. R.

China
c
College of Resources and Environmental Sciences, Nanjing Agricultural University, Nanjing

210095, P. R. China
d
Culture and Communication School, Shaanxi University of Science & Technology, Xian 710021,

P. R. China

*
Corresponding Author.

Tel.: +86 29 86168825; fax:+86 29 86168291.

E-mail address: mahr@sust.edu.cn (H.R. Ma).

 ACCEPTED MANUSCRIPT

Abstract: Bioleaching has been demonstrated as a feasible and effective technology

for removing Cr(III) from tannery sludge, but the recovery of bioleachate derived
from tannery sludge by bioleaching is rarely reported. The purpose of this study was
therefore to figure out the components of bioleachate and develop a chromium-iron
tanning agent using the bioleachate and reuse it in tanning process. Component
analysis indicated that the bioleachate contained high concentrations of Cr and Fe, as
well as small quantities of other elements. The dissolved organic matter in the
bioleachate was detected to be less than 1000 mg/L, which was mainly composed of
polysaccharide, aliphatic or aromatic carboxylic acid compounds. A chromium-iron
tanning agent was then prepared using the bioleachate, iron and chromium salts in a
suitable ligand environment, and reused for tanning. In the tanning experiments, the
pickled pigskins were tanned with this prepared tanning agent and the results
indicated that chromium-iron tanned crust leather presented comparable physical and
mechanical properties as well as air permeability when compared with conventional
chromium tanned crust leather, but the thermal shrinkage temperature was about 4 C
lower than that of the chromium tanned crust leather. Therefore, this study provides
not only a reuse route for tannery sludge bioleachate but also a clean tanning agent for
leather processing.
Keywords: chromium recovery, bioleachate, reuse, chromium-iron tanning agent,
tannery sludge.
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1 Introduction
In the leather industry, chromium(III) salts are the most widely used tanning
materials in tanning process because of the excellent properties, such as the particle
size, the bond capacity and the penetration ability, etc, and Cr(III) is an important source
of environmental pollutants since large quantities of tannery wastewater and sludge are
produced (Kilic et al., 2011; Wang et al., 2014). In the tanning process, a great deal of
Cr remains in the tannery wastewater, which subsequently discharges into the tannery
wastewater treatment plant, and ultimately goes into the excess sludge during the
wastewater treatment process (Basegio et al., 2002; Dhal et al.,
2013; Erdem, 2006; Wang et al., 2007). As a result, about 1.0% to 4.0% of Cr(III)
remains in the dry tannery sludge and almost one million tons of this kind of sludge is
generated annually by the tanneries in China. Because of the high content of Cr(III),
tannery sludge is classified as hazardous waste by many nations, the disposal and
resource recovery are therefore strictly restricted, which limits the use of chromium
salts (Zhou et al., 2006). The urgency of economically and safely disposing the
tannery sludge to prevent chromium accumulation and its release into the
environment has been raised (Chuan and Liu, 1996), thus to avoid menacing human
and animal health (Gupta and Sinha, 2007; Silva et al., 2010).
More recently, bioleaching has been developed as a successful and cost-effective
way to remove Cr(III) from tannery sludge over other physical or chemical methods
(Fang and Zhou, 2007; Wang et al., 2007; Zheng and Zhou, 2011; Zheng et al., 2009;
Zhou et al., 2006). During the bioleaching process, Cr(III) can be solubilized by tannery
sludge acidification through both direct and indirect mechanism driven by
Acidithiobacillus species (Rawlings, 2005; Rohwerder et al., 2003; Wang et al., 2010;
Zheng et al., 2009), mainly Acidithiobacillus ferrooxidans and/or Acidithiobacillus
thiooxidans (Chen and Lin, 2004; Mercier et al., 2006; Wang et al., 2007; Zheng,
2016). After this process, the supernatant obtained by phase separation was the
bioleachate, and the residual tannery sludge could perfectly keep its soil conditioning
and fertilizing properties for the future land application (Couillard and Mercier, 1993;
Fang and Zhou, 2007). Obviously, bioleaching technique has a great economic profit
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considering large annual consumption of Cr-containing tanning agent on a global

scale. However, to date, limited information on the recovery of bioleachate
(containing high content of Cr) and its application is available. Therefore, it is
interesting to investigate the feasibility of bioleachate reuse in tanning process.
It was found that bioleaching of Cr(III) from tannery sludge using the mixture of
indigenous iron- and sulfur-oxidizing bacteria (co-addition of Fe2+ and elemental
sulfur) could result in that almost 100% of Fe2+ was oxidized to Fe3+ in the
bioleachate, while dissolved Cr concentration reached its maximum removal of 95.6%
(Zhou et al., 2006). Undoubtedly, tannery sludge bioleachate usually contains high
concentrations of Cr, Fe, some suspended solids and soluble organic matter.
According to previous study (Ma et al., 2005), the recovered Cr derived from
bioleaching process could be reused in the tanning process, but the bioleachate
contained large amount of Fe which would affect the Cr absorption by wet blue to a
certain extent. At present, obtaining Cr from the bioleachate through alkali precipitation
makes the chromium mud unrecyclable because the addition of alkali may precipitate
Fe(III) and Cr(III) at the same time. Therefore, it is worthwhile to reuse Fe(III) and
Cr(III) in the tanning process rather than to separate them from the bioleachate.
Thanikaivelan et al. (2000) developed a novel chromium-iron tanning agent to replace
the commonly used chromium salts and various organic acids were applied as masking
agents to improve the stability of the new developed products. Besides, Rao et al.
(2002) reported that the leather tanned with chromium-iron tanning agent and
complexed with different vegetable tanning materials show different colors, such as
brown, black and grey. Furthermore, Kleban (2003) from Bayer Company used
special masking agents to pretreat the pickled hides, basic iron sulphate for tanning and
newly-developed syntans for retanning, this is a new technique for the production of
chrome-free car seat leather and the products presented pleasing appearances, good
color-fastness and good physico-mechanical properties. Based on these information, it
is helpful to develop a chromium-iron tanning agent from bioleachate and reuse it in
the tanning process.
Therefore, the objectives of the present study were (1) to analyze the component
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of bioleachate after tannery sludge bioleaching processes by inductively coupled

plasma-atomic emission spectrometry (ICP-AES), fourier translation infrared
spectrum (FT-IR) and gel permeation chromatography (GPC), etc., (2) to develop a
new chromium-iron tanning agent from the bioleachate and test the feasibility of its
reuse in the leather tanning process. Ultimately, the expected outcome of this study
will expand our knowledge of the component of the bioleachate and provide
theoretical foundation and practical evidence for the development of a bioleachate reuse
strategy in the leather tanning process.

2 Materials and methods

2.1 Bioleachate sample and pretreatment
The bioleachate used throughout this study was provided by the research team of
Dr. Lixiang Zhou from Nanjing Agricultural University, Zhejiang, China. The
biotechnology process (bioleaching of Cr from tannery sludge) was performed by using
A. ferrooxidans LX5 and A. thiooxidans TS6, Fe2+ and elemental sulfur were added
as the main energy source. After bioleaching, the liquid was phase separated and the
supernatant was the bioleachate. Since the bioleaching process produced a large
amount of sulphide, suspended solids and dissolved organic matter (DOM), an aeration
treatment would be necessary before analysis and reuse of the bioleachate. Aeration
was performed for 2d by using a compressed air pump, no obvious smell could be
detected after the treatment, meanwhile, a large number of suspended solids coagulated
and the liquid was nearly clear. The 0.45 m cellulose acetate membrane was then used
to filter the clear solutions, the obtain samples were stored at 4 C before use.
All reagents used in this study were of analytical grade.
2.2 Component analysis of the bioleachate
The initial pH range of the bioleachate was around 0.9 to 1.8. In this experiment,
each batch of 50 mL bioleachate was condensed to about 5 mL by evaporation after
pretreatment, ICP-AES (IRIS Intrepid II, America) was then employed to determine the
metal content in the solution after digestion with HCl + HNO3 + HF + HClO4
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(1:4:1:1) at 180 C. To decrease the impact of a variety of metals in the bioleachate on

tanning, main metallic elements content changes were analyzed at pH from 0.5 to 8.5,
and the changes of total organic carbon (TOC) were also measured by TOC analyzer
(TOC 5000, Japan).
The DOM were extracted as described (Reemtsma, 1999; Zhan et al., 2001): 300
ml bioleachate was measured and NaOH solution was added to adjust pH to 10 to
precipitate enough amount of metal, the obtained samples were subsequently
centrifuged at 12000 g for 20 min at 4 C to separate the solid and the liquid, the
supernatant was filtered through 0.45 m membrane and then freeze dried until
determination; eventually, DOM concentration was measured by FT-IR spectrometer
(VECTOR-22, Germany). The molecular weight distribution of DOM was measured
by GPC (G02515 911M, America). To compare the difference of the DOM between
bioleachate and original tannery sludge, the DOM in tannery wastewater was also
analyzed by FT-IR and GPC, the separation and extraction of the DOM in tannery
wastewater and bioleachate were carried out under the same conditions.

2.3 Preparation of chromium-iron tanning agent

The chromium-iron tanning agent was prepared using tannery sludge bioleachate,
iron and chromium salts, these materials were combined in a suitable ligand
environment, and the detail of the process is listed as follows.
The pretreated bioleachate, sodium dichromate and sulfuric acid solution were
added into a three-necked flask equipped with a reflux condenser, a stirrer and a
temperature controlled heat source, the flask was stirred at 95 C for 120 minutes. Then,
the pre-dissolved (in sulfuric acid medium) ferrous sulfate was added and stirred
for 30 minutes. After that, the unreduced Cr(VI) was tested by adding several drops of
the above prepared solution into the phosphoric acid solution, mixed well and
detected by adding drops of starch-iodide indicator. The absence of blue color indicated
that there was no Cr(VI) left in the solution. Otherwise, more ferrous sulfate solution
should be added until Cr(VI) can not be detected. In order to improve the stability of
the tanning agent and provide bridging groups which will join up Cr(III) and Fe(III),
organic ligands were added at the end of the above reaction. Sodium
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tartrate and sodium citrate were added as masking agents to promote the formation of
the chromium-iron tanning agent under the heating conditions. The amount of each
addition was based on the following equation:
S+98Y/278=0.49(100-B)(6X/298+3Y/278)+0.33X (1)
where S is the total sulfuric acid quantity (g), B is the basicity (%), X is the quantity
of sodium dichromate (g), Y is the quantity of ferrous sulfate (g).
Using this procedure, chromium-iron tanning agents were prepared with Cr/Fe
ratio of 2:1 and the basicity was adjusted to 20%.

2.4 Tanning experiments

The tanning experiments were carried out in a laboratory-scale tanning drum
using pickled pigskins. Two types of tanning agent were compared: (1) conventional
chromium tanning agent, and (2) the newly prepared chromium-iron tanning agent
(see Table 1). The pickled pigskins were provided by Lifeng tannery, Zhejiang, China.
Chromium salts (as chromium tanning agent) and Tanigan PAK-NC were supplied by
Bayer Leather Chemical Co., Ltd, Wuxi, China. Additionally, L-3, SES201 and LF-1
were supplied by Tingjiang chemical plant, Sichuan, China. Tap water was used for
all the tanning experiments.
As shown in Table 1, the pigskins were pickled at pH 3.0 for 90 min in the presence
of 5.0% NaCl and 1.0% organic acid, and then tanned with chromium or chromium-
iron tanning agent for 120 min. After basification, the exhausted chromium bath
revealed a pH value of about 4.0, and the resulting pig leather was horsed up for
24h to ensure the fixation of the chromium salts. After that, the finished leather was
washed with water, neutralized, fatliquored and fixed with 1.3% HCOOH. During the
tanning process, the amount of added materials in each process are changed accordingly
with the weight of pickled pigskins.
After tanning process, the spent tan liquor was analyzed for chromium and iron
concentration using an ICP-AES spectrometry and the uptake ratio of Cr was
calculated. Determination of chromic oxide in crust leather was performed by the
China light industry standard QB/T 2720-2005.
2.5 Leather testing
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To determine the quality of crust leathers and compare the two tanning agents,
the property tests of all the samples were carried out according to the official
requirements.

2.5.1 Physical and mechanical properties of crust leathers

The resulting leather was cutted into rectangular strip-like samples and kept
under standard atmospheric conditions for 48 h prior to detection of the physical and
mechanical properties. The properties tested including the tensile strength and the
percentage of extension, tear strength, break load and height, water vapor permeability,
air permeability as well as the thickness of the resulting leather. These tests were
performed according to the standards of QB/T 2710-2005, QB/T 2711-2005, QB/T
2712-2005, ISO 14268-2002, QB/T 2799-2006 and QB/T 2709-2005, respectively.
2.5.2 Differential Scanning Calorimetry (DSC) of crust leathers
Denaturation temperature (Td) of leather samples tanned with different tanning
agent were determined by using the differential scanning calorimeter (DSC-Q200,
America). The leather samples were weighed (3-5 mg by weight) into a hermetic
aluminum pans, which were then sealed using a sample pan crimper. The pans were
then transferred to a differential scanning calorimetric cell while nitrogen was purged
in the system (at 20 mL/min; nitrogen purity of 99.999%), and heated from 20 C to
250 C at the rate of 10 C/min, 5 C/min, 2 C/min. An empty hermetic aluminum
pan was used as reference in the system. The temperature was calibrated effectively
using the standard indium. The Td of the crust leather was obtained from the peak
temperatures.
2.5.3 Aging qualities of crust leathers
(1) Hot air aging
The leather samples were divided into two groups: the first group was submitted
to the physical and mechanical property tests after being air conditioned at (202) C
with relative humidity of 65%2% over a period of 48 hours, the second group was
submitted to the physical and mechanical property tests after aged in an electro
thermostatic blast oven at 80 C for 6 hours and then air conditioned for 48 hours.
(2) Hydrothermal aging
The leather samples were aged in a constant temperature humidistat at 70C with
relative humidity of 95% for 7 days and then air conditioned for 48 hours before
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submitted to the physical and mechanical property tests.
(3) Hot oxygen aging
The leather samples were aged in an air-tight container full of oxygen for 4 days
at 70 C, and then air conditioned for 48 hours before submitted to the physical and
mechanical property tests.

3. Results and discussion

3.1 Characteristics of the bioleachate
3.1.1 Metal composition in bioleachate and its change with pH
Metal compostion of the bioleachate are presented in Table 2. Metal ions with
tanning property were mainly Cr(III) and Fe(III), and their concentration was at a
range of 2100 to 2500 mg/L, this could be mainly attributed to the unabsorbed
trivalent chromium in the leather tanning process and the added ferric iron (as
bacterial energy) in the tannery sludge bioleaching process (Zhou et al., 2006). The
bioleachate also contained large amount of Ca, Na, Mg, K (4377, 2463, 1066, 552 mg/L,
respectively) and other base cations caused by adding the neutral salt in the tannery
production process. In addition, small amounts of Zn, Al, Cu, Pb etc. still existed in
the bioleachate (29.1, 43.1, 19.7 and 0.7 mg/L, respectively). According to Mella et
al. (2015), the leather samples treated with Cr recovered by electrocoagulation
using Fe electrodes presented a dark brown color and showed bad hydrothermal
stability because of the chromium and oxidized Fe. Fe affects the Cr distribution in the
leather because both Cr and Fe have tanning property, but the presence of other metals
do not have a negative effect on the tanning process, this was previously described by
other authors (Babu et al., 2007; Ma et al., 2005).
As shown in Fig. 1, Cr(III) and Fe(III) could be separated by adjusting the pH of
the bioleachate. Cr(III) began to precipitate at pH of 4.60 and was completely
precipitated at pH of 5.60, while Fe(III) began to precipitate at pH of 1.81 and was
completely precipitated at pH of 2.81. Theoretically, Cr(III) and Fe(III) can be
separated by adding alkaline to the solution. However, our results indicated that Cr(III)
and Fe(III) cannot be effectively separated by directly adding hydroxide to regulate
pH, which might due to the co-precipitation during the process. Therefore, it is
difficult to separate Cr(III) and Fe(III) in the bioleachate by adjusting the pH value.
As demonstrated in Fig. 2, DOM concentration in bioleachate was about 300 mg/L
and remained stable when the pH varies from 1.2 to 5.5. Even when the pH was
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in the range from 5.6 to 8.0, the concentration of DOM was also above 200 mg/L,
which indicated that the concentration of soluble organic matters were relatively
stable in the bioleachate at different pH values.
3.1.2 Analysis of DOM in bioleachate

The FT-IR spectra of bioleachate and tannery wastewater are showed in Fig. 3.
The infrared spectrum of DOM in bioleachate was similar with that of tannery

wastewater (similar absorption peaks: 3500-3300 cm-1, 1637 cm-1, 1500-1320 cm-1,
1210-1000 cm-1, 879 cm-1 and 640-580 cm-1), while the absorption peaks significantly
dropped at 1500-1320 cm-1 and increased greatly between 1210-1000 cm-1 and
640-580 cm-1.
According to Chen (1993) and Jing et al. (1992), the existence of the absorption
peaks between 3600-3000 cm-1, 1637 cm-1, 879 cm-1 and 626 cm-1 indicated that both
the wastewater and the bioleachate contained benzene ring and phenolic functional
group, while the existence of absorption peak between 3600-3000 cm-1, 1500-1320
cm-1 was associated with the presence of carboxyl groups. Therefore, both the
wastewater and bioleachate contained aromatic carboxylic acids and polysaccharides.
The peaks around 1147 cm-1 suggested that the wastewater contained large amounts of
fatty substances (Reemtsma and Jekel, 1997). Although the wastewater and
bioleachate contained the same groups of DOM, the intensity of the absorption peaks
varies. This phenomenon can be attributed to the oxidative degradation of large
amount of organic matters under strong acidic conditions, resulting in the dramatic
decline of organic acid concentration and the formation of large amount of
structurally stable aromatic substances.
Fig. 4 and Table 3 show the average relative molecular weight segments of
DOM in both bioleachate and tannery wastewater. In the bioleachate, the mass
fraction is 74.12% for the average molecular weight of 1923, and the average molecular
weight of 147 components accounted for 25.68% of the total. In the tannery wastewater,
the average molecular weight of 1909 accounted for 89.27% of the components
of the total, and the average molecular weight of 721 components accounted for 10.73%
of the total, indicating that the oxidative degradation degree of organic matter during
the bioleaching was significantly higher than that of the aerobic treatment of tannery
wastewater. The relative molecular weight of the main components of DOM in the
bioleachate was between 2128 and 1702. Although their
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molecular weight range is equivalent to that of certain vegetable tanning agents, it will
have less impact on the leather tanning because DOM has no tanning property. The
components of soluble organic matter in low acidity are mainly organic acids, and the
tanning property of organic acids with the large molecular weight may decrease or
disappear.
3.2 Crust leathers properties and chromium exhaustion
3.2.1 Physical and mechanical properties

Based on industrial aspects the physical and mechanical properties must be taken
into consideration when the structural properties are studied. Accordingly the physical
and mechanical properties of the tanned leather samples are showed in Table 4. The
physical and mechanical tests include the measurement of the tensile strength,
elongation under specified load, elongation at break, tear strength, water vapor
permeability and air permeability, etc. The improvement of physical and mechanical
properties of crust leather are fundamental criteria for confirmation of the effect of fixed
chromium tan with the leather proteins (Nashy et al., 2012). Since a successful tanning
agent is the one that interacts with the collagen matrix of the leather, which provides
stability to some extent. Strength determination of crust leathers are of great concern
for assessing crust leather, because it gives indication of the fiber bundles.
It can be concluded from Table 4 that, compared to chromium tanned leather, the
chromium-iron tanned leather showed better physical, mechanical and sanitation
properties except for the slightly lower water vapor permeability, but the air
permeability was excellent. The better performance in tensile strength, tear strength and
break load revealed that Fe in the prepared chromium-iron tanning agent could enhance
toughening of leather collagen. The air permeability of chromium-iron tanned
leather was found much superior to that of the conventional chromium tanned leather,
which could also satisfy consumers requirements by providing leathers of better
sanitary property. These results showed that the cross-linking of collagen with Cr(III)
and Fe(III) during chromium-iron tanning process could endow the resulting leather
with favorable mechanical properties. The physico-mechanical properties of the
resulting leather samples met the International Organization for Standardization (ISO)
standards for sofa leather, hence the quality of crust leather was ensured. Besides,
it is worth to mention that the requirement of less chromium for tanning had
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been proved to be practical based on the properties of the resulting leather. Recent focus
of leather tanning is to discover an alternative tanning material to minimize the adverse
environmental effect of chromium tanning but confer similar properties as chromium
salts. Several efforts have been made aiming at using aluminum(III) (Wolf et al., 2001),
titanium(IV) (Crudu et al., 2014; Peng et al., 2007), zirconium(IV) (Covington, 2011),
iron(II) (Chen et al., 2011), their mixed salts (Roca et al., 2008; Wang et al., 2012)
and other tannages (Bacardit et al., 2014; Krishnamoorthy et al.,
2012) as alternatives to chromium(III). Although the tanning ability of these metal
salts is not as good as that of chromium (Covington, 2011), their mixed salts can be
successfully used in all proportions in the tanning process.
3.2.2 DSC analysis

The Td of chromium and chromium-iron tanned leathers were studied by DSC

analysis. The width, height, position and symmetry of the thermogram peak gives
information about the thermal denaturation of leather samples over a range of defined
temperature (Krishnamoorthy et al., 2012). The Td generally correlated with the onset
temperature of its peak in a DSC curve, which can be used as a measure of the
thermal stability of tanned leathers with different tanning agents. Fig. 5 shows the
DSC curves of chromium or chromium-iron tanned leathers at different heating rate.
The exothermic transitions recorded for the crust leathers consist of at least two
peaks, indicating the continuous denaturation processes. The first peak is recorded for
temperatures within the range of 120 C and 140 C, which indicated the existence of
weakened or broken molecular chain bonds between collagen fibers. The second peak
is located between the temperature of 145 C and 190 C, which suggested the fibers
were totally disintegrated. At the same heating rate, the temperature of chromium
tanned leather was higher than that of the chromium-iron tanned leather at the first
peak, which indicated the thermal stability of the crust leathers. For leathers treated
with chromium-iron, the Td was only 4 C lower than that of the chromium tanned
leather at the first peak (see Table 5). Moreover, when heating at the increasing rate of
5 C/min, the Td of the leather reaches 158.0 C for chromium-iron tanned leather and
it is higher than that of chromium tanned leather. Thus, comparatively better thermal
stability can be observed for chromium and chromium-iron tanned crust leathers. In
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chromium tanning process, Cr(III) mainly interacts with the carboxyl group of collagen,
and result in the formation of cross-links between collagen and Cr(III), which play
the key role in the thermal stability of the leather (Liu et al., 2016; Ma et al., 2014).
The mechanism involved in iron tanning is considered to be similar to that involved in
chromium tanning (Sreeram and Ramasami, 2003). Therefore, the cross-links of
collagen formed not only with chromium but also with iron in chromium-iron tanning
process, this could efficiently improve the thermal stability of the leather. In addition,
the capillary structure of collagen fibers seems to be affected by interaction with various
chemicals used in each process. For instance, sodium chloride can remove hyaluronic
acid completely in the soaking process and facilitate fiber structure opening and
splitting up, which enables good penetration and fixation of chromium(III) species with
the purified collagen (Siddique et al., 2015).
Besides, the thermal stability of the chromium-iron tanned leather can still match
the chromium tanned leather despite reduced amount of chromium was used. As
mentioned in the introduction, chromium tanning is one of the most
environmentally-unfriendly processes in leather tanning industry owing to the
presence of Cr in the wastewater. It is certain that the increasing use of chromium-iron
tanning will decrease the use of Cr salts.
3.2.3 Aging qualities of crust leathers
Table 6 shows the aging test results, including hot air aging test, hydrothermal
aging test and hot oxygen aging test. The properties of chromium-iron tanned leather
did not show significant change after hot air aging. According to Hummel and
Germann (2003)s results regarding to the correlation between natural and artificial
aging, hot air aging under such condition was equal to the effect of around one-year
natural aging. Hence, leathers tanned by chromium-iron tanning agent will still be in
good condition after one year's storage. For hydrothermal aging, the property of
chromium-iron tanned leather was weakened and the damage degree was close to the
chromium tanned leather. For hot oxygen aging, the tear strength of chromium-iron
tanned leather was almost unchanged while the tear strength of the chromium tanned
leather was obviously weakened, the stability and other properties of chromium-iron
tanned leather were comparable to that of the chromium tanned leather.
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Shrinkage temperature (Ts) is one of other important parameters to indicate the
degree of cross-linking of collagen and the hydrothermal stability of the leather, high
hydrothermal stability can be processed through the subsequent mechanical
operations of splitting and shaving (Liu et al., 2016). The Ts of the chromium tanned
leather was 114 C. When Fe(III) was applied in combination with Cr(III) in the tanning
process, the Ts of the leather sample was 105 C, which was slightly lower than that
of the chromium tanned leather. During the combination tanning process, stable
intramolecular and intermolecular cross-linking could form by multipoints cross-
linking of collagen with Cr(III) and Fe(III) (Krishnamoorthy et al., 2012, 2013; Liu et
al., 2016). This was achieved through the complexation of chromium with iron in a
proper ligand environment when the chromium-iron tanning agent was prepared. After
air and oxygen aging, the Ts of the chromium-iron tanned leather decreased from
105 C to 97 C. However, the Ts of the chromium-iron tanned leather did not change
after hydrothermal aging. The softness of the original sample tanned with chromium-
iron decreased by 1.0 mm in comparison with that of the sample tanned with chromium.
After the aging treatment, the softness of leather tanned with chromium-iron had no
significant changes when compared with that of the chromium tanned leather. It could
be explained by the fact that Fe(III) could form strong intramolecular and
intermolecular cross-linking and decrease the softness, which was also consistent with
the physico-mechanical properties.
Various studies have reported the inferior strength and poor aging properties of
the iron tanned leather (Babu et al., 2007; Gaidau et al., 1998; Sreeram and Ramasami,
2003). However, in this study, the poor aging qualities of chromium-iron tanned
leather was greatly improved compared to that of the chromium tanned control group.
Moreover, the aging stability was comparable to that of the chromium tanned leather
or even superior under hot oxygen aging conditions.
3.2.4 Chromium exhaustion
The chromium and iron content in spent tanning liquors are presented in Table 7.
In the case of chromium-iron tanning agent based tanning, the content of chromium and
iron were 1.19 g/L and 0.62 g/L, respectively, and the uptake rate of chromium and
iron were 91.20% and 89.52%, respectively. A similar observation is reported by Rao
et al. (2002). The amount of Cr2O3 (dry weight basis) presented in the chromium-
iron tanned leather was 2.48%, resulting in the properties of chromium-iron
tanned leather was satisfactorily. The content of chromium in the
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spent tanning liquor was significantly increased upon the usage of chromium tanning
agent compared to the chromium-iron tanning agent. These results demonstrated that
the usage of the prepared chromium-iron tanning agent can not only guarantee the
quality of the tanned leather but also reduce the dosages and emission of chromium.
The recovery and recycle of chromium from tannery sludge by bioleaching
technique can not only reduce environmental impact but also effectively promote
clean production in leather industry. Chromium-iron tanning agent was prepared using
the bioleachate derived from bioleaching process, which can reduce the costs of Cr
and Fe separation, the tanning process with less chromium is a kind of eco-friendly
and attractive tanning process, it not only reduce the costs of leather production but
also contribute to the development of cleaner process. Therefore, chromium recovery
and its reuse in tanning process have positive impact on the economic, environmental
and social aspects.

4. Conclusions
1) This study exhibited that tannery sludge bioleachate contained large amounts
of Cr(III) and Fe, it also contained Ca, Na, Mg, K and small quantities of other elements,
among which mainly Fe presented an impact on tanning. The TOC in bioleachate
was generally lower than 1000 mg/L, the average relative molecular weights were
mainly from 1923 to 147, the mass fractions were 74.1% and 25.7%, respectively, and
the TOC components were polysaccharide, aliphatic or aromatic carboxylic acid
compounds.
2) A chromium-iron tanning agent was prepared in this study by using
bioleachate from tannery sludge, it was used for tannage in tanning process. Tanning
experiments were carried out using this prepared chromium-iron tanning agent, and
the results indicated that the physico-mechanical properties and air permeability of
chromium-iron tanned leathers were better than those of the chromium tanned leathers.
By using this new tanning agent, we can reduce the usage of chromium during
tanning process. As the DSC scanning was carried out under the same heating rate
conditions, the shrinkage temperature of chromium-iron tanned crust leather was
about 4 C lower than that of the chromium tanned leather. Compared with chromium
tanned leather, chromium-iron tanned leather did not present significant difference on
heat aging properties after hot air aging tests (equivalent to about a years natural aging).
After hot oxygen aging tests, the tear strength of chromium-iron tanned leather
 ACCEPTED MANUSCRIPT
was almost unchanged, and its tensile strength decrease span was slightly larger than
that of the chromium-tanned leather but its softness showed little change compared
with the chromium tanned leather. Thus, this study throws light on a new avenue in
the leather processing by employing a novel and clean tanning agent.

Acknowledgements
This work was supported by National Natural Science Foundation of China (No.
21177079).

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Table 1
Tanning formulations.
Process Percentage Material Temperature Time Remark
(%) (C) (min)
Pickle 100 H2O 25
5.0 NaCl
1.0 Organic acid 90 pH: 3.0
Tanning 1.8 Tanning agent 25 120 Tanning through
Basify 2.7 NaHCO3 (1:10) 150 pH: 4.0-4.2
100 H2O 35 30
100 H2O 45 30 Stop overnight, drum
30 min the next day

Horse up for 24h

Wash 300 H2O 35
0.5 Degreasing agent 10 Drain

Neutralize 150 H2O 35

3.0 Tanigan PAK-NC

1.0 CH3COONa 30
0.8 NaHCO3 (1:10) 60 Check with B.C.G
pH:5.5/Drain/Wash

Fatliquor 150 H2O 45

6.0 L-3
4.0 SES201
2.0 LF-1 60
Fix 1.3 HCOOH (1:10) 30 pH: 3.8
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Table 2
Concentrations of different metals in the bioleachate sample.
Elements Content (mg/L)
K 552.4
Ca 4377
Na 2463
Mg 1066
Al 43.1
Zn 29.1
Cu 19.7
Cr(III) 2126
Fe(III) 2338
Mn 16.4
Ni 8.9
Pb 0.7
Mo 0.5
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Table 3
Different distribution ranges of molecular weight of DOM in the bioleachate and
tannery wastewater.
Tannery wastewater Bioleachate
Molecular Molecular
Percentage Percentage
weight weight
(%) (%)
range range
2141-2861 7.20 2141-2549 7.37
1702-2128 70.55 1702-2128 59.40
1104-1692 11.52 1032-1692 7.35
721 10.73 147 25.68
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Table 4
Physical and mechanical properties of crust leathers.
Parameters Chromium Chromium-iron
Tensile strength N/mm2 15.4 21.4
Elongation under specified load % 17.0 14.0
Elongation at break % 40.0 41.0
Tear strength N/mm 67.9 84.6
Break load kg 10.0 21.0
Break height mm 9.8 12.0
Water vapor permeability mg/(10cm2 24h) 271.2 230.5
Air permeability mL/(cm2 h) 7.26 50.57
Substance increase % 25.4 42.3
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Table 5
DSC analyses of crust leathers at different heating rate.
Heating rate
Crust leathers
10 C/min 5 C/min 2 C/min
tanned by
Peak 1 Peak 2 Peak 1 Peak 2 Peak 1 Peak 2
Chromium 134.8 C 176.5 C 131.2 C 147.7 C 129.8 C 163.5 C
Chromium-iron 130.9 C 164.9 C 128.3 C 158.0 C 125.8 C 166.0 C
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Table 6
Aging qualities of crust leathers.
After After After
Original
Index Leather tanned by air hydrothermal oxygen
sample
aging aging aging
Tensile strength Chromium 16.7 18.0 12.2 13.0
(N/mm2) Chromium-iron 20.8 20.3 15.2 24.4
Break elongation Chromium 48 42 48 35
(%) Chromium-iron 42 43 40 37
Tear strength Chromium 67.9 64.5 61.1 47.5
(N/mm) Chromium-iron 84.6 80.1 73.2 86.0
Chromium 114 103 115 106
Tsa (C)
Chromium-iron 105 97 105 97
Chromium 4.5 3.6 3.8 3.9
Softnessb (mm)
Chromium-iron 3.5 3.4 3.2 3.2
a
The shrinkage temperatures (Ts) of crust leathers were measured using a Shrinkage
Tester (MSW-YD4).
b
The softness of crust leathers were determined by the ST-300 Leather Softness
Measuring Instrument.
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Table 7
The analysis of spent tanning liquors.
Chromium chromium-iron
Parameters
tanning tanning
Chromium in spent
2.05 1.19
tanning liquor (g/L)
Iron in spent
- 0.62
tanning liquor (g/L)
Chromium
84.84 91.20
exhaustion (%)
Iron exhaustion (%) - 89.52
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Figure captions

Fig. 1. Variation of the concentration of Cr(III) and Fe(III) at the different pH values.

Fig. 2. The content of DOM in the bioleachate at different pH values.

Fig. 3. FT-IR spectra of DOM in the bioleachate and tannery wastewater.

Fig. 4. GPC curve of DOM in the bioleachate (a) and tannery wastewater (b).
Fig. 5. DSC plot of chromium (a) or chromium-iron (b) tanned crust leathers at
different heating rate.
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R
Fig. 1. C
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Fig. 2. C
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T
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R
C
S
Fig. 3. U
N
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C
S
U
N
A
M
D
E Fig. 4.
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I
R
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SN
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Fig. 5.
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Highlights
Component analysis was carried out for broadening our knowledge of
bioleachate.
A new chromium-iron tanning agent was prepared by using bioleachate.
The chromium-iron tanning agent was successfully reused in tanning process.
The recycle of Cr within bioleachate can effectively improve the leather industry
cleaner.