Journal of Cleaner Production 154 (2017) 276e283

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Journal of Cleaner Production

journal homepage: www.elsevier.com/locate/jclepro

An integrated technology to minimize the pollution of chromium in

wet-end process of leather manufacture*
Chunxiao Zhang a, b, Fuming Xia a, Jiajun Long a, Biyu Peng a, b, *
a
National Engineering Laboratory for Clean Technology of Leather Manufacture, Sichuan University, Chengdu 610065, PR China
b
Key Lab. of Leather Chemistry and Engineering of Ministry of Education, Sichuan University, Chengdu, Sichuan 610065, PR China

a r t i c l e i n f o a b s t r a c t

Article history: In order to minimize chromium pollution, based on tracing the life cycle of chromium in whole leather
Received 30 September 2016 wet-end processing, an integrated technology comprising of a novel salt-free and high-exhaustion
Received in revised form chrome tanning process, modified chrome retanning, direct recycling of tanning wastewater and high-
16 March 2017
ly efficient removal of Cr from post-tanning floats was developed. The results indicated that, in the novel
Accepted 29 March 2017
Available online 31 March 2017
technology, the total Cr utilization ratio reached to 98.6% (conventional 91.2%), the total chromium
discharge was reduced by 84.2% from the source, and the spent tanning liquor could be completely
recycled for at least 10 cycles, whilst the leather properties were not impaired. Furthermore, the
Keywords:
Salt-free pickling
remained Cr in the wastewater without reused value was removed by means of precipitation with
High chromium exhaustion optimized bases, and the residual Cr was at the level of 1.0e1.2 mg/L, the produced chrome-contained
Life tracking sludge was reduced by 28.1%. The novel technology integrating reduction at source and end treatment
Chromium recovery can reduce the total Cr discharge with effluent to 4.604 g/t salted-wet hide and the chrome concentration
Wastewater recycling in mixed wastewater streams is 0.354 mg/L, and achieve near zero emission of chromium in leather
processing.
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction with chloride ion, in effluent to near zero emission is a matter of

Nowadays, environmental protection has become one of the
most concerned issues in global industrial activities. Among typical
pollutants from leather industry, chrome discharge is especially
concerned, because chrome is put in the list of the strict controlled
discharging metals in most countries, and chrome tanning is still
the most important and widely used tanning method for quite a
long time in the future, which is characterized by giving leather top
handing quality, high hydrothermal stability, user-specific proper-
ties and versatile applicability. (Sundar et al., 2011).
However, in the conventional chrome tanning process, only
60%e80% of the offering chrome is effectively utilized. As a result,
the chrome concentration in spent float is in a range of
2500e3,000 mg/L, (Sundar et al., 2002) which poses a significant
disposal problem. Hence, minimizing the residual chrome, together
*
A Technical Paper including the contents of an oral presentation at the 11th
National Conference on Leather Chemicals at Qilu University of Technology, Ji-nan,
Shandong Province, China, on July 29, 2016.
* Corresponding author. National Engineering Laboratory for Clean Technology of
Leather Manufacture, Sichuan University, Chengdu 610065, PR China.
E-mail address: pengbiyu@scu.edu.cn (B. Peng).
great concern to tanners.
There is a huge volume of research work in reducing chrome
discharge, which can be classified into two categories, i.e. reduction
from the source and by end treatment. High-exhaustion chrome
tanning is the major technology focused on reducing chrome con-
centration in the residual float, which is the foremost source of
chrome discharge (Rivela et al., 2004). There are two main ap-
proaches to increasing the chrome uptake, which mainly involve
modifying chrome complexes by use of sodium citrate, sodium ox-
alate and orthophtalate (Gregori et al., 1993), and increasing the
collagen reactivity with the participation of auxiliaries including
oxazolidine (Sundarapandiyan, et al., 2011), the multi-functional
group agent containing carboxyl, hydroxyl and tetra-amino
(Shifang et al., 2007), glyoxylic acid (Fuchs et al., 1993). Modifying
tanning process through raising the beginning pH can also increase
the chromium absorption ratio. (Jiping et al., 2006; Legesse et al.,
2002) However, there are some problems limiting their widely
commercial acceptability, i.e., it is still necessary to add enough
dosage of neutral salts, the operations are more complicated, the
residual chrome in the effluent is still at a rather high level, and lastly
but most significantly, the leather properties and the following

http://dx.doi.org/10.1016/j.jclepro.2017.03.216
0959-6526/© 2017 Elsevier Ltd. All rights reserved.
 C. Zhang et al. / Journal of Cleaner Production 154 (2017) 276e283
recycling of the spent tanning float may be negatively affected.
By measured the residual Cr concentrations in the wastewaters
of the operations during leather processing, Jian et al. (2011) found
that, besides the high-concentration chrome wastewater from
chrome tanning and retanning processes, the low-concentration
chrome wastewater from post-tanning processes resulting from
chrome leaching out from chrome-tanned leather should be paid
more attention, because the limit of total chrome discharge in
effluent is set on 1.5 mg/L for discharging into sewage systems in
most countries. The former can be direct recycled back into tanning,
or the residual chrome can be recovered and reused. All chrome-
tanned floats should be further treated to separate chrome before
bumped to the integrated wastewater treatment plant in order to
avoid chrome-containing effluents mixing with other wastewater,
thus producing a huge amount of chrome-containing sludge.
Recycling the high-concentration chrome-containing effluent
directly back into tanning and recovering chrome from effluent are
the practicable methods to prevent Cr from being discharged into
sewage systems (Sreeram et al., 2005; Panswad et al., 1995; Panov
et al., 2008). However, the chemical constituents of the spent
chrome effluent in the conventional tanning process, comprising of
neutral salts, chromium complexes, masking agents, etc., are so
complex that it’s hard to maintain the chemistry equilibrium of
recycled floats after several cycles. The chrome tanning effective-
ness will be negatively influenced by the accumulation of residual
components. In addition, because of high concentration Cr residual
in spent float, it is difficult to completely replace fresh water with
the wastewater, otherwise, the residual Cr will quickly combine
with the surface of pelts to cause coarse grain (Cranston et al.,
1997), hence usually more float is available for recycling than can
actually be used. The compositions of the spent liquors in the above
high-exhaustion chrome tanning processes are more complicated
with the introduction of auxiliaries; therefore, the recycling process
becomes unmanageable. (Nacheva et al., 2004).
Generally, it is not considered to recycle and reuse the low-
concentration chrome wastewater from post-tanning processes,
because the chemical constituents are more complicated. Some
approaches have been researched to remove Cr from spent liquors,
including nanofiltration (Das and De, 2006), constructed wetlands
(Dotro et al., 2012), activated carbon (Fahim et al., 2006), brown
seaweed (Aravindhan et al., 2004a, b), cation exchange resin (Sahu
et al., 2009) and the alkalis of sodium carbonate, magnesium oxide,
calcium hydroxide (Guo et al., 2006). Hitherto, alkali precipitation
is one of the effective and practical ways. The alkali precipitation
effectiveness is adversely affected by residual organic chemicals
(Remoudaki et al., 2003). The keys are how to improve the pre-
cipitation efficiency and reduce the amount of produced chrome-
containing sludge, which mainly depends on the amount of resid-
ual chrome.
Aiming at realizing the near zero discharge of chromium in
leather processing, an integrated technology composing of a novel
salt-free and high-exhaustion chrome tanning conducted at a high
initial pH with aromatic sulphonic acid, modified chrome retan-
ning, recycling of chrome tanning wastewater and highly efficient
removal of Cr from post-tanning wastewater is designed. Firstly,
with the use of the novel high-exhaustion chrome tanning and
modified chrome retanning methods, the chrome emission is
reduced to a maximum degree at the source in tanning processing,
the constituents of the spent tanning liquor are simplified because
of high exhaustion of added chemicals and being free of sodium
chloride and additional masking agents. Secondly, the high-
concentration chrome-containing floats can be completely recy-
cled back into process as many times as possible because of the low
chrome concentration and less accumulation effect of other com-
ponents. Thirdly, the releasing amount of chrome from the leather
277
tanned under the novel process into floats will also go down in the
post-tanning processes, thus reducing the amount of produced
chrome-containing sludge from alkali precipitating. According to
the above design, the key process parameters and effectiveness
were optimized and evaluated.
2. Experimental and methods
2.1. Materials and instruments
Salted-wet cattle hides from Sichuan, China, were purchased
from a local tannery (Chengdu Xinshi Leather Industry CO., Ltd.).
Chromosal B (a chromium tanning agent with 33% of basicity and
26% of Cr2O3 (0.177% of Cr) content) was purchased from LANXESS
Inc. Naphthalene sulfonic acid (NSA), was synthesized as per the
standard synthesizing procedures in our laboratory. The following
applied leather chemicals, including syntans, fatliquors, polymers,
filling agents, etc. were of industrial grade and from Sichuan Dowell
Science & Technology Co., Ltd China. The other chemicals were of
analytic grade.
Stainless Experimental Drum (GSD400-4, Wuxi Xinda Light In-
dustry Machinery Co., Ltd.), Inductively Coupled Plasma Emission
Spectrometer (AES-ICP, 2100DV, Perkin Elmer Inc. America), Pre-
cision Slice Machine (C520L, Camog (a) Inc., Italy), Digital Deter-
minator of Shrinkage Temperature (MSW-YD4, Shanxi University of
Science and Technology, China).
2.2. Methods
2.2.1. Novel salt-free and high-exhaustion chromium tanning and
retanning processes
Ten pieces of salted-wet cattle hide conducted soaking, fleshing,
liming, splitting, deliming and bating procedures as normal, and
then were divided into two groups. Among them, a whole grain-
layer limed cattle hide with thickness of 2.8e3.0 mm after split-
ting was cut into two half sides along with the backbone line,
symmetrically, and they were distributed to different tanning
groups for evaluating and comparing tanning effects. As shown in
Fig. 1, the two groups were carried out a conventional chrome
tanning (at pH 2.8 around with 6.5% Chromosal B) and a novel high-
exhaustion (at pH 5.0 around with 5.0% Chromosal B), respectively.
After stacked and aged for 7 days, the tanned leathers were carried
out sammying, shaving (thickness 1.1e1.2 mm), wetting as normal
operations. Then the shaved tanned leathers were put back to a
drum and conducted a normal chrome retanning (at pH 3.5 around
with 3.5% Chromosal B) and a modified retanning (at pH 4.5 around
with 3.0% Chromosal B) correspondingly. Following on that, the
chrome retanned leathers were neutralized, retanned with organic
syntans, dyed and fatliquored as the normal shoe upper leather
procedures (See Table A, Appendices).
2.2.2. The recycle of spent chrome tanning liquors
As shown in Fig. 1, the spent chrome tanning liquors from the
above two tanning processes were completely collected and reused
after filtrated through a 20 mesh filter. A whole grain-layer limed
cattle hide with thickness of 3.0e3.2 mm after splitting was divided
into pieces adjacently and symmetrically, and they were distrib-
uted to different tanning groups for evaluating and comparing
tanning effects in spent liquors. The spent liquors were reused in
two steps, i.e., used as the pickling float and supplement water at
the later stage of tanning. The bated pelts were soaked in 50% of the
filtered spent tanning liquors at 23
C with or without adding 6% of
sodium chloride, and the float pH was adjusted to about 2.8 or 5.0
with a certain amount of sulfuric acid or NSA, respectively, corre-
sponding to the conventional or novel high exhaustion chrome
278 C. Zhang et al. / Journal of Cleaner Production 154 (2017) 276e283

Conventional chrome Salt-free and high-exhaustion

tanning processing chrome tanning processing
Water 50%; 18H Bated pelts Bated pelts
NaCl 6.0-8.0%;
Formic acid 0.5%; Water 50%; 18H
Pickling(pH2.8 0.2) Pickling(pH5.0 0.2)
Sulfuric acid 1.0%; NSA 1.0-1.5%
3H ; 3H;
Chromosal B 6.5%; Chrome tanning Chrome tanning Chromosal B 5.0%
HCOONa 0.5% Wastewater 1
NaHCO3 1.6-1.8%; Basifying Wastewater 1 Basifying NaHCO3 1.0-1.2%;
pH 4.20 around pH 4.20 around

2-4H; Complement water Complement water 2-4H;

Constant 40 C to 200% to 200% Constant 40 C

Stacking/Sammying Stacking/Sammying
Wastewater 2

Water200%; 1H; Shaved leather Wastewater 2 Shaved leather Water 200% ; 1H;
NaHCO3 0.3% ; NaHCO 3 0.3%;
pH 4.50 around Wetting pH 4.50 around
Wetting
Water 200%; 2H; Water
HCOOH 0.3%; sludge Cr<1.5mg/L Water 200%; 2H;
Chromosal B 3.5%; Chrome retanning Chrome retanning Chromosal B 3.0%;
HCOONa 0.5% HCOONa 0.1%

Post tanning as Wastewater 3 Post tanning as

normal process Wastewater 3 normal process

the route of the route of the route of the water the route of the water
operations recycled water before precipitated after precipitated

Fig. 1. Flowchart of the two chrome tanning processes and recycling route of spent chrome-containing wastewater.

tanning process. Then 5.0% of Chromosal B was added, and 150% of
filtered spent tanning liquor was replenished into the corre-
sponding drum after basification. All the other operations were the
same as the above. The spent liquors were collected and recycled
again for several times as the same procedures.
2.2.3. Removal efficiency of chromium in effluents by alkali
precipitation
Every batch of the chromium-containing wastewater from wet-
end processing, including the spent liquors of chrome tanning and
post-tanning operations, was collected, separately, and the chrome
concentration were analyzed. The chrome removal efficiency of the
serials of spent liquors by alkali precipitation was also investigated.
20.00 ml of each spent liquor was put in a beaker, and a varying
amount of NaOH solution (0.1 mol/L) or powder MgO was slowly
added to adjust the solution pH to a different value in the range of
6.0e11.0. Then the total solution volume was set to 100.00 ml by
adding deionized water. After settled for 24 h, the supernatant
solution was filtered and chromium concentration was measured
with AES-ICP. At the same time, the amount of sludge sedimenta-
tions was evaluated as per the standard method (GB 11901e89).
leather was calculated.
2.2.5. Determination of Cr concentrations in spent liquors
The spent chrome-containing liquors were filtered with 100
mesh filter cloth and digested with the mixture of sulfuric acid and
nitric acid at 120
C for 120min. The digestion solutions were
appropriately diluted and their chromium concentrations were
measured with AES-ICP. The chromium concentrations of spent
tanning liquors were calculated.
2.2.6. Test of physical and mechanical properties of crust leather
Dried crust leather samples of each tanning group were taken
out in the adjacent and symmetrical parts of the same hide for
testing physical and mechanical properties. Samples were condi-
tioned as per IUP method (IUP 2, 2000). Physical properties, such as
tensile strength, elongation at break, tear strength and bursting
strength, were examined as per the standard procedures (IUP 6,
2000; IUP 8, 2000; IUP 9, 1996). The Shrinkage Temperatures of the
leather were measured as per the standard of ISO3380-1975.
3. Results and discussions

2.2.4. Determination of chromium content and distribution in
leather
The chrome-tanned leather samples of each tanning group were
taken out in the adjacent and symmetrical parts of the same hide,
and washed thoroughly to remove uncombined chromium. Then
the samples were freeze-dried at 55
C and 20pa vacuum for 24 h.
The dried leathers were averagely split into three layers using
Precision Slice Machine. A certain quantity of the dried leather
sample was completely digested with the mixture of nitric acid and
chloride acid at 120
C for 120min. The digestion solutions were
appropriately diluted and their chromium concentrations were
measured with AES-ICP. The chromium content in each layer of the
3.1. The significance of high-exhaustion chrome tanning technology
in reducing chromium discharge
3.1.1. Effectiveness of the novel main chrome-tanning and modified
chrome retanning processes on reducing chromium discharge at the
source
To significantly increase chromium uptake is a prerequisite to
achieving near zero discharge of chromium in leather making pro-
cessing. Aiming at eliminating the use of sodium chloride and
minimizing the discharge of chromium, a salt-free and high-
exhaustion chrome tanning method has been established in our
laboratory and commercially accepted. In the novel process (Zhang
 C. Zhang et al. / Journal of Cleaner Production 154 (2017) 276e283
et al., 2016), the bated pelts are preprocessed with naphthalene
sulfonic acid (NSA) to a relative high pH value of about 5.0, then the
other chrome tanning operations are almost the same as the con-
ventional process, what was more, the novel method integrates the
advantages of salt-free pickling and chrome tanning at a high initial
pH, and also ensures the chrome-tanned leather excellent quality
and property, when the Cr absorption rate in the novel process is
increased from 97% to 72% of the conventional process, whilst the
residual Cr concentration in effluent is decreased by 90.8% and at a
rather low level of about 107.7 mg/L, and without differing the Cr
contents and distributions of the wet-blue, exhibiting obvious
effectiveness on minimizing the discharge of chrome and sodium
chloride.
However, generally, after aged for more than a week, chrome-
tanned leather is conducted sammying and shaving steps to
ensure the leather being with a certain and even thickness. The
shaved wet-blue leather is wetted and then retanned with chro-
mium to improve the uniformity of chrome distribution and the
reactivity of leather fibers with chemicals, which is beneficial to the
following post tanning operations. Obviously, the chrome retan-
ning wastewater is another main source of chrome-contained
effluent because of the addition of chrome agents. On basis of the
novel high-exhaustion chrome tanning, the wet-blue leather was
conducted with a little modified chrome retanning operation
shown in Fig. 1, and the effectiveness in reducing chrome discharge
was examined and the results in Fig. 2.
The results in Fig. 2 indicate that, though the chrome offer is
decreased by 15%, from 0.62% to 0.53% (i.e. the dosage of chrome
tanning agent with 0.177% Cr content was reduced from 3.5% to
3.0%), in the modified chrome retanning process, both the Cr con-
tent and distribution in the retanned leather keep almost the same
level with that of the leather from conventional processing, whilst
the residual Cr in the spent effluent is further decreased by 61%,
from 434 mg/L to 167 mg/L.
3.1.2. Tracing chrome discharge in whole leather wet-end
processing
As mentioned before, apart from the high-concentration
chrome-containing effluents from chrome tanning, sammying
and chrome retanning, actually, chrome staying in leather will also
leach out at varying levels in the following post-tanning operations,
including wetting, neutralizing, organic retanning/filling and
dyeing/fatliquoring, thus all the spent liquors contain chrome (See
Fig. 1 and Table A in Appendices). The Cr concentrations of the spent
liquors from main wet-end processes were traced. And the results
are shown in Table 1.
Table 1 indicates that the total Cr utilization ratio is increased to
96.7% from 79.9%, the chromium concentration of each wastewater
Fig. 2. Effectiveness of the modified chrome retanning process.
279
is decreased by 13.1%e90.8% and the total chromium discharge
amount is reduced by 87.6% in the novel chrome tanning process
comparing with the corresponding one from the conventional
process. What’s more, though the total Cr offering is decreased by
22.2%, the comprehensive properties of the crust leather, including
organoleptic properties and physical-mechanical performances,
aren’t negatively influenced (Table 2).
Although there is still 0.362 kg/t (salted-wet hide) Cr remaining
in the tannery wastewater, which must be further treated in order
to meet with increasingly stringent Cr emission regulations, it is no
doubt that the novel salt-free and high-chrome exhaustion chrome
tanning technology can play an important role in reducing chrome
pollution from the source, and increasing the technical feasibility
and economical acceptability of following recovering and removing
of chrome from chrome-contained wastewater.
3.2. Direct recycling of the spent chrome tanning float
The spent chrome tanning float with high concentration chrome
can be collected, and directly recycled back into tanning. There are
two usual ways of the recycling, i.e. the wastewater can be added as
the pickling float and/or the supplement water at the later stage of
tanning after basifying, shown as Fig. 1.
As previously mentioned, in the conventional chrome tanning,
because of high concentration Cr residual in spent float, it is diffi-
cult to completely replace fresh water with the wastewater,
otherwise, the residual Cr will quickly combine with the surface of
pelts (Sreeram et al., 2005). Moreover, the accumulation of salts,
masking agents and organic components with cycle-index makes
maintaining the chemistry equilibrium of recycled floats more
complicated, (Theis and Goet, 1932; Panov et al., 2008) and the
tanning effect and leather quality will be obviously negatively
affected. Hence, the recycled amount of the spent liquors and cycle-
index of spent liquors are limited. Correspondingly, for the above
established novel chrome tanning process, the residual Cr con-
centration is quite low, and the other constituents in spent liquor
are relatively simple because of no addition of NaCl and masking
agents, hence, the main problems appeared in recycling of con-
ventional spent tanning liquor will be overcome. It can be expected
that the cycle-index should be increased, and the spent tanning
float can also be recycled to make up the whole volume of the
pickling float, thus preventing excess volume build-up.
The effectiveness of recycling of the two spent floats was eval-
uated and compared. The spent liquor was added as both the
pickling float and the supplement water at the later stage of tan-
ning, completely replacing fresh water The dosage of chrome tan-
ning agent was 5.0% when the other operating parameters were the
same as that of the first corresponding tanning process, respec-
tively. The results are shown in Table 3.
Table 3 indicates that the tanning process and leather quality are
not apparently negatively affected by the recycling of the spent
float from the novel tanning process, the residual Cr concentrations
in the recycling spent floats are kept stable at a rather low level of
about 200 mg/L, the shrinkage temperatures (Ts) of the wet-blue
are also kept stable at 110
C around and Cr contents in leathers
are also stable at about 2.9% in ten cycles; the total Cr discharge is
reduced by 84.2%. However, in the conventional process, the re-
sidual Cr concentration in the wastewater increases whilst the Cr
content of the wet-blue goes down with the recycling times,
especially after three cycles; comparing the seventh cycle with the
first one, the residual Cr concentration increases 60% and the Cr
content of leather decreases 14%. What’s the worse, the Ts of the
wet-blue are reduced about 2e4
C, the color of the wet-blue
leathers and the comprehensively organoleptic properties of the
final leather, including softness, fullness, grain smoothness, and
280 C. Zhang et al. / Journal of Cleaner Production 154 (2017) 276e283

Table 1
Tracing Cr discharge in whole leather wet-end processing a.

Operations Conventional (mg$L1) Novel (mg$L1) Decrease rate (%)

chrome tanning 1172.0 ± 60.8 107.7 ± 10.4 90.8

samming 398.7 ± 25.9 38.7 ± 8.4 90.3
Wetting 13.1 ± 1.2 9.3 ± 1.1 29.0
Chrome retanning 433.5 ± 28.2 167.3 ± 12.7 61.4
Neutralizing 14.1 ± 1.1 6.7 ± 1.3 52.5
Washing 7.0 ± 1.2 4.1 ± 1.1 41.4
Organic retanning/Filling 18.8 ± 1.5 10.8 ± 1.3 42.6
Washing 10.5 ± 1.2 6.5 ± 1.5 38.1
Dyeing/Fatliquoring 24.5 ± 2.3 21.3 ± 2.5 13.1
b
The input and output of the Cr in whole process (kg/t salted-wet hide)
Total Cr offer 14.411 11.205 22.2
Total Cr discharge 2.930 ± 0.187 0.362 ± 0.026 87.6
Total Cr utilization ratio (%) 79.9 96.7 e
a
The experiment was repeated three times and the values reported are average of three values.
b
1.0t salted-wet hide was changed into 1.1t limed hide and 0.262t shaved grain chrome-tanned leather, and the samming water amount is 200 kg/t.

Table 2
Physical properties of Crust leathers.

Samples Ts of wet-blue (
C) Tear strength (N/mm) Tensile strength (N/mm2) Elongation at break (%) Bursting strength (N/mm)

Conventional 124.5 ± 2.4 15.4 ± 1.3 8.6 ± 1.2 32.4 ± 1.6 117.8 ± 1.3
Novel 125.1 ± 1.7 17.1 ± 1.9 8.7 ± 0.5 33.8 ± 1.3 122.3 ± 2.3

Table 3
Comparison of recycling spent chrome tanning floats from novel and conventional tanning a.

Process Recycling times Appearance of wet blue (b) Ts of Wet-blue (
C) Cr in wastewater (mg$L1) Cr in wet blue leather (%) Organoleptic properties c

Novel 1 blue (1.0) 109.5 ± 2.1 236.7 ± 12.3 2.89 ± 0.05 8.0
2 blue (1.0) 111.1 ± 1.0 219.6 ± 22.5 2.93 ± 0.08 8.0
3 blue (1.0) 112.5 ± 1.6 168.4 ± 12.2 2.86 ± 0.10 8.0
4 blue (1.0) 110.2 ± 1.8 237.2 ± 11.7 2.93 ± 0.05 8.0
5 blue (1.0) 111.6 ± 2.0 175.4 ± 18.1 3.04 ± 0.03 8.0
6 blue (1.0) 112.0 ± 2.0 247.0 ± 15.7 2.88 ± 0.09 8.0
10 blue (1.0) 112.4 ± 1.6 206.7 ± 16.0 2.89 ± 0.02 8.0
Conventional 1 light blue (0.5) 112.0 ± 1.1 1257.8 ± 77.5 2.71 ± 0.06 7.5
2 light blue (0.5) 109.4 ± 1.6 1310.8 ± 72.0 2.66 ± 0.04 7.5
3 light blue (0.5) 110.9 ± 1.4 1283.5 ± 81.2 2.61 ± 0.11 7.0
4 greenish blue (3.0) 106.3 ± 1.9 1384.5 ± 91.6 2.48 ± 0.04 6.5
5 dusty blue (4.0) 108.2 ± 1.3 1513.7 ± 99.3 2.52 ± 0.08 6.5
6 blue green (4.5) 107.9 ± 2.0 1758.3 ± 87.3 2.36 ± 0.06 6.3
7 blue green (4.5) 106.2 ± 1.9 2013.5 ± 97.7 2.33 ± 0.11 6.3

Conventional (recycling 3 times) Novel (recycling 10 times) Decrease rate (%)

The input and output of the Cr in whole process (kg/t salted-wet hide)
Total Cr offering 12.007 11.205 6.7
Total Cr discharge 1.057 ± 0.062 0.167 ± 0.013 84.2
Total Cr utilization ratio (%) 91.2 98.6 e
a
The experiment was repeated three times and the values reported are average of three values.
b
“0” means the color of the wet blue leather looks the same as the one from conventional process without wastewater recycling; “5.0” means the color of the wet blue
leather significantly differs from the one from conventional process without wastewater recycling.
c
“8.0”means the leather quality is nice and without obviously negative effects; “5”means that the leather quality is obviously negative influenced and cannot be accepted.

tightness, are adversely influenced. The negative impacts are
aggravated after the third recycling of conventional chrome tanning
wastewater, which can be ascribed to that the accumulation of Cl,
masking agents (sodium formate) and other organic components to
a rather high concentration will weaken the affinity of chromium
species to collagen and change the color of chrome complexes (Rao
et al., 1997; Cranston et al., 1997).
It can be concluded that recycling of the chrome tanning waste-
water from the novel tanning process has significant advantages over
the conventional process in chrome combination, leather quality and
recycling cycles etc. Accordingly, it can be anticipated the integration
of the novel high-exhaustion chrome tanning and recycling of the
spent liquor technologies can achieve the closed-circuit circulating of
spent tanning float with zero chrome discharge in chrome tanning
stage for a quite long period, at least 10 times.
3.3. Recovery/removal of chromium from the spent liquors
In order to eliminate the chrome from wastewater to a greatest
possible extent, all chrome-containing spent floats from post-
tanning operations, together with the tanning wastewater after
recycled for several times, have to be treated to precipitate chrome.
Given the presence of organic substances in spent floats emanating
from post tanning, the chrome sediment cannot be reused due to
containing numerous impurities, and must be safely disposed of or
deposited in special landfill sites.
For a long time, as mentioned before, many technologies have
been developed focusing on removing the ionic chromium from
spent floats, and alkali precipitation is one of the effective and
practical ways. The base used to precipitate the chrome can vary.
When recovering chrome for reuse from high concentrations
 C. Zhang et al. / Journal of Cleaner Production 154 (2017) 276e283 281

chrome-containing floats, sodium hydroxide or sodium carbonate

is often selected in order to reduce impurities and the possibly
negative impact on following redissolving and tanning. (Kilic et al.,
2011) Calcium hydroxide and MgO are most frequently used to
achieve better full chrome precipitation from post-tanning liquors
without considering of reuse.
Therefore, the effects of removing chrome in chromium-
containing wastewater from different processes based on the
above two chrome tanning methods by means of NaOH precipita-
tion were investigated firstly, and the results are shown in Fig. 3.
Fig. 3 illustrates that, except the wastewater from filling/organic
retanning and dyeing/fatliquoring, the optimum condition for
precipitation is pH 8.0e10.0, in which the chrome concentration in
the supernatant is near 1.0 mg/L. When the pH value exceeds 10.0,
the concentrations of the soluble chromium increase again, because
chromium hydroxide redissolves at a higher pH.
What’s more, it is found that the efficiency of recovering chro-
mium from wastewater of filling/organic retanning and dyeing/ Fig. 4. The concentration of the soluble Cr changes with the dosage of MgO.
fatiliquoring with NaOH is lower than that of other processing
floats, and it is difficultly to reduce the residual Cr concentration of possible. As shown in the Fig. 1, the chrome in wastewater 2,
these two kinds of wastewater to lower than 2.0 mg/L, especially comprising of the effluents from chrome tanning after recycled,
fatliquoring float. As we known, organic syntans and fatliquors samming, wetting and chrome retanning, is precipitate Cr with
contained typically anionic sulfonic and carboxyl groups can co- NaOH, and the chrome in wastewater 3, including the wastewaters
ordinate with Cr(III) ions resulting in a competition with collagen from neutralizing, filling/organic retanning and dyeing/fatliquor-
carboxyl groups, which make more Cr release from leather into ing, is removed with MgO.
float (see Table 1) and difficult to precipitate Cr through increasing
basicity (Remoudaki et al., 2003). 3.4. Environmental benefits
MgO, which has better ability to remove the chromium from the
spent tanning liquor, (Guo et al., 2006) was chosen to treat the The main objective of the study is to reduce chromium pollution
wastewater of filling/organic retanning and dyeing/fatiliquoring from both the origin and end-of-pipe treatment of leather pro-
further. And the results are shown in Fig. 4. cessing. The comprehensive efficiency of integrated technology on
Fig. 4 shows that with increasing the dosage of MgO, until pH reducing chrome emission is summarized in Table 4.
reaches to over 10.0, the residual chrome concentration begins Table 4 indicates that, the total volume of the Cr containing
dramatically decreasing. Actually, a slurry of MgO is formed with wastewater, the total residual Cr in spent floats and the total Cr-
increasing dosage, and the undissolved/solid MgO can destroy the containing sludge is decreased by 19.5%, 84.2% and 28.1%, respec-
stability of the colloidal and emulsion particles of large molecular tively, which are attributed to the high exhaustion and fixation of
retanning agents and fatliquors through the surface adsorptive chrome and the significant increase of recycling cycle of the spent
force (Pasti et al., 2015; Mohr et al., 2016), thus to form co- main tanning liquor in the novel integrated technology. The effi-
precipitation of chrome with MgO. After precipitation with MgO, ciency on reducing Cr-Containing sludge amount comes mainly
finally, the residual Cr concentrations of all the post-tanning from precipitating Cr in wastewater 2 with NaOH (reducing 77.4%).
wastewater can arrive at a quite low level of lower than 1.5 mg/L, Although residual Cr concentration in wastewaters of filling/
which can meet with the strict limit of total chrome discharge in organic retanning and dyeing/fatliquoring is quite low, the required
effluent for discharging into sewage systems as per the latest amount of added MgO is fairly large, 1.0e1.5 g/L, to remove the Cr to
“Discharge Standard of Water Pollutants for Leather and Fur Mak- lower than 1.5 mg/L. The amount of this part of Cr containing sludge
ing Industry” of China (GB30486-2013). is still relatively large. Thus it needs to find a more high efficient
According to the above results, the Cr-containing wastewaters method to remove Cr and reduce sludge generation, because Cr-
are classified treated in order to efficiently precipitate Cr and containing sludge is regarded as a hazardous waste and must be
decrease the output of chrome-containing sludge as much as safely disposed of by qualified professional plants, and the cost is a

Fig. 3. The concentration of the soluble Cr changes with pH (NaOH).

282 C. Zhang et al. / Journal of Cleaner Production 154 (2017) 276e283

Table 4
Efficiency of the integrated technology on reducing chrome emission a.

Operations Conventional Novel Decrease rate (%)

Volume of Cr-containing Wastewater (L/t salted-wet hide) (L/t salted-wet hide)

wastewater 2 1798 ± 123 1448 ± 132 19.5
wastewater 3 2489 ± 149 2489 ± 89 0.0
Total volume 4287 ± 105 3937 ± 97 8.2
b
Amount of Cr-containing Sludge (kg/t salted-wet hide) (kg/t salted-wet hide)
Sludge from wastewater 2 c 2.364 ± 0.191 0.535 ± 0.044 77.4
Sludge from wastewater 3 d 4.237 ± 0.261 4.212 ± 0.236 0.6
Total Cr containing sludge 6.601 ± 0.323 4.747 ± 0.235 28.1

Amount of Cr Discharge (g/t salted-wet hide) (g/t salted-wet hide)

Cr discharge in sludge 1.052 ± 0.062 0.162 ± 0.013 84.6
Cr discharge in wastewater (4.768 ± 0.338)  103 (4.604 ± 0.284)  103 3.4
Total Cr discharge 1.057 ± 0.062 0.167 ± 0.013 84.2
a
The experiment was repeated three times and the values reported are average of three values.
b
Dry sludge.
c
Precipitating Cr with NaOH at pH 9.0e10.0.
d
Precipitating Cr with the excessive dosage of MgO, 1.5 g/L.

financial burden for a tannery (50-80US dollars/ton in China). After
the classified precipitating, the total Cr discharging amount with
wastewater is further decreased to 4.604 g/t salted-wet hide, and
the Cr concentration of the comprehensive sewage will be at the
level of 0.354 mg/L when the treated Cr-containing wastewater is
pumped to the sewage system and mixed with the other wasters
from beamhouse processes, and the total amount of comprehensive
sewage is about 13,000 kg/t salt-wet hide (Rivela et al., 2004). The
novel integrated technology has exhibited remarkable advantages
in environmental and economic benefits.
the end-of-pipe water is at the level of 0.354 mg/L and the total Cr
containing sludge is decreased by 28.1%.
The results obtained from this life tracking study highlight the
opportunities for improving chrome tanning leather processing,
and serve as the basis for improving chromium management op-
tions, from its emission source to end-of-pipe treatments. The in-
formation can be used to make further environmental
improvements in leather industry.
Acknowledgements

4. Conclusions This work was financially supported by the National Key Tech-
nology R&D Programs of the Ministry of Science and Technology
Tracing the life cycle of Cr in leather processing, near zero (2014BAE02B01) and College Students Innovation& Entrepreneur
emission of chromium in leather processing can be achieved step Training Plan of Sichuan University, China (201510610267).
by step through integrating the salt-free and high-exhaustion
chrome tanning process, modified chrome retanning, direct recy-
cling of tanning wastewater and highly efficient removal of Cr from Appendices
wastewater. The total Cr utilization is raise to 98.6%. The total Cr
discharge is decreased to 4.604 g/t salted-wet hide, while the Cr in

Table A
Post-tanning Processes for Shoe Upper Leather
a
Operations Chemicals Dosages (%) Controlling constants Comments

Neutralizing Water 150 40
C

Neutralizing Syntan 1.5 30min
NaHCO3 1 90min, pH5.5
Draining Cr sewage 150%
Washing Water 200 30min Cr sewage 200%
Organic retanning/Filling Water 150 40
C
Synthetical Fatliquor 2 30min Dilution with 3 times hot water
Polyacrylate Retanning Agents 9 40min Dilution with 3 times hot water
Phenolic Resin Syntan 3 Dilution with 3 times hot water
Polysulfone Syntan 3 40min
Polynaphthalene Sulphonate 2
Melamine Resin 3
Protein Filling 2
Vegetable Tannin 2 90min
HCOOH 0.5 30min, pH4.5 Dilution with 10 times water
Draining Cr sewage 200%
Washing Water 200 10min Cr sewage 200%
Fatliquoring/Dyeing Water 150 55
C
þ Dyestuffs 3 30min Dilution with 3 times hot water
þ Fatliquor Compound 10 90min
þ HCOOH 1.5 pH3.6 Dilution with 10 times water
Draining Cr sewage 200%
Vacuum Drying
Hanging Drying
Stacking
a
Based on the weight of the shaved chrome tanned leather.
 C. Zhang et al. / Journal of Cleaner Production 154 (2017) 276e283 283

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