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Dechroming of Chromium-containing Leather Waste with Low Hydrolysis

Degree of Collagen

Article  in  Journal- Society of Leather Technologists and Chemists · June 2015

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 Volume 99 Page 129

Dechroming of Chromium-containing Leather Waste

with Low Hydrolysis Degree of Collagen
WEI DING1, XUEPIN LIAO1, WENHUA ZHANG2 and BI SHI1, 2*
1
The Key Laboratory of Leather Chemistry and Engineering of Ministry of Education,
Sichuan University, Chengdu 610065, P. R. China
2
National Engineering Laboratory for Clean Technology of Leather Manufacture,
Sichuan University, Chengdu 610065, P. R. China

Abstract
Dechroming is essential for utilization of chromium-containing leather wastes. Strong hydrolysis
conditions favour breaking of the Cr and collagen linkage, but lead to a high degree of hydrolysis of
the collagen so that the separation of chromium from the gelatinous hydrolysates becomes difficult.
In this research, a mild acid-alkali alternate treatment of the waste with hydrolysis assistants was
investigated, so as to develop a technology that has high dechroming level and low hydrolysis degree
of collagen. A satisfactory dechroming method with four steps was finally obtained and the reaction
conditions for each step were optimized as follows. Step 1 – waste in the solution with 2g/L NaOH and
40g/L urea (hydrolysis assistant) was stirred for 0.5 hours at 40°C. Step 2 – waste in 50g/L sulfuric acid
solution was stirred for 1 hour at 40°C. Step 3 – waste in 40 g/L Ca(OH)2 suspension was stirred for
2 hour at 30°C. Step 4 – waste in 50g/L sulfuric acid solution was stirred for 1 hour at 30°C. With this
method, total extent of the dechroming of the waste was higher than 97% while the hydrolysis degree
of collagen was lower than 10%.

摘要：研究了一种含铬废皮渣脱铬方法，它是在温和的条件以及水解助剂的辅助作用下，用酸和碱
交替处理废皮渣。该法通过4步处理，实现了含铬废皮渣脱铬率高且胶原水解率低的目的。第一步，含
铬废皮渣在NaOH（2g/L）和尿素（水解助剂，40g/L）的溶液中于40°C下搅拌0.5h；第二步，皮渣在硫
酸溶液（50g/L）中于40°C下搅拌1h；第三步，皮渣在氢氧化钙悬浊液（40
g/L）中于30°C下搅拌2h；第四步，皮渣在硫酸溶液（50g/L）中于30°C下搅拌1h。采用该四步法，含铬
废皮渣最终的脱铬率高于97%，且胶原水解率低于10%。

1. INTRODUCTION chromium from the thick hydrolysates, which largely

The leather industry inevitably generates a large
amount of chromium-containing leather wastes, such
as trimmings and shavings of chrome tanned leather.1
These wastes are rarely utilized directly due to their
high content of chromium. Most of these wastes are
still in packaged, landfilled, and burned.2 However, the
environmental concerns of these approaches are
escalating. Landfill cost is increasing and incineration
in air atmosphere results in other forms of pollutants
(gas and ash discharges).3-6 Therefore, it is essential to
develop feasible ways to convert these wastes into
more valuable products. During the past decades,
some methods of reusing these wastes have been
proposed. Acid hydrolysis, alkali hydrolysis and
enzymatic hydrolysis have been widely used for
separation and recovery of chrome and collagen
material from the wastes.7-13 Sulfuric acid hydrolysis of
the wastes gives a low level of dechroming at low
temperature (61.28% at 40°C),14 or leads to severe
hydrolysis of collagen at high temperature (70°C) so
that the separation of chromium from the thick
hydrolysates is difficult.15 Therefore, this kind of
hydrolysate was usually used as chromium-containing
retanning agent. Dechroming of the leather wastes by
organic acids or enzymes was also studied.16-19
However, these methods still lead to severe hydrolysis
of the collagen and thus difficulty in separation of
* Corresponding author: E-mail: sibitannin@vip.163.com
restricts the value-added applications of the
hydrolysates. Calcium hydroxide or sodium hydroxide
+ calcium oxide are often used to dechrome the wastes
at 80°C~100°C.20 These methods only achieve a
protein recovery of around 70%, while producing a
large amount of chrome cake. The chrome cake, as a
hazardous solid waste, is difficult to utilize. In addition,
alternate treatments by acid and alkali were also
employed by some researchers.21 This method can
give a collagen product with chromium content around
100mg/kg, however, a part of the Cr(III) is oxidized to
Cr(VI) during strong alkali treatment in this method,
which would be hazardous to operators and cause
secondary pollution in the environment.
Generally, in the conventional methods as above,
there is a contradiction between Cr-collagen breaking
and separability of Cr from hydrolysates. The strong
hydrolysis conditions favour the breaking of Cr-
collagen linkage, but produce a high hydrolysis degree
of the collagen that restricts the separation of Cr from
hydrolysates.
The aim of present work is to hydrolyze the
chromium-containing leather wastes in conditions that
not only break the linkage between Cr and collagen
effectively, but also keep a low hydrolysis degree of
collagen so that the Cr can be easily separated from
the hydrolysates. In this way, chromium could be
recovered as a possible raw material for making a

129
chrome tanning agent, while the collagen hydrolysates
with low Cr content would be used to prepare more
valuable industrial products. In the present work, with
this aim in mind, relatively weak acid and alkali
alternate treatments assisted by hydrolysis assistants
were investigated.
in both the filtrate and leather waste. The determination
of hydroxyproline content was carried out according to
the method of ISO 3496:1994.22 The hydrolysis degree
of collagen was calculated by the Equation (2) (below).
3. RESULTS AND DISCUSSION

2. MATERIALS AND METHODS 3.1 Effect of hydrolysis assistant on extent of

dechroming
2.1 Materials
Leather shavings were collected from a local tannery.
Their moisture and Cr2O3 contents were 19.84% and

Dechroming extent (wt %)

4.71%, respectively. The hydrolysis assistants, including
ammonia water, diethanolamine, methylurea, guanidine
hydrochloride and urea, were analytical grade. Sulfuric
acid, sodium hydroxide, calcium hydroxide and other
chemicals were also all analytical grade.
2.2 Dechroming procedure of the leather waste
The dechroming was carried out in 4 steps.
Step 1 – alkali pretreatment of the waste assisted by
Hydrolysis assistant
hydrolysis assistant. 5.0g leather waste was suspended
in 100mL distilled water, and then 0.2g sodium Figure 1. Effect of hydrolysis assistant on dechroming
hydroxide and a certain amount of hydrolysis assistant extent in first two steps.
were added. The mixture was stirred for 0.5 hour under
a fixed temperature.
Step 2 – partly dechroming by sulfuric acid. The
pretreated waste was suspended in 100mL distilled
Dechroming extent (wt %)

water, and then a certain amount of sulfuric acid was

added. The mixture was stirred for 1 hour under a fixed
temperature.
Step 3 – further dispersing of collagen fibres. The
sulfuric acid dechromed waste was suspended in
100mL distilled water, and then a certain amount of
calcium hydroxide was added. The mixture was stirred
for 2 hours under a fixed temperature.
Step 4 – further removing of chromium from the
waste. The calcium hydroxide treated waste was again
dechromed by sulfuric acid to remove the remained
chromium. The operation conditions were as the same
as step 2.
At the end of each step, the mixture was filtered and
rinsed. The filtrate was collected for determination of
chromium content. The effects of hydrolysis assistants
on improvement of the dechroming extent were
investigated. The influences of dechroming temperature
and offers of sulfuric acid and calcium hydroxide on the
dechroming extent were also observed. The extent of
dechroming was determined by Equation (1) (below).
2.3 Estimation of the degree of hydrolysis of
collagen
The hydrolysis degree of collagen in the waste was
determined according to the content of hydroxyproline
Concentration of urea (g/L)
Figure 2. Effect of urea concentration on extent of
dechroming in first two steps.
Figure 1 demonstrates the effects of hydrolysis
assistants on dechroming of the waste after the first two
steps, where the concentration of hydrolysis assistant
in the first step was 40g/L and the concentration of
sulfuric acid in second step was 50g/L. The reaction
temperature of both of these two steps was 40°C.
Obviously, all the amino-compounds were able to
increase the extent of dechroming, and urea achieved
a highest extent (65.66%). Therefore, urea was
adopted as the hydrolysis assistant in the following
experiments. The effect of urea concentration on the
total dechroming extent in the first two steps is
presented in Figure 2. It is shown that the dechroming

Chromium content in solution

Dechroming extent (wt %) = x 100% (1)
Chromium content in leather waste

Hydroxyproline content in solution

Hydrolysis degree of collagen (wt%) = x 100% (2)
Hydroxyproline content in leather waste

130
extent increased with increasing urea concentration
and the optimal concentration of urea was 40g/L.
Furthermore, a decrease in dechroming was observed
when the concentration of urea was higher than 40g/L.
Urea and other amino-compounds can break
hydrogen bonds of proteins to denature them. The
structure of proteins after treatment by urea becomes
relatively loose.23-25 In alkaline medium (step 1), this
action of urea can promote the penetration of hydroxyl
anions into the protein molecules and accelerate the
detanning reaction. Moreover, due to the loosened
collagen structure in step 1, sulfuric acid is able to
penetrate into the collagen molecules more easily to
remove chromium from collagen in step 2. In a low
concentration range of urea, the structure of collagen is
better opened up and thus a higher dechroming extent
is obtained. However, collagen might be swollen when
the urea concentration exceeds 40g/L due to over
breaking of collagen hydrogen bonds, which then
restrains the penetration of alkali and acid. As a result,
the dechroming extent is decreased. The lower
dechroming extent apparent with the use of other
hydrolysis assistants is probably due to their weaker
ability in breaking hydrogen bonds of collagen.
3.2 Effect of reaction temperature on dechroming
extent
Each step of the dechroming process was controlled
to a set temperature, as shown in Table I. It was found
that, with the same offers of chemicals as noted in
Table I, the dechroming extent was increased when the
temperature increased from 25°C to 35°C. However,
serious hydrolysis of the waste was observed in steps 3
and 4 when temperature was higher than 35°C. As a
result, the separation of Cr from hydrolysates became
difficult. It is well known that the denaturation
temperature of collagen is around 37°C and that
denatured collagen is easier to hydrolyze. In steps 1 and
2, most of the Cr was removed from the leather waste
at temperatures higher than 35°C, while collagen was
partly denatured by hydrolysis assistant. Therefore, the
waste was easily hydrolyzed by acid and alkali in steps
3 and 4, thus a high hydrolysis degree of collagen was
observed, which is an unfavorable condition for
separation of Cr from hydrolysates. Accordingly, in the
following experiments, 40°C was adopted in steps 1 and
2, and 30°C was adopted in steps 3 and 4.
TABLE I
Effect of reaction temperature on dechroming extent (wt %) a
Temperature Procedure
(°C) Step 1 Step 2 Step 3 Step 4 Total
25 5.05 31.09 0 45.82 81.96
30 5.84 39.65 0 40.10 85.59
35 6.70 49.69 0 32.69 89.08
40 7.97 58.58 Hyd. Hyd. Hyd.
45 8.90 60.55 Hyd. Hyd. Hyd.
Hyd. – Hydrolyzed
a
NaOH and urea concentrations were 2g/L and 40g/L in step 1,
respectively; H2SO4 concentration was 50g/L in step 2 and step
4; Ca(OH)2 concentration was 40g/L in step 3.
3.3 Effect of sulfuric acid concentration on
dechroming extent
The same concentration of sulfuric acid was used in
steps 2 and 4. The effect of sulfuric acid concentration on
dechroming extent in these two steps was summarized
in Table II. It was clearly observed that the total
dechroming extent increased from 61.19% to 99.89% as
sulfuric acid concentration increased from 20g/L to
60g/L. In general, chromium complex particles will
become smaller in acidic condition, and possess a
weaker tanning effect on collagen. On the other hand,
the high concentration of hydrogen cation will suppress
the dissociation of collagen’s carboxyl groups, which
further reduces the interaction of chromium complexes
with collagen. In addition, the introduction of a large
number of sulfate ions will destroy the cross links
between collagen carboxyl and chromium.26 These
should be the reasons why dechroming extent increased
with increasing sulfuric acid concentration in steps 2 and
4. However, it was observed that the hydrolyzation of
waste collagen became serious when sulfuric acid
concentration exceeded 60g/L, which led to difficulty in
filtering the hydrolysates. Consequently, the optimal
concentration of sulfuric acid in steps 2 and 4 was kept
at 50g/L.
TABLE II
Effect of sulfuric acid concentration in step 2 and step 4 on
dechroming extent (wt %) a
H2SO4 conc. Procedure
in step 2 & 4 Step 1 Step 2 Step 3 Step 4 Total
(g/L)
20 7.29 53.32 0 0.58 61.19
30 6.55 55.53 0 1.64 63.72
40 7.94 57.54 0 10.85 76.33
50 6.50 59.16 0 32.18 97.84
60 7.07 59.23 0 33.59 99.89
a
NaOH and urea concentrations were 2g/L and 40g/L in step 1,
respectively; Ca(OH)2 concentration was 40g/L in step 3; step 1
and step 2 were undertaken at 40°C; step 3 and step 4 were
undertaken at 30°C.
3.4 Effect of calcium hydroxide concentration on
extent of dechroming
The influence of calcium hydroxide concentration on
dechroming in step 3 is presented in Table III. It was
found that the waste collagen was seriously degraded
when the concentration of calcium hydroxide was
10g/L. As a result, the partly dechromed waste was
hydrolyzed to a small molecular gelatinous substance
and then it was difficult to separate the chrome from the
collagen hydrolysates.
It is worth to note that the hydrolysis of leather waste
was inhibited at a relatively higher calcium hydroxide
concentration. It has been reported that Ca2+ at a high
concentration exhibits a compression effect on collagen
fibre,27 and thus protects the collagen fibre from
excessive damage. However, this compression effect
at relatively low concentration of Ca2+ is negligible.
Therefore, the waste collagen was easily hydrolyzed
by alkali and acid when a low Ca2+ concentration was
131
employed in step 3. The dechroming extent in step 4 4. CONCLUSIONS
decreased sharply when the calcium hydroxide
By using amino-compounds, like urea, as hydrolysis
concentration in step 3 was increased to 50g/L,
assistants, the extent of dechroming chromium
although no serious hydrolysis of waste collagen was
containing leather wastes was higher than 97% using
observed, this led to a great decrease of the total
the mild acid-alkali alternate treatments of four steps.
dechroming extent. This should be due to the fact that
The high dechroming extent is mainly due to the fact
most of the sulfuric acid was consumed in neutralizing
that collagen in the waste was kept to a low hydrolysis
the calcium hydroxide and the residual sulfuric acid was
degree during dechroming so that Cr was easily
insufficient to fully remove chromium from collagen.
separated from the hydrolysates. The Cr in the waste
Thus, the concentration of calcium hydroxide used
can be fully recovered by this technology, and is quite
should be in the range of 30g/L ~ 40g/L.
suitable for re-use as chrome tanning agent through
simple treatment since only a few organic substances
TABLE III are included in it. On the other hand, the dechromed
Effect of calcium hydroxide concentration in step 3 on collagen that is kept in the fibre state and is seldom
dechroming extent (wt %) a destroyed, would be more suitable for diverse
Conc. of Procedure utilization.
Ca(OH)2 in Step 1 Step 2 Step 3 Step 4 Total
step 3 (g/L)
ACKNOWLEDGEMENTS
10 6.46 55.58 Hyd. Hyd. Hyd.
20 8.22 54.60 0 30.68 93.50 The work was financially supported by the National
30 6.34 57.45 0 32.78 96.57 High-Tech Research and Development Program of
40 6.50 59.16 0 32.18 97.84 China (2011AA06A108) and the Fundamental
50 8.41 53.13 0 3.37 64.91 Research Funds for the Central Universities.
Hyd. – Hydrolyzed (Received September 2014)

in association with
a
NaOH and urea concentrations were 2g/L and 40g/L in step 1,

respectively; sulfuric acid concentration in step 2 and step 4
was 50g/L; step 1 and step 2 were undertaken at 40 °C; step 3
and step 4 were undertaken at 30 °C.
3.5 Hydrolysis degree of collagen
Based on the results above, the optimal conditions for
dechroming leather waste are summarized in Table IV.
TABLE IV
The optimal conditions for dechroming of leather waste
Step 1 NaOH 2g/L, urea 40g/L, 40°C, 0.5h
Step 2 Sulfuric acid 50g/L, 40°C, 1h
Step 3 Ca(OH)2 40g/L, 30°C, 2h
Step 4 Sulfuric acid 50g/L, 30°C, 1h
The hydrolysis degree of waste collagen under the
optimal conditions was estimated according to the
content of hydroxyproline in filtrate and leather waste.
As we know, hydroxyproline, an imino acid, is unique to
collagen. Compared with other mammalian proteins,
collagen has a high content of hydroxyproline (up to
14% of dry collagen weight). Therefore, the amount of
hydroxyproline has been used historically to estimate
collagen levels.28-29 Our experiments showed that the
standard curve for determining hydroxyproline content
can be expressed as y=0.10441 + 0.02005, R2=0.9963.
The hydroxyproline contents in the waste and in the
hydrolysate filtrates were determined on the basis of
the standard curve. Under the optimal experimental
conditions, the dechroming extent exceeded 97% and
the hydroxyproline contents in the filtrate and in the
leather waste were 23.34mg and 317.47mg,
respectively. It can be calculated, according to Eq. (2)
that the hydrolyzation degree of collagen under the
optimal conditions was 7.35%.
China Leather
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