A Rationalized Leather Process for Wet-end: Pre-tanning－Integrated

Post-tanning System

Tao Zhang1, Wuyong Chen1,* , Jie Tian1,Guoshu Luo2, Fusheng Ling2

1
National Engineering Laboratory for Clean Technology of Leather Manufacture, Sichuan University,
Chengdu 610065, P.R.China
2
Guangdong Shengfang Chemical Co.,Ltd, Guangdong 529162, P.R.China

Abstract: The conventional leather process is related to huge consumption of water, chemicals and time. To
alleviate these problems, a new process for tanning and post-tanning was developed. In this process, bated pelt was
directly pre-tanned with a melamine resin. Then, the pre-tanned pelts were split and shaved. As for post-tanning,
several operations including, chroming, retanning, dying and fatliquoring were effectively integrated in the same
one bath: a moderate quantity of dyes and fatliquors were employed firstly; then a chrome agent was added into the
same bath; when the chromium absorbed almost completely, the bath pH was raised and the retanning and filling
materials were added; at last, some fatliquors were employed to obtain the high oil content leather. Comprehensive
analysis of leather properties, environmental and economic benefits were carried out for the conventional and the
experimental process. The results indicate that the functional properties of the experimental leathers had no
significant difference to the leathers from conventional process, but there is a considerable reduction in cost of
leather production in the modified process. Furthermore, the new process results in remarkable reduction in
pollution parameters such as BOD load, COD load, TSS and chroma by 55.04%, 58.04%, 39.42%, and 90%,
respectively. Also, the consumptions for water and chemicals were reduced by 42.73% and 40.29%, respectively.
Key words: leather-making; clean technology; tanning; post-tanning; environmental benefits

1 Introduction
Conventional chroming process generally involves in pickling, chroming and basifying, and there
are several defects existing in the process[1,2]: ⑴8-10% salt and 1.0-1.2% sulfuric acid were used in
pickling, which results in higher contents of chlorides, sulfates and chemical oxygen demand (COD) in
the effluent. ⑵The uptake of chromium in conventional chroming is lower (70-80％), a considerable
amount of chromium left in the effluent may result in environmental problems[3]. ⑶ A great deal of
chrome containing solid wastes such as splittings and shavings are produced, which is certainly difficult
to be degraded and harmful on the environment if discharged directly.
Conventional post-tanning process involves in a variety of operations comprising rehydration,
rechroming, basification, neutralization, washing, retanning, filling, washing, dying, fatliquoring, fixing
and washing. Post-tanning processes hold a pH range of 3.8-6.5. A large amount of water and chemicals
are consumed in post-tanning processes. Usually, only about 60-80% chemical is absorbed in the
post-tanning. The residual chemicals are drained with wastewater, which cause seriously environmental
pollution. According to information available[4], the post-tanning account for about 50％ of COD of
tannery effluent. Additionally, the water consumption should not be belittled because of so many
washings existing in the conventional process, the post-tanning occupies about 40-45％ water usage in
leather manufacture[5].

*
Corresponding author. Phone: +86-(0)28-85404462. E-mail: [email protected]
 The conventional tanning and post-tanning process holds a large amount of water usage because of
numerous operations followed with several washings. So, a question is posed: will the water consumption
be reduced significantly if several operations are integrated in the same bath? Also, a conventional
process subjects the skin to wider pH variations, which results in a net increase in TSS, COD, chlorides
and sulfates in the effluent and also impairing the surface properties of the skin matrix[6]. So, another
question is: if the variations of pH in the process are limited, will the pollution loads in effluent be
lowered, and then will the physical strengths of final leather be improved?
Due to the considerations on the questions mentioned above, recently, the rationalization of tanning
and post-tanning processes was studied and a optimized leather process was developed, that is the
Pre-tanning－Integrated Post-tanning System(Fig.1). In this work, the entire process has been changed to
achieve water and chemicals saving and emission reduction as well as better quality of leather production.
Spent liquors from all the unit operation were mixed to analyze for pollutants. Then the accounts of
chemicals and water consumption have been carried out for both the conventional and the experimental
processes. Also, the physical and chemical characteristics as well as hand and visual evaluation have been
carried out for leathers with the both processes. At last, the environmental and economic auditing has also
been conducted for the experimental process.

Conventional Pickling Chroming Rechroming

Bated
Dying Retanning Neutralization Spliting
skins

Experimental Pretanning Splitting Integrated post-tanning

Fig. 1 Flow chart for conventional and experimental processes

2 Experimental
2.1 Materials
Wet salted pigskins were treated from soaking to bating as usual. The bated pelts were cut along the
backbone line, left parts for the conventional process, and right parts for the experimental ones.
The pre-tanning agent was a kind of low-polymerized melamine resin (effective constituent is about
40-50%). The chemicals employed in the experiment are of commercial grade, the chemicals used for
analytical technique are of reagent grade. Several main chemicals used for control and experimental
processes are described as follow: the Basyntan AN (Retanning agent), Relugan GTW (Glutaraldehyde)
and Lipoderm A1 (Fatliquor) are provided by BASF Ltd; the fatliquors such as PELASTOL 94S and
PROVOL BA are provided by Zschimmer&Schwarz Ltd; the retanning agent ART-1 come from the
Chinese Academic of Science (Chengdu); the pickle-less chrome agent C-2000 come from Xinhui Ltd
(Guangdong).
2.2 Experimental and Conventional Leather Process
Experimental and conventional processes are provided as Tab.1 and Tab.2 respectively.
As Tab. 1 showing, bated pelts were directly pre-tanned with melamine resin. The bated pelts were
of high pH value (6.8-7.0) and most active groups of collage were exposed. Hence, the reactivity of
pre-tannage could be fully reflected. Then, the pre-tanned pelts were split and shaved. Since there was no
chromium existed in the splittings and shavings, the wastes could be treated and reused more easily.
Furthermore, a moderate quantity of dyes and fatliquors were employed. Negative charge is dominant in
the skin because of no chromium in pre-processing, therefore the electronegative dyes and fatliquors may
penetrate smoothly into the collage fibers. Also, a pickle-less chrome agent was added into the same bath,
neither chromium deposition nor course grain was caused. Meanwhile, the pH value of bath and inner
skins was decreased to 3.2-3.6 with the adding of the tanning agent[7], this pH condition helped the
syntans, dyestuffs and fatliquors permeated into collage matrix to aggregate and combine additionally.
When chromium absorbed almost completely, the bath pH was increased by adding sodium bicarbonate,
then the retanning and filling materials were added in the bath. At last, some fatliquors could be employed
if high oil content leathers were needed.

Tab. 1 Experimental process (E)

Process + % Chemicals T(℃) Time(min) Remarks
Pre-tanning 100 Water 40 The final pH should be 6.1-6.3
+ 10 Malamine resin 6×60 O/N, run for 0.5 hour
The leathers were piled for 24 h, then split and shaved to a uniform thickness (1.1-1.2mm), and weighted.
Rehydration 200 Water 25 120
Integrated 80 Water 25
Post-tanning + 1.2 Acid black dye NBK
+ 1.5 Aluminium chloride 40 40
+ 2.0 Basyntan AN 30
+ 2.0 Lipoderm A1 60
+ 6.0 C-2000 120
+ 1.0 Relugan GTW 60
+ 2.0 ART-1 60
+ 1.5 Sodium bicarbonate 30 pH5.0-5.5
100 Water
+ 2.0 Lipoderm A1 58 60
3.0 PELASTOL 94S
3.0 PROVOL BA
+ 0.5 Formic acid 20 pH4.0
Washing 200 Water 25 10

2.3 Appearance and Hand Evaluation of Leathers

Crust leathers from the conventional as well as the experimental process were assessed for softness,
fullness, grain smoothness, surface color and general appearance by hand and visual examination.
2.4 Physical Testing of Leathers
Samples for various physical tests from the experimental and the conventional crust leathers were
obtained as IUP method[8]. Physical properties such as tensile strength, tear strength, grain crack strength
and rubbing fastness were examined as the standard procedure[9].
2.5 Chromium and Oil Content and Shrinkage Temperature of Crust Leathers
Samples from the experimental and control leathers were split into three average layers, respectively.
The chromium content of each layer was estimated as potassium chlorate standard procedure[9], and the
oil content as methylene dichloride extraction standard procedure[9]. Samples were initially analyzed for
moisture content[10] and the final results were expressed on dry weight basis of leather. The shrinkage
temperature of the leather was measured using the Hg Shrinkage Temperature Tester. The uniformity of
chromium and oil distribution in the leathers was calculated as following formula:
2 × Cr2 O 3 in Middle layer
Uniformity(%)= × 100%
Cr2 O 3 in Grain layer + Cr2 O 3 in Flesh layer

Tab. 2 Conventional process (C) for control

Process + % Chemicals T(℃) Time(min) Remarks
Pickling 100 Water 22 pH 2.5-3.0.
+ 8.0 Sodium chloride 5 O/N, run for 0.5 hour
+ 0.5 Formic acid 20
+ 1.2 Sulphuric acid 120
Chrome 50 Water 38 2×60 50% pickling bath was
tanning + 0.5 Cationic oil 20 drained.
+ 8.0 Basic chromium sulphate
1.0 Sodium acetate 120
Basification 1.2 Sodium bicarbonate pH3.8-4.0
The leathers were piled for 24 h, then split and shaved to a uniform thickness (1.1-1.2mm), and weighted.
Rehydration + 200 Water 25 120
Rechroming 150 Water 38
+ 3.0 Basic chromium sulphate 120
+ 3.0 Relugan GTW 60
Washing Water 5 Twice
Neutralization 150 Water 34
+ 1.0 Ammonium bicarbonate 60
1.0 Sodium acetate
+ 3.0 ART-1 60
3.0 Basyntan AN pH5.5-5.8
Dyeing and 200 Water 55
Fatliquoring + 3.0 Acid black dye NBK 60
+ 4.0 Lipoderm A1 60
3.0 PELLASTOL 94S
4.0 PROVOL BA
Fixing 0.5 Formic acid 25 20 pH4.0
Washing 200 Water 25 10

2.6 Analysis of Chromium in Spent Liquor

Chromium liquor collected from the conventional tanning was analyzed for chromium content as the
H2O2 standard procedure[11]. The liquor was pre-treated by 1mol/L NaOH and 3% H2O2 to decrease the
influence of the residual dyestuff and retanning agent, then, analyzed as the H2O2 standard procedure [12].
2.7 Analysis of Composite Waste Liquors
 Composite liquors from the conventional and experimental processes were collected from all unit
processes except from soaking to bating. The pollution indicators such as COD, BOD, TSS and Chroma
were examined after 15 hours as the standard procedure [11]. From this, COD load and BOD load were
calculated, the calculation formula is provided as follow:

Test value (mg/L) × Volume of effluent (L)

Pollution load (mg/kg raw skins) =
Weight of raw skins(kg)
3 Results and discussion
3.1 The pH Variations
The pH behavior of unit process in the experimental and the conventional leather production is
presented in Fig.2. It is evident that the experimental process possess a narrow pH range and small
variation frequency of pH compared to the conventional process, this is due to the presence of several
acid-basification reaction in the traditional processing[6]. By contrast, the new process holds a narrow pH
variation between two successive processing which may be helpful for the properties of final leathers.
8
7
6
5
pH

4
3
C
2
E
1
0
1 2 3 4 5 6 7 8 9
operations

Fig. 2 The pH variations of unit operations in the conventionalc and the experimental processe
c: 1 Bating, 2 Pickling, 3 Chroming, 4 Basification, 5 Rechroming, 6 Neutralization, 7 Dying, 8 Fatliquoring,
9 Fixing; e: 1 Bating, 2 Pretanning, 3 Dying( Fixing), 4 Chroming, 5 Neutralization, 6 Fatliquoring, 7 Acidification.

3.2 Physical Characteristics and Hand Evaluation

Tab. 3 Several properties of crust leathers from the two processes
Ts(℃) Changes of Thickness (%) Changes of Area (%)
Process
Pretanned skin Crust leather Belly Back and Butt
C - 114.3 17.63 17.04 -6.75
E 87.5 107.5 42.26 26.34 -9.01

The Ts of pre-tanned pelts are increased evidently in the new process and meets the requirements of
the hydrothermal stability for splitting (Tab.3). In addition, the thicknesses of experimental sample are
increased much more than the controls, especially in the belly area, this is helpful for the evenness of
leathers and the area of splits.
The average ratings of visual and hand performance for the leathers were evaluated by three
experienced tanners (Fig.3). The experimental leathers exhibit better fullness compared to the contrasts
due to the better filling of the melamine resin. Others properties such as softness, grain smoothness, and
surface color are comparable with that of the conventional process, or even better. The general
appearance of the experimental leathers was similar to the control.
 10

8
C
E
7

5
softness fullness grain surface general
color appearance

Fig. 3 Properties of the leathers

Tab.4 shows the strength properties of the leathers, such as tensile, tear and grain crack strength. It
can be seen that the experimental leathers possessed varying degrees improvement in tensile, tear and
grain crack strength by 4.89%, 19.07% and 39.39%, respectively. The reason may be that pickling was
avoided in the modified chroming and the collagen was not damaged by salts and strong acids, so little
collagen was hydrolyzed in the experimental process compared to the control.
Tab. 4 Physical strength data of conventional and experimental leathers
Tear strength Tensile strength Elongation at Rubbing fastness Grain crack
2 2
Sample (N/mm ) (N/mm ) break（10N）% strength
Parallel Vertical Parallel Vertical Parallel Vertical Dry Wet (kgF/cm2)
C 68.61 55.32 28.16 18.09 64.35 82.34 4.5 4.5 29.40
E 74.28 55.72 28.43 26.63 70.16 75.34 4.5 4 40.98

3.3 Chemical Characteristics

Tab.5 shows the uptake of chromium was improved remarkably in the experimental compared to the
control. The chrome complex bound not only with collagen, but also with the melamine resin that had
been linked to collagen through one end, which caused many cross-links between chromium and collagen.
The shrinkage temperature of the leathers from the modified process was higher than 100℃, which meets
the requirements for shoe upper. This indicates that 6% chrome agent offer is sufficient for leather in the
new process.
Tab. 5 Comparison of leathers from the conventional and the experimental process
Chromium Uptake of Chromium content
Sample Ts(℃) Moisture content (%)
usage（%） chromium (%) of effluent (g/L)
C 11 114.0 82.48 1.54 18.38
E 6 107.5 96.21 0.15 18.59

Tab. 6 Distribution of chromium and oil content in leathers

Sample Grain Middle Flesh Average Uniformity(%)
C 7.21 5.90 7.11 6.74 58.35
Oil(%)
E 8.20 6.04 7.01 7.08 56.84
C 3.99 3.27 4.37 3.88 78.23
Cr2O3(%)
E 3.74 3.52 4.12 3.79 89.57
 Tab.6 shows that the leather with the new process exhibits a uniform chromium distribution along
the entire cross section. The reason may be that pelts were previously treated by melamine resin, which
increased the porosity of skin matrix, and promoted the permeation of chromium. Also, the leather from
modified process enjoyed higher amount of oil compared to the conventional leather in the middle layer
as well as average level.
3.4 Environmental Benefits
Tab. 7 Analysis of composite effluents
COD BOD Volume of
Process TSS(mg/L) Chroma
Value(mg/L) Load Value(mg/L) Load effluent(L)
C 5643.75 51.21 285 2.58 312 200 33.8
E 5132.05 21.49 278 1.16 189 20 15.6

The composite effluents were collected from all the unit process after bating. The impact of the
composite liquors on environment are evaluated by four pollution parameters such as BOD, COD, TSS
and Chroma, a direct comparison of the observed BOD and COD values may not give proper results.
Hence, theses values have been converted into emission loads, see Tab.7. It can be seen that the modified
process possess an evident reduction in BOD load, COD load, TSS and chroma by 55.40%, 58.04%,
39.42%, and 90%, respectively. Also, the amount of composite liquor is decreased by 53.84%. So the
potential of the new process for reducing water consumption is remarkable, which is important to the
developing of leather industry.
3.5 Economic Benefits
The technical feasibility as well as cost effectiveness is generally required on commercialization of
any newly developed process in the industry. So, the input of the chemicals has been monitored for the
conventional and the experimental process. The observed values have been calculated for processing 1
metric ton of pigskins. The total amount of chemicals consumed in the conventional and the experimental
processes is 489 and 292 kg, respectively. That is to say, the new process possesses a reduction in total
chemical consumption by 41% compared to the control.
For the time-consuming, the new process is 27.6 hours, which is 14.9 hours less than the
conventional process. So, the process is able to improve the production efficiency and lower the energy
consumption in leather manufacture.

4 Conclusions
In this work, a modified process has been developed for clean leather manufacture. The leathers
obtained with the experimental process hold comparable or superior functional properties than that of
leathers from the conventional process. Also, there is a considerable reduction in the cost of leather
production in the modified process. Most importantly, the new process results in remarkable reduction in
pollution parameters such as BOD load, COD load, TSS and Chroma by 55.04%, 58.04%, 39.42%, and
90%, respectively. Also, the consumptions for water and chemicals were reduced by 42.73% and 40.29%,
respectively. This is a significance achievement on current circumstance.

Acknowledgment
The authors wish to thank the Ministry of Science and Technology of China for the financial support
(Item NO. 08c26214401265 ).
References
[1] R. L. Sykes; S. B. Coning; N. J. Earl. JALCA, 1981, 76 (3): 102-125.
[2] H.P. Germann. JSLTC, 1995, 79(3):82-85.
[3] J. Ludvik. UNIDO Report US/RAS/92/120, 1997:15.
[4] W. Y. Chen; G. Y. Li. Tanning Chemistry, Beijing: Light Industry Press, 2005: 209-220.
[5] S. Saravanabhavan; P. Thanikaivelan; J. R. Rao. Environ. Sci. Technol, 2006, 40 (3): 1069 -1075.
[6] P. Thanikaivelan; J. R. Rao; B. U. Nair. JSLTC, 2000, 84: 276-284.
[7] Z. G. Chen; W. Y. Chen; Z. S. Zhang. China Leather, 2001, 30(5): 13-15.
[8] IUP 2, Sampling. J Soc Leather Technol Chem., 2000, 84: 303-309.
[9] W. Q. Jiang. Physical and Chemical Analysis of Leather, Beijing: Light Industry Press, 1999: 49-98.
[10] IUC 5. JSLTC, 2002, 86: 277-280.
[11] C. Z. Yu ; K. Y. Wang. Analytical Method of Leather Processing, Beijing: Light Industry Press, 2006.
[12] Y. J. He; J. Zhao; B. Shi. Leather Science and Engineering, 2003, 13(6): 14-18.