Research Article

Role of Phthalic and Glycolic Acids to Increase

Chromium Uptake in Leather Tanning Process
A. I. Nasr1, M. G. Taha2, H. E. Ali3, R. M. Ali4

Abstract
Evaluate phthalic (PhA) and glycolic (GA) acids as inducer agents in chrome tanning has been attempted
in the present study. Based on pelt weight, three concentrations from PhA or GA (0.5%, 1% and 2%) were
studied in pickling step then pelts were tanned with chromium sulphate. Chrome exhaustion, leather
uptake, scanning electron micrographs, mechanical and chemical properties were determined for each
experimental groups. Using PhA or GA was improved the chromium leather uptake, mechanical properties
and reduce chromium waste in spent liquors. Chrome exhaustion greater than 95% and 85% has been
achieved when added PhA or GA, respectively. While increasing concentration was enhanced chromium
exhaustion, leather uptake and mechanical properties were improved with added concentration 0.5% better
than other concentrations. scanning electron micrographs (SEM), fiber bundles were more cementation,
cross-linking and higher fullness in added chelating groups than chrome alone.

Keywords: Chrome, Chelating, Glycolic, Leather, Phthalic, Tanning

Introduction
Tanning of skins or hides is one of the oldest industries in the world, to make the raw material resistant to putrefaction,
heat and chemical effects. Mineral tannage involves interaction and cross-linking of skin proteins with metals such as
chromium (III), aluminum (III), titanium (IV) and zirconium (IV). Among them, tanning with partially basified chromium
(III) sulphate is the most commercially favored process in the manufacture of a variety of high quality leathers.1

Chrome tanning is featuring with many advantages such as the production of high hydrothermal stability that cannot be
achieved by any alternative single metal tanning method. Also, it is strongly required for the most modern applications
of leather, particularly for upper and automotive leathers.2 On the other hand, the environmental restrictions to the
disposal of chromium containing solids and effluents, as well as speculations concerning the presence of toxic and
carcinogenic chromium (VI) traces in finished products, have already directed the industry towards using alternatives
or increase chromium (III) utilization, to minimize the environmental impact of the process.3

The uptake of chromium from tanning bath under normal conditions of tanning is of the order of 40-70% of used
chromium. It is now possible to increase the absorption levels of chromium in the tanning bath.4-6 These strategies
include (a) changing conditions of tanning such as mechanical action, time, float length, pH and temperature (b) use
of exhaust aids (c) modifying BCS salts and (d) modifying protein substrate.2,7

Increasing collagen reactivity is mainly depending on increasing the number of carboxylic groups on the amino acid side
chains, which provide more sites for cross-linking with chromium salts and increasing exhaustion. On the other hand,

1
Wool Production and Technology Department, Desert Research Center, Cairo, Egypt.
Biochemistry Department, Faculty of Agriculture, Azhar University, Cairo, Egypt.
2,3,4

Correspondence: Dr. A.I. Nasr, Wool Production and Technology Department, Desert Research Center, Cairo, Egypt.

E-mail Id: ainasr@yahoo.com

Orcid Id: http://orcid.org/0000-0001-8422-8667

How to cite this article: Nasr A.I, Taha M.G, Ali H.E, Ali R.M. Role of Phthalic and Glycolic Acids to Increase Chromium Uptake in
Leather Tanning Process. J Adv Res Glass Leath Plast Tech 2017; 2(3): 5-11.

© ADR Journals 2017. All Rights Reserved.

Nasr A.I et al.
chrome masking is defined as the incorporation of certain
reactive groups into chrome tannin complexes to enhance
the chrome penetration rate and permit basification to
higher pH.1,8
Literature reveals that glycolate and phthalate are from the
pre-tanning additives, led to increase collagen reactivity
and chelating chrome, respectively.1,8-10
GA is a low molecular weight compound but has dual
functionality of alcohol and acid. Because of its small
molecular weight and size, it has a better capability to use
in leather tanning.11,12 On the other hand, PhA is phenolic
acid that has two carboxyl groups on its aromatic ring which
give it acidic properties and produce less cationic complexes
with chromium salts. Thus it is reducing the astringency or
affinity to the collagen, penetrate more easily and make
the distribution more uniform.1,2,8
In this work, studies on the development of high exhaust
chrome tanning process based on increasing collagen
reactivity by GA and chrome in combination with PhA has
been attempted. The high exhaust conditions, mechanical
and chemical properties of this tanning have been compared
with conventional chrome alone.
Materials and methods
Tanning chemicals used in subsequent operations were
commercial grade products, those normally used in
leather industry. PhA (white powder) and GA (clear liquid
concentration 70%) were purchased from El-Gomhouria
Company for Chemicals.
Raw material used for tanning processing was after deliming
and bating processed from wet-salted sheep skins. Skins
were weighted and then three concentrations (0.5%, 1%
and 2% from skin weight) from PhA and GA were used in
pickling. Thus, sheep skins were divided into seven groups
to compare within each acid concentration additive with
traditional tanning process as basic chromium sulphate
(BSC) control group.
According to Covington1, pickling was done by adding salt
to pickling bath and run for 15 min. About 10% salt was
Figure 1.Proposed structure of PhA, GA and BCS (According to Ramamurthy et al.15)
J. Adv. Res. Glass Leath. Plast. Tech. 2017; 2(3)
enough to obtain Bé 8. PhA or GA concentrations were
then added and drum was still run for another 15 min.
After that, pH was adjusted to 3.5-3.8 using sulphuric acid.
Pickling process was carried out for 1h and then 8% basic
chromium sulphate (33% basicity) was added. Tanning
drum was run for 1h then basification was carried out by
addition of 1% sodium bicarbonate in four installments at
an interval of 15 min. Finally, the tanning drum was run for
90 min. then was stopped overnight. Boiling test was done
after basification to ensure if process was done correctly.
The chromium content of the spent liquor and wet blues in
each of the trials was estimated by perchloric acid digestion
methods.
After finishing leathers, samples for various mechanical and
chemical tests from all tanned leathers were obtained as
per ASTM13 methods. Specimens were conditioned at 20°C
± 2°C and 65% ± 4% R.H. over a period of 48 hrs. Mechanical
properties such as tensile strength, elongation percentage
at break, split tear strength and flexibility were measured
as per standard procedures. Each value reported is an
average of four samples (2 values along the backbone and
2 values across the back bone). Chemical properties such
as moisture, total ash content, chromic oxide and pH have
been carried out for BCS control, PhA and GA experimental
leathers according to standard procedures.
The morphological characteristics of tanned leathers
were analyzed using Scanning Electron Microscopy (SEM).
Samples were cut from official sampling position. The
specimens were cut with uniform thickness without any
pre-treatment. The micrograph for the cross section was
obtained by operating the SEM.
Data were analyzed using GLM procedure of SAS14 to
evaluate the differences among produced leathers.
Significant differences were detected using the Duncan
Multiple Range Test.
The fixed effect model used was Yij = µ + Ti + eij , where Yij is
the observation taken on leather (j), µ is overall mean, Ti is
a fixed effect of the (i) chelating material (PhA or GA) and
eij is a random error assumed to be normally distributed
with mean = 0 and variance = σ2e.
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J. Adv. Res. Glass Leath. Plast. Tech. 2017; 2(3)
Results and Discussion
PhA is a phenolic acid and GA is a hydroxyl aliphatic acid
contains two functional groups and these can be considered
as representatives of high chelating chrome tanning agents
(Fig. 1). Covington1 explained that phthalate contains two
carboxyl groups and has been used as chelation agent;
the dicarboxylate compound reacts with a single metal
ion. With respect to glycolate contains one carboxylic and
hydroxyl groups. It has been used as cross-linking agent,
when the compound’s groups react with two metal ions
(Fig. 2).
The interactions are usually done with active group located
in amino acids residue of collagen, such as amino (NH2) or
hydroxyl (OH) groups and interact with metal complexes.
These interactions are very important for the stability of
proteins.15 Thus, the effect of both PhA and GA used as
high exhaustion of chrome tanning on enhancing the ability
of uptake of tanning agent and reduction of chromium in
Figure 2.Schematic presentation of chelating Cr(III) by glycolic cross-linking or phthalic chelation
(According to Covington1)
Effect of PhA and GA on Cr(III) exhaustion
As chrome chelating agents, PhA or GA involve two-steps
reaction in the tanning process. Initially they react with
collagen and/or Cr(III) presents in basic chromium sulphate.
In the second stage, collagen in leathers reacts both with
free Cr(III) and other complex. Fixation of PhA and GA in
leathers generates additional carboxyl and hydroxyl groups
which have high affinity with Cr(III). As resulting of this
reason, uptake of Cr(III) was enhanced.
After the completion of chrome tanning, the Cr(III) content
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Nasr A.I et al.
waste water were documented.
The tanning process in this study was similar to that
introduced by Ramamurthy et al.15, who used gallic acid
as chelating agent. Delimed sheep skin was selected for
high exhaust chrome tanning; the process is shown in
Fig. 3. As the delimed sheep skins are partially anionic in
charge, it is treated with sulphuric acid to convert it to
cationic charge prior to chrome tanning. Salt is used to
suppress the swelling of sheep skin by maintaining the
ionic balance. During chrome tanning process, Cr(III) is
irreversibly bound with the skin matrix by cross-linking with
collagen carboxylic and added PhA or GA acids carboxylic
groups through coordinate covalent linkage, as seen in Fig.
3. The tanned leathers are neutralized to avoid the surface
fixation of negatively charged post-tanning chemicals on
the positively charged chromium cross-linked matrix. This
is achieved using mild alkalies like sodium bicarbonate.
During neutralization, the pH is raised to 5.0–5.2 for further
post tanning operation.
was estimated quantitatively in exhaust liquor and tanned
leathers in each trial and the result are presented in Fig. 4.
It is revealed that Cr(III) in exhaust liquor was decreased
in PhA and GA groups than control group (chrome alone),
which also reflected in exhaustion percentages. Chrome
alone group was the lowest in exhaustion (78.8%) while
maximum corresponding values were 95.9% and 85.6% for
PhA and GA groups, respectively. This trend was expected
because Covington1 explained that the relative affinity
of potential chelating agents for reacting in the chrome
complex sphere is higher in phthalate than glycolate.
Nasr A.I et al. J. Adv. Res. Glass Leath. Plast. Tech. 2017; 2(3)

Figure 3.Schematic presentation of Cr(III) complexes formed during basification and its
complexation with collagen carboxyl groups (According to Ramamurthy et al.15)
Except group GA 2%, increasing the concentration of behavior especially concentration effect.1,8-10
added PhA or GA was led to decrease the Cr(III) in exhaust
liquor and increase chrome exhaustion and leather uptake From Cr(III) exhaustion and uptake trends, the exhaustion
in tanned leathers. That gave an indicator about GA, percentages of PhA were better than those corresponding
after concentration 1% this relation was changed to be values of GA. However, the opposite was found in the
counterproductive. Although few previous investigators tanned leathers uptake. Obviously from exhaustion data,
were indicated to using glycolate as chelating agents in the better concentrations of added PhA and GA were 2%
tanning, unfortunately it was not illustrated their chelating and 1%, respectively to achieve maximum utilization of
Cr(III) in tanning.

Figure 4.Percentages of Cr(III) in exhaust liquor, exhaustion and change in leather

uptake for control and experimental groups

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J. Adv. Res. Glass Leath. Plast. Tech. 2017; 2(3) Nasr A.I et al.

Tanned Leather Properties tanned leathers then BCS control leathers.

Mechanical and chemical properties of experimental tanned
leathers; tensile strength (kg/cm2), elongation (%), tear
strength (kg/cm), moisture (%), total ash (%), chrome
content (%) and pH value were compared with chrome
alone (Table 1). Flexibility test was done on all tanned
leathers until fifty thousand flexures without any cracks.
About the effect of added chelating agents before tanning
on the leather quality, the additions of PhA or GA were
improved the leathers properties than BCS control.
Obviously, tensile, tearing strengths and elongation values
were higher significantly (P<0.05) in PhA and GA tanned
leathers than BCS control leathers.

About leather quality for manufacturing uses, the By comparing corresponding mechanical properties of PhA
mechanical and chemical properties values were showed and GA tanned leathers, the differences were insignificant
the possibility of using all tanned leathers in different although the superiority of GA tanned leathers in values.
manufacturing uses such as shoe upper or garments
according to limitation range.10,16,17 With respect to the relation between chrome content
in tanned leathers and their mechanical properties, it
Chemical properties values were significant differed only was incomprehensible because the increasing in leather
in total ash percentage (P<0.05) and chrome content chrome content was not corresponded with improving in
percentage (P<0.01) while moisture and pH values were the mechanical properties. On the other hand, adding PhA
insignificant differed. That is due to the similarity between or GA with concentration 1% were produced leathers lower
all tanned leathers in tanning process except the tanning in quality than other concentrations 0.5% and 2%, while
step, which differed due to chelating agent added and concentration 0.5% is considered the highest strengths,
their concentration. GA tanned leathers were the highest elongations values and also in quality.
value for chrome and total ash contents followed by PhA
Table 1.Least square means ± SEM of leather mechanical and chemical properties for BCS control and
experimental tanned leathers
Treatment Mechanical properties Chemical properties
Tensile Elongation Tear Moisture Ash Cr pH
strength (%) strength (%) (%) (%)
(kg/cm2) (kg/cm)
BCS Control 133.31b 63.14 b
17.43c 13.43 5.48ab 2.96e 4.49
0.5%phthalic 178.60ab 77.58 a
20.90ab 13.44 5.47ab 2.99e 4.47
1% phthalic 155.82b 70.30ab 20.64abc 13.38 5.57ab 3.07d 4.49
2% phthalic 167.25ab 75.19 ab
19.31abc 13.23 5.72ab 3.24c 4.48
0.5% glycolic 206.80a 78.57 a
20.64abc 13.34 5.20b 3.28c 4.47
1%glycolic 154.15b 73.91ab 19.03bc 13.44 6.25a 3.74a 4.47
2%glycolic 167.58ab 75.22 ab
22.45a 13.52 6.06a 3.54b 4.49
SEM 6.36 1.72 0.44 0.05 0.10 0.05 0.01
Significance * * * NS * ** NS
Means in the same column having different superscripts are significantly different (P<0.05).
a,b,c

SEM: standard error of mean; Significance: NS Not Significant, *P<0.05, **P<0.01.

Scanning Electron Microscopy it would exhibit principally increasing in leather fullness.

The SEM analysis of all tanned leather samples showing
cross section at a magnification of x1500 are depicted in
Fig. 5.
Tanned leather without adding chelating agent (BCS control)
shows fiber structure throughout the cross section with
highest separation of fibers. Since the tanned leathers with
adding PhA or GA exhibit slightly dispersed fiber structure,
That explains the weakness in strengths and elongation of
BCS control leathers than other groups. In the meantime
when comparing effect of added chelating materials, PhA
tanned leathers was showed fiber bundles more swell but
less cross-linking than those in GA tanned leathers. Also,
concentration 0.5% of added PhA or GA was the better in
effect than other concentrations, 1% and 2% which shows
on fibers appearance as increasing in fibers cementation
and compactness.

9
Nasr A.I et al.
Figure 5.Electron micrographs of BCS control and experimental groups
Conclusion
This study demonstrated the eco-friendly tanning process
and thereby reduces pollution caused due to the chromium
effluent and hence contributes to the development of
cleaner process. Adding PhA or GA in pickling step (before
tanning) as chelating agents is improving chromium
utilization. This behavior can be enhanced by means of
introducing the additional carboxyl groups. The introduction
of these additives can efficiently enhance the Cr(III)
absorption but change the traditional chrome tanning
mechanism. Therefore, adding PhA or GA acid with 0.5%
concentration from pelt’s weight is enough to produce
leathers higher in quality than conventional chrome
tanning process. While the increase in addition increases
the chrome exhaustion in tanning without improvement
in leather quality.
Acknowledgment
This study has been achieved within the PROCAMED project
funded by European Union within the program ENPI-
CBC-MED, reference number I.B/1.1/493. The content of
the present document is under the responsibility of the
PROCAMED partners and could not be considered as the
J. Adv. Res. Glass Leath. Plast. Tech. 2017; 2(3)
position of European Union.
Authors would like to proprietor of Timex tannery, Cairo,
Egypt for his help and support in the practical part.
References
1. Covington AD. Tanning chemistry the science of leather
Cambrige, London: RSC publishing, 2009.
2. Özlem M. Fundamental aspects of the chrome tanning
reaction: PhD. Thesis, British School of Leather
Technology, University College Northampton. 2002.
3. Morera JM, Bartolí E, Chico R. Minimization of the
environmental impact of chrome tanning: a new
process reusing the tanning floats. J. of Cleaner Prod.
2012; 19: 2128-32.
4. Kedlaya KJ. Recent technological progress and
innovations in the application of chrome in leather
making. Leather Sci. 1974; 21: 1-11.
5. Prasad BGS, Chandrasekaran B, Rao JR, Chandrababu
NK, Kanthimathi M, Ramasami T. Prospects for
chromium management in tanneries: a critical review.
Leather Sci. 1987; 34: 132-48.
6. Mu C, Lin W, Zhang M. Towards zero discharge of
chromium-containing leather waste through improved
10
J. Adv. Res. Glass Leath. Plast. Tech. 2017; 2(3)
alkali hydrolysis. Waste Management 2003; 23: 835-43.
7. Sreeram KJ, Ramasami T. Sustaining tanning process
through conservation, recovery and better utilization
of chromium. Resources, Conservation and Recycling
2003; 38: 185-212.
8. Ludvík. Chrome management in the tanyard. regional
programme for pollution control in the tanning industry
in South-East Asia. Vienna, 2000.
9. Wang H, Zhou X. A new pretannage with glyoxal and
N-thiouridopyromelliatimac acid for high exhaust
chrome tannage. JALCA 2006; 101: 81-5.
10. BASF. Pocket book for leather technologist. 4th ed.
Badische Anilin und Soda-Fabrik, 67056 Ludwigshafen,
Germany. 2007.
11. Sangeeta P. Micellar Catalysis of Oxidation of Glycolic
acid by N-Bromophthalimide. Colloid J. 2012; 74: 582-8.
11
Nasr A.I et al.
12. Anonymous. DuPont Glycolic Acid, Technology
for a changing environment. 2006. Available
from: https://chemical-centre.com/d/982327/d/
glycolicacidbrochure-extended.pdf.
13. ASTM. Books of standards Vol.15.04 American Society
for Testing and Materials, USA. 2014.
14. SAS. SAS/STAT 9.2 User’s guide. 2nd ed., SAS Institute
Inc., Cary, NC. 2008.
15. Ramamurthy G, Krishnamoorthy G, Sastry TP, et al.
Rationalized method to enhance the chromium uptake
in tanning process: role of Gallic acid. Clean Techn.
Environ. Policy 2013; 16(3): 647-54.
16. UNIDO. Acceptable quality standards in the leather
and footwear industry. Vienna, 1994.
17. A handbook on mandatory and voluntary standards
on leather and footwear products. India, 2007.