You are on page 1of 32

View Article Online

View Journal

RSC Advances
This article can be cited before page numbers have been issued, to do this please use: S. Silambarasan,
R. Aravindhan, J. R. Rao and T. Palanisamy, RSC Adv., 2015, DOI: 10.1039/C5RA11740B.

This is an Accepted Manuscript, which has been through the


Royal Society of Chemistry peer review process and has been
accepted for publication.

Accepted Manuscripts are published online shortly after


acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. This Accepted Manuscript will be replaced by the edited,
formatted and paginated article as soon as this is available.

You can find more information about Accepted Manuscripts in the


Information for Authors.

Please note that technical editing may introduce minor changes


to the text and/or graphics, which may alter content. The journals
standard Terms & Conditions and the Ethical guidelines still
apply. In no event shall the Royal Society of Chemistry be held
responsible for any errors or omissions in this Accepted Manuscript
or any consequences arising from the use of any information it
contains.

www.rsc.org/advances
Page 1 of 31 RSC Advances
View Article Online
DOI: 10.1039/C5RA11740B

Waterless tanning: Chrome tanning in ethanol and its derivatives

S. Silambarasan, R. Aravindhan, J. Raghava Rao* and P. Thanikaivelan*


Published on 24 July 2015. Downloaded by UNIVERSITY OF OTAGO on 27/07/2015 06:50:19.

RSC Advances Accepted Manuscript


Central Leather Research Institute (Council of Scientific and Industrial Research), Adyar, Chennai

600020, India. E-mail: thanik8@yahoo.com; thanik@clri.res.in; jrrao_clri@yahoo.co.in

Electronic supplementary information (ESI) available. See DOI: 10.xxxx

1
RSC Advances Page 2 of 31
View Article Online
DOI: 10.1039/C5RA11740B

Summary

Approach towards waterless tanning is crucial to address present challenges faced by humanity

such as global warming and depletion of water resources. Here, green solvents alternate to water

such as ethanol, ethyl acetate and ethyl lactate were employed for both pickle-based and pickle-
Published on 24 July 2015. Downloaded by UNIVERSITY OF OTAGO on 27/07/2015 06:50:19.

less chrome tanning. Results show that ethanol medium appears to be the best solvent for chrome

RSC Advances Accepted Manuscript


tanning in terms of color, chromium uptake and other bulk properties of tanned leathers.

Extensive studies indicate that the chrome tanning in ethanol medium leads to higher exhaustion

(87% for pickle-based and 95% for pickle-less), better chromium content, distribution and

shrinkage temperature and low chromium leaching in tanned leathers compared to water

mediated tanning. Both visual and electron microscopic analyses demonstrate comparable grain

structure and fiber architecture in tanned and crust leathers. Similarly, strength and organoleptic

properties of crust leathers are also comparable between ethanol and water mediated tanning.

The process enables reduction of COD, BOD and TS loads in composite liquor by 14-26, 21-28

and 42-46%, respectively. The leather properties are not altered upon recycling of chromium

containing ethanol liquor up to two times. These results suggest that it is possible to replace

water by ethanol for chrome tanning, which offers great potential for sustainable leather

manufacture with solvent recycling.

2
Page 3 of 31 RSC Advances
View Article Online
DOI: 10.1039/C5RA11740B

Introduction

Sustainable production and consumption is gaining importance in all spheres of human


1, 2
civilization including industries . The challenges of global warming such as environmental
Published on 24 July 2015. Downloaded by UNIVERSITY OF OTAGO on 27/07/2015 06:50:19.

pollution, resource depletion and threats to food, water and energy securities require a paradigm

RSC Advances Accepted Manuscript


shift in production and consumption pattern 3. Leather making is one such sector wherein the

aforementioned factors are being scrutinized globally to ensure sustainable production 4. Chrome

tanning is a popularly employed process to convert the skins and hides into leather by stabilizing

the collagen matrix 4. Currently the process is carried out in aqueous medium. Aqueous medium

is helpful in solubilizing the tanning agent, basic chromium sulphate, and aiding the penetration

into the collagen matrix. Further, water is essential for hydrolysis and olation of chromium

molecules and to form various oligomeric species 5. Nevertheless, the conventional chrome

tanning process suffers from poor chromium uptake in the skin matrix and therefore significant

amount of chromium molecules remain in large amount of water and released as effluent 6. This

large amount of wastewater contains potentially toxic chromium molecules and the disposal of

the same remains as a major problem in leather industry. To address this issue, a number of
4, 7
researchers have developed various chromium management technologies . Chrome recovery

and reuse 8, direct chrome liquor recycling 9, high exhaust chrome tanning and tanning salts 6, 10,
5
closed loop aluminium-chrome combination tanning, pickle-basification free chrome tanning
11
and two-stage tanning are some examples of recent development in this area by our group as

well as others. Some advanced and futuristic clean chrome tanning systems have also been
12, 13 14, 15
developed by our group such as the three-step tanning and reverse tanning processes ,
16
which are now being further investigated globally . In addition to reducing the chromium

emission, these advanced processes also lead to other benefits such as reduced water

3
RSC Advances Page 4 of 31
View Article Online
DOI: 10.1039/C5RA11740B

consumption and discharge and reduction in the amount of use of chemicals, power, time and

cost compared to conventional tanning process. However, in view of the increased demand and

reduced supply of water coupled with projected global water scarcity, the development of
17-19
waterless tanning technology is need of the hour . Solvent based chrome tanning techniques
Published on 24 July 2015. Downloaded by UNIVERSITY OF OTAGO on 27/07/2015 06:50:19.

20-23
have already been reported in the literature . Chagne et al. and Silvestre et al. employed

RSC Advances Accepted Manuscript


200% trichlorotrifluoroethane or Forane 113 solvent along with 250% water based on dry weight

of the pickled skins20, 21


. Manfred et al. and Renner et al. carried out chrome tanning using

carbon dioxide as medium at high pressure (few experiments at supercritical fluid state) with

considerable savings in time and chromium usage22, 23.

The present investigation aims to develop a chrome tanning process using green solvents

chosen from a set of GSK green chemistry principles such as LD50, environment and health

hazards 24. The approach relies on the fact that the free water present in the pelt is sufficient for

the diffusion and fixation of chromium in the skin matrix, which was recently established based

on a systematic investigation using lyophilization technique19. Based on green chemistry

principles, we have shortlisted three solvents namely ethanol, ethyl acetate and ethyl lactate24.

Further, Capello et al. assessed substance-specific hazards with the quantification of emissions

and resource use over the full life-cycle of a solvent and found that ethanol was Greener in

comparison to other solvents25. Besides, ethanol and its derivatives are produced by fermentation

with renewable resources such as sugar-containing feeds in comparison to solvents obtained

from petrochemical route leading to avoidance of fossil resource use and CO2 emission to the

environment. In this work, pickle-based and pickle-less chrome tanning5 processes have been

examined in non-aqueous medium such as ethanol, ethyl acetate and ethyl lactate. Based on the

results of these preliminary tanning experiments, ethanol medium was chosen for carrying out

4
Page 5 of 31 RSC Advances
View Article Online
DOI: 10.1039/C5RA11740B

chrome tanning in matched pair experiments along with control followed by a conventional post

tanning process in aqueous medium. Detailed analysis on the quality of the wet blue leathers as

well as effluent characteristics and emission factors was carried out. Crust leathers were

examined for the physical, chemical and organoleptic properties.


Published on 24 July 2015. Downloaded by UNIVERSITY OF OTAGO on 27/07/2015 06:50:19.

RSC Advances Accepted Manuscript


Materials and methods

Materials

Wet salted goat skins with an average area and weight of 4.51 sq.ft. were procured from local

suppliers at Chennai and conventionally processed into pickled/delimed pelts at the Pilot

Tannery, Central Leather Research Institute. For all the tanning trials, commercial grade

chemicals such as sodium formate, sodium bicarbonate, acetic acid, basic chromium sulphate, etc

were employed. Analytical grade ethanol was procured from M/s Hayman and used without

further purification. Analytical grade ethyl acetate and ethyl lactate were procured from M/s

Loba Chemicals Pvt. Ltd. and used without further purification. Tanning trials were carried out

in a stainless steel drum.

Preliminary chrome tanning trials in ethanol and its derivatives

Three solvents namely, ethanol, ethyl lactate, ethyl acetate were chosen for the preliminary

tanning trials. Pickled/delimed goat pelts were cut into small pieces measuring 10.2 sq.ft. and

used for the preliminary tanning trials. In the case of pickle-based chrome tanning, two pickled

pelt cut pieces (each measuring 10.2 sq.ft.) were treated with 7% basic chromium sulphate

(BCS) salt (percentage based on pelt weight) in stainless steel drums for 1 h. Then 100% v/w of

the chosen solvents (individually) was added as a medium and drummed for 30 min. After

5
RSC Advances Page 6 of 31
View Article Online
DOI: 10.1039/C5RA11740B

ascertaining the penetration of chromium, the pH was found to be 2.90.2. In the subsequent

basification step, pH of the tanning bath was increased to 3.70.2 using 1% sodium formate for

10 min drumming followed by the addition of 1% sodium bicarbonate in 3 installments at 10 min

interval and finally drummed for 1 h. In the case of pickle-less chrome tanning, the pH of two
Published on 24 July 2015. Downloaded by UNIVERSITY OF OTAGO on 27/07/2015 06:50:19.

delimed pelt cut pieces (each measuring 10.2 sq.ft.) was adjusted to 5.50.5 using 0.5% acetic

RSC Advances Accepted Manuscript


acid on the weight of the pelt. The pH adjusted delimed pelt was drummed with 7% BCS for 1 h.

Then 100% v/w of the chosen solvents (individually) was added as a medium and drummed for 2

h. After ascertaining the penetration of chromium, the pH was found to be 4.00.2. The total

duration of both pickle-based and pickle-less chrome tanning was around 3 h. The tanned

leathers were assessed by experienced leather technologist for their quality through organoleptic

examination. The chrome content in the tanned leathers was also analyzed as described in the

forthcoming section.

Chrome tanning in ethanol medium followed by conventional post tanning process

Ethanol medium employed for tanning yielded good chrome tanned leather compared to its

counterparts such as ethyl lactate and ethyl acetate. Hence, ethanol was selected for further

experiments. Two pickled/delimed goat pelts were used for each experiment employing pickle-

based and pickle-less chrome tanning in ethanol medium as described in the previous section

along with control trials in water medium. The control and experimental chrome tanned leathers

were converted into crust upper leathers employing a conventional post tanning process in

aqueous medium.

6
Page 7 of 31 RSC Advances
View Article Online
DOI: 10.1039/C5RA11740B

Analysis of chrome tanned leathers

The shrinkage tester apparatus (SATRA STD 114, SATRA Technology Centre) was used for

determining the shrinkage temperature of chrome tanned leathers. The tanned leathers were

analysed for moisture content in the hot air-oven for 5 h at 1042oC 26


. The chrome tanned
Published on 24 July 2015. Downloaded by UNIVERSITY OF OTAGO on 27/07/2015 06:50:19.

27
leathers were analysed for chromium content employing the standard procedure using a UV-

RSC Advances Accepted Manuscript


Visible spectrophotometer (UV 1800, Shimadzu) and chrome content was expressed as moisture-

free basis. Triplicate measurements were carried out for each analysis and the average values

were calculated. Bulk properties of chrome tanned leathers such as fullness, grain smoothness,

color and wrinkles were assessed by experienced leather technologist through organoleptic

examination.

Analysis of leachable chromium

A known weight of experimental chrome tanned leather sample was placed in a beaker with 50

ml of distilled water and ethanol separately. In the case of control leathers (water mediated), a

known weight of tanned leather sample was placed in a beaker with 50 ml of distilled water. It

was agitated in a shaker at low rpm for 3 h. The chromium content in the solution was analyzed

using alkaline peroxide procedure and the concentration of chromium was determined at 372 nm

using a UV-Visible spectrophotometer (UV 1800, Shimadzu)28. The amount of chromium was

then calculated using molar absorption coefficient () value of 4.8 103 M-1cm-1 based on Beer-

Lambert law. Triplicate measurements were carried out and the average values were calculated.

Chromium leached from Cr-tanned leather sample (Cr2O3 %) was calculated by dividing the

amount of chromium in the leachate by the amount of chromium in the chrome tanned leather

sample and multiplying by 100.

7
RSC Advances Page 8 of 31
View Article Online
DOI: 10.1039/C5RA11740B

Analysis of spent chrome liquor

Spent chrome liquor was collected from both control and experimental pickle-based and pickle-

less chrome tanning processes. Liquors were acid digested and analyzed for chromium using
Published on 24 July 2015. Downloaded by UNIVERSITY OF OTAGO on 27/07/2015 06:50:19.

alkaline peroxide procedure as described above28. The percentage exhaustion of chromium was

RSC Advances Accepted Manuscript


calculated from the amount of spent liquor collected. Triplicate measurements were carried out

and the average values were calculated.

Composite liquor analysis

Composite liquors from control and experimental leather processing were collected from chrome

tanning up to post-tanning. The liquors were analyzed for chemical oxygen demand (COD),
26
biological oxygen demand (BOD), and total solids (TS) as per the standard procedures .

Emission loads were calculated by multiplying concentration (mg/L) with the volume of effluent

(L) per ton of raw skins processed.

Scanning electron microscopic analysis

The chrome tanned leather samples were dehydrated gradually using acetone and methanol as
29
per standard procedure . Excess solvent was removed from the samples by placing them

between filter papers. Crust leathers were directly analyzed without dehydration. Samples were

then cut into specimens of uniform thickness and coated with gold using an ion-sputtering

device. The samples were mounted on aluminium stubs and analyzed using scanning electron

microscope (SEM, Tescan Vega 3 SB) at an accelerating voltage of 3 kV in different

magnifications.

8
Page 9 of 31 RSC Advances
View Article Online
DOI: 10.1039/C5RA11740B

Analysis of crust leathers

Samples for various physical tests were obtained from control and experimental crust leathers as

per IUP method 30. Samples were conditioned at 804oF and 652% R.H. over a period of 48 h.
Published on 24 July 2015. Downloaded by UNIVERSITY OF OTAGO on 27/07/2015 06:50:19.

Physical properties such as tensile strength, % elongation at break, tear strength and grain crack

RSC Advances Accepted Manuscript


31-33
strength were then investigated employing standard procedures . Control and experimental

crust leathers were assessed for softness, fullness, grain smoothness and general appearance by

organoleptic examination. The leathers were rated on a scale of 010 points for each property by

experienced leather technologist, where higher points indicate better properties.

Studies on recycling of spent ethanol liquor

In order to find the feasibility of recovering and recycling the ethanol used in chrome tanning, a

limited study was conducted employing pickle-based chrome tanning. One pickled goat pelt was

used for each experiment employing pickle-based chrome tanning in ethanol medium as

described above. At the end of the chrome tanning process for the first batch, the spent ethanol

liquor was collected, filtered and analyzed for the chromium content as described above. In the

1st recycling process, BCS equivalent to the balance amount of the spent ethanol liquor was

added to the pelt and drummed for 1 h. Then the chromium containing spent ethanol liquor was

added and the total volume was adjusted to 100% v/w by the addition of fresh ethanol and

drummed for 30 min. After confirming the penetration of chromium, the pH was found to be

3.20.2. During basification, 0.5% sodium formate was added and drummed for 10 min followed

by the addition of 0.8% sodium bicarbonate in 3 installments at 10 min interval and finally

drummed for 1 h. The pH of the tanning bath was found to be 3.80.2. At the end of the chrome

tanning process for the second batch, the spent ethanol liquor was collected, filtered and
9
RSC Advances Page 10 of 31
View Article Online
DOI: 10.1039/C5RA11740B

analyzed for the chromium content. The collected spent ethanol liquor was reused in the third

batch (2nd recycling process) as described above.

Results and discussion


Published on 24 July 2015. Downloaded by UNIVERSITY OF OTAGO on 27/07/2015 06:50:19.

Preliminary trials

RSC Advances Accepted Manuscript


Preliminary trials were carried out using three solvents namely ethanol, ethyl acetate, and ethyl

lactate employing both pickle-based and pickle-less chrome tanning processes with pickled and

delimed pelts, respectively. Although chrome tanning is possible in all the selected solvents,

quality of the tanned leather depended on the solvent used for the process as shown in Table 1.

Visual assessment of chrome tanned leathers processed through pickle-based and pickle-less

chrome tanning in ethyl acetate and ethyl lactate medium shows slight swelling, coarse grain and

moderate penetration of chromium. Chrome tanned leathers processed through ethyl acetate did

not show significant color change from the conventional wet blue, however ethyl lactate medium

yielded bluish leathers with green tinge. On the other hand, chrome tanned leathers (pickle-based

and pickle-less) prepared using ethanol medium are bluish comparable to the conventional wet

blue without any coarse grain and swelling effect. Further, leathers prepared in ethanol medium

show high uptake of chromium compared to those prepared in ethanol derivatives. This could be

due to the fact that the dispersion and diffusion of BCS in the skin matrix is better in ethanol

medium compared to other two solvents assuming that the internal moisture present in the pelt is

constant for all the three systems. Therefore, ethanol was selected for further detailed analysis

using matched pair experiments.

10
Page 11 of 31 RSC Advances
View Article Online
DOI: 10.1039/C5RA11740B

Ethanol mediated chrome tanning

Digital images of control and experimental chrome tanned leathers and respective process liquors

(insets) are shown in Fig. 1. It is evident that the color of pickle-based chrome tanned leathers is

light blue for both ethanol and water mediated processes, whereas the pickle-less chrome tanning
Published on 24 July 2015. Downloaded by UNIVERSITY OF OTAGO on 27/07/2015 06:50:19.

yields slightly dark blue leathers. Chromium exhaustion, distribution and shrinkage temperature

RSC Advances Accepted Manuscript


of pickle-based and pickle-less chrome tanning systems in ethanol and water medium are shown

in Table 2. Exhaustion levels of chromium for both pickle-based and pickle-less chrome tanning

in ethanol medium are higher compared to similar processes carried out in water medium

(control). This may be due to the limited solubility of BCS in ethanol medium, which drives

more chromium in the skin matrix containing internal water. The color variations in the process

spent liquors (see insets of Fig. 1) also demonstrate the higher exhaustion in ethanol mediated

processes. The improved uptake of chromium is also reflected in the chromium distribution data.

It is seen that the leathers processed in ethanol medium possess higher amount of chromium in

all the regions of leather, namely butt, neck, and belly, compared to those processed in water

medium. Further, both ethanol and water mediated chrome tanning processes yield leathers with

reasonably uniform chromium distribution in all the regions of leathers. The shrinkage

temperature of leathers processed in ethanol medium is slightly higher than that of control

leathers (water mediated). These results suggest that replacing water with ethanol for chrome

tanning improves the chromium uptake and thermal stability of leathers.

The extent of chromium leaching and the amount of chromium present before and after

leaching in the tanned leathers processed through pickle-based and pickle-less chrome tanning in

ethanol and water medium are shown in Table 3. We observed lower leaching of chromium from

both control and experimental leathers when water and ethanol were used as leaching solvents. A

11
RSC Advances Page 12 of 31
View Article Online
DOI: 10.1039/C5RA11740B

maximum of 2% Cr2O3 was leached from chrome tanned leather when water was used as tanning
19
as well as leaching medium. This value is lower than those reported in the literature . This

indicates that the remaining chromium (~ 98%) is fixed chemically with the leather matrix. The

experimental leather shows fairly reduced chromium leaching when compared to control leather.
Published on 24 July 2015. Downloaded by UNIVERSITY OF OTAGO on 27/07/2015 06:50:19.

In addition, the amount of chromium present in leathers after leaching is comparable to the

RSC Advances Accepted Manuscript


values obtained before leaching.

The organoleptic assessment data of both control and experimental chrome tanned leathers

prepared through pickle-based and pickle-less chrome tanning processes using ethanol and water

medium is given in Table 4. It is seen that leathers tanned in ethanol medium show either

comparable or even better color, grain smoothness and fullness in comparison to leathers tanned

in water medium. However, leathers tanned in ethanol medium through pickle-less chrome

tanning show slightly more wrinkles in comparison to their counterparts processed in water

medium. This problem needs to be addressed separately, probably during a semi-commercial

trial, to improve the appearance of tanned leathers.

Scanning electron micrographs showing the grain surface of control and experimental

chrome tanned leathers are given in Fig. 2. The grain surface of experimental leathers shows

clear hair pores without any deposition of chromium comparable to the control leather. The

cross-sectional images of control and experimental chrome tanned leather samples (Fig. 3) show

fiber bundles with comparable porosity and architecture. Similar observation has been made on

the surface and cross section of the control and experimental crust leathers (Fig. S1 and S2).

These results suggest that the microstructure of the leather is not altered significantly upon

tanning in ethanol medium.

12
Page 13 of 31 RSC Advances
View Article Online
DOI: 10.1039/C5RA11740B

Composite liquor analysis

The chrome tanned leathers processed through pickle-based and pickle-less chrome tanning in

ethanol medium were post tanned in water medium. Composite liquors collected by mixing spent

liquors from chrome tanning, neutralization, washing, retanning, fatliquoring, dyeing and fixing
Published on 24 July 2015. Downloaded by UNIVERSITY OF OTAGO on 27/07/2015 06:50:19.

process steps for both control and experimental processes, were analyzed for COD, BOD, and

RSC Advances Accepted Manuscript


TS and the values are given in Table 5 along with emission loads. It is seen that both pickle-

based and pickle-less chrome tanning in ethanol medium lead to significant reduction in the

COD/BOD/TS loads by 14-26, 21-28 and 42-46%, respectively compared to control processes

carried out in water. The observed reductions in pollution loads could be due to the improved

uptake of chromium, syntans, fatliquors and dyes.

Evaluation of crust leathers

The physical properties such as tensile, tear and grain crack strength of control and experimental

chrome tanned leathers processed through pickle-based and pickle-less chrome tanning were

analyzed and the values are given in Table 6. It is seen that the strength characteristics of

experimental leathers are comparable to that of control leathers. Hence, it is seen that the chrome

tanning process in ethanol medium did not critically affect the strength properties of leathers in

comparison to conventional water-mediated tanning process.

The organoleptic properties of control and experimental crust leathers processed through

pickle-based and pickle-less chrome tanning are given in Fig. 4. The properties of the leathers

made using chrome tanning in ethanol medium are comparable to those of leathers made using

the conventional chrome tanning process in water medium. The grain smoothness, softness and

general appearance of crust leathers processed through pickle-based and pickle-less chrome

13
RSC Advances Page 14 of 31
View Article Online
DOI: 10.1039/C5RA11740B

tanning in ethanol medium are comparable to the control leathers tanned in water medium. There

seems to be a slight decrease in the fullness of experimental leathers processed through pickle-

less chrome tanning in ethanol medium when compared to control leathers. In general, chrome

tanning in ethanol medium did not adversely affect the organoleptic properties of leathers in
Published on 24 July 2015. Downloaded by UNIVERSITY OF OTAGO on 27/07/2015 06:50:19.

comparison to leathers tanned in water medium.

RSC Advances Accepted Manuscript


Recycling studies

A paramount requirement of solvent based processes is the ability to recover and recycle the

used solvent in the subsequent processing, which would reduce the cost and environmental

burden. Here, the results of recycling of the spent ethanol liquor in the pickle-based chrome

tanning for two times are given in Table 7. It is seen that nearly 65% spent ethanol liquor can be

collected during recycling up to three batches. Therefore, the fresh solvent requirement during

recycling can be minimized significantly. As can be seen, the collected ethanol liquor contain

chromium equivalent to about 0.7 to 0.9% BCS, which means that the BCS offer can be reduced

from 7% up to 6.1% (for the 4th batch) leading to cost saving to some extent. Lower amount of

chromium in the spent ethanol liquor evidences higher uptake of chromium in the tanned leathers

as observed earlier. The color of chrome tanned leathers by recycling of spent ethanol liquor is

comparable to the first batch of ethanol-mediated pickle-based chrome tanning process. The

recycling of spent ethanol liquor does not seem to affect the thermal stability of the tanned

leathers. The results suggest that it is possible to recycle the used solvent up to two times

without affecting the properties of the tanned leathers, which can be beneficial in cost

effectiveness.

14
Page 15 of 31 RSC Advances
View Article Online
DOI: 10.1039/C5RA11740B

Conclusions

In search of alternatives for water based chrome tanning, an attempt has been made in the present

study to perform chrome tanning in ethanol and its derivatives such as ethyl acetate and ethyl

lactate employing both pickle-based and pickle-less method. Although all the three solvents
Published on 24 July 2015. Downloaded by UNIVERSITY OF OTAGO on 27/07/2015 06:50:19.

enabled the chrome tanning process, ethanol medium provided better chrome tanned leathers in

RSC Advances Accepted Manuscript


terms of color, chrome content and organoleptic properties. Detailed studies on the use of ethanol

medium for chrome tanning show comparable shrinkage temperature, grain and fiber

architecture, strength and bulk properties and reduction in chromium discharge in contrast to

water mediated processing. The amount of leachable chromium in the tanned leathers is also low

compared to leathers tanned in water medium. Tanning in ethanol medium also helps in

minimizing waste generation such as chromium, TS, COD, and BOD loads. Further, we proved

that the ethanol liquor from chrome tanning can be recovered and recycled up to 2 times without

affecting the properties of the leathers. The results of this limited study show that ethanol

mediated chrome tanning is feasible and helpful in preventing the environmental pollution and

improving the sustainability of tanning industry.

Acknowledgements

Financial support from CSIR under XIIth plan project Research Initiatives for Waterless

Tanning (RIWT-CSC0202) is greatly appreciated. We also thank Department of Mechanical

Engineering, Anna University for providing SEM facility. CSIR-CLRI Communication No.

1087.

15
RSC Advances Page 16 of 31
View Article Online
DOI: 10.1039/C5RA11740B

Notes and References

1. J. Brizga, Z. Mishchuk and A. Golubovska-Onisimova, J Clean Prod, 2014, 63, 45-53.

2. P. Vergragt, L. Akenji and P. Dewick, J Clean Prod, 2014, 63, 1-12.


Published on 24 July 2015. Downloaded by UNIVERSITY OF OTAGO on 27/07/2015 06:50:19.

3. S. R. Wan Alwi, Z. A. Manan, J. J. Kleme and D. Huisingh, J Clean Prod, 2014, 71, 1-

RSC Advances Accepted Manuscript


10.

4. P. Thanikaivelan, J. R. Rao, B. U. Nair and T. Ramasami, Crit. Rev. Env. Sci. Tec., 2005,

35, 37-79.

5. W. Legesse, P. Thanikaivelan, J. R. Rao and B. U. Nair, J. Am. Leather Chem. Assoc.,

2002, 97, 475-486.

6. V. Suresh, M. Kanthimathi, P. Thanikaivelan and J. R. Rao, J. Clean. Prod., 2001, 9,

483-491.

7. V. J. Sundar, J. Raghava Rao and C. Muralidharan, J. Clean. Prod., 2002, 10, 69-74.

8. M. Fabbricino, B. Naviglio, G. Tortora and L. d'Antonio, J. Environ. Manag., 2013, 117,

1-6.

9. J. R. Rao, B. Chandrasekaran, B. U. Nair and T. Ramasami, J. Sci. Ind. Res., 2002, 61,

912-926.

10. A. Bacardit, J. M. Morera, L. Oll, E. Bartol and M. Dolors Borrs, Chemosphere, 2008,

73, 820-824.

11. T. Ramasami, C. Muralidharan, V. J. Sundar and V. S. S. Rao, J. Am. Leather Chem.

Assoc., 2001, 96, 61-66.

12. S. Saravanabhavan, R. Aravindhan, P. Thanikaivelan, J. R. Rao and B. U. Nair, Green

Chem., 2003, 5, 707-714.

16
Page 17 of 31 RSC Advances
View Article Online
DOI: 10.1039/C5RA11740B

13. P. Thanikaivelan, J. R. Rao, B. U. Nair and T. Ramasami, Environ. Sci. Technol., 2003,

37, 2609-2617.

14. S. Saravanabhavan, P. Thanikaivelan, J. R. Rao, B. Chandrasekarn, B. U. Nair and T.

Ramasami, J. Am. Leather Chem. Assoc., 2008, 103, 303-313.


Published on 24 July 2015. Downloaded by UNIVERSITY OF OTAGO on 27/07/2015 06:50:19.

15. S. Saravanabhavan, P. Thanikaivelan, J. R. Rao, B. U. Nair and T. Ramasami, Environ.

RSC Advances Accepted Manuscript


Sci. Technol., 2006, 40, 1069-1075.

16. C. Wu, W. Zhang, X. Liao, Y. Zeng and B. Shi, J Am Leather Chem As, 2014, 109, 176-

183.

17. O. Tnay, I. Kabdali, D. Orhon and G. Cansever, Water Sci. Technol., 1999, 40, 237-

244.

18. R. Bagatin, J. J. Klemes, A. P. Reverberi and D. Huisingh, J Clean Prod, 2014, 77, 1-9.

19. S. Silambarasan, R. Aravindhan, J. R. Rao and P. Thanikaivelan, J Clean Prod, 2015, 87,

567-572.

20. V. Chagne, F. Silvestre and A. Gaset, J Am Leather Chem As, 1993, 88, 426-439.

21. F. Silvestre, C. Rocrelle and A. Gaset, J. Am. Leather Chem. Assoc., 1993, 88, 440-452.

22. R. Manfred, W. Eckhard, J. Bjrn and G. Helmut, The Journal of Supercritical Fluids,

2012, 66, 291-296.

23. M. Renner, E. Weidner and G. Brandin, Chemical Engineering Research and Design,

2009, 87, 987-996.

24. K. Alfonsi, J. Colberg, P. J. Dunn, T. Fevig, S. Jennings, T. A. Johnson, H. P. Kleine, C.

Knight, M. A. Nagy and D. A. Perry, Green Chem., 2008, 10, 31-36.

25. C. Capello, U. Fischer and K. Hungerbuhler, Green Chem, 2007, 9, 927-934.

17
RSC Advances Page 18 of 31
View Article Online
DOI: 10.1039/C5RA11740B

26. L. S. Clesceri, A. E. Greenberg and R. R. Trussell, American Public Health Association,

Washington, DC, 1989.

27. IUC8, J. Soc. Leather Technol. Chem., 1998, 82, 200-208.

28. A. Oumedjbeur and O. Thomas, Analusis, 1989, 17, 221.


Published on 24 July 2015. Downloaded by UNIVERSITY OF OTAGO on 27/07/2015 06:50:19.

29. P. Echlin, Academic Press, London, 1971.

RSC Advances Accepted Manuscript


30. IUP2, J. Soc. Leather Technol. Chem., 2000, 84, 303-309.

31. IUP8, J. Soc. Leather Technol. Chem., 2000, 84, 327-329.

32. SLP9, J. Soc. Leather Technol. Chem., 1996, Northampton.

33. IUP6, J. Soc. Leather Technol. Chem., 2000, 84, 317-321.

18
Page 19 of 31 RSC Advances
View Article Online
DOI: 10.1039/C5RA11740B

Table 1

Results of the preliminary trials using ethanol, ethyl acetate and ethyl lactate solvents employing

pickle-based and pickle-less chrome tanning processes


Published on 24 July 2015. Downloaded by UNIVERSITY OF OTAGO on 27/07/2015 06:50:19.

RSC Advances Accepted Manuscript


Parameters Ethanol Ethyl acetate Ethyl lactate

Chrome tanned
leather (Pickle-
based)

Comparable to No color issues, slightly Greenish blue color,


conventional wet blue coarse grain, slight swelling effect, Slightly
Visual assessment
color, no swelling, good swelling, reasonable coarse grain, reasonable
penetration. penetration. penetration.
Cr2O3 % (dry
5.470.18 3.50.12 3.920.15
weight basis)

Chrome tanned
leather (Pickle-
less)

Comparable to
No color issues, slightly
conventional pickle-less Bluish green color, coarse
Visual coarse grain, slight
processed wet blue grain, swelling effect,
Assessment swelling, reasonable
color, no swelling, good reasonable penetration.
penetration.
penetration.

Cr2O3 % (dry
6.450.21 4.350.16 4.760.14
weight basis)

19
RSC Advances Page 20 of 31
View Article Online
DOI: 10.1039/C5RA11740B

Table 2

Exhaustion, chromium distribution and shrinkage temperature data of pickle-based and pickle-

less chrome tanning in ethanol and water medium


Published on 24 July 2015. Downloaded by UNIVERSITY OF OTAGO on 27/07/2015 06:50:19.

RSC Advances Accepted Manuscript


Exhaustion of Cr2O3 % (dry weight basis) Shrinkage
Sample chromium Temperature
(%) Butt Neck Belly (C)

CP 772 5.12 5.09 5.10 1042

EP 873 5.47 5.45 5.46 1081

CPL 912 6.20 6.16 6.17 1061

EPL 953 6.45 6.42 6.43 1082


CP Control pickle-based; EP Experimental pickle-based; CPL Control pickle-less; EPL
Experimental pickle-less.

20
Page 21 of 31 RSC Advances
View Article Online
DOI: 10.1039/C5RA11740B

Table 3

Analytical data on leaching studies in control (C) and experimental (E) chrome tanned leathers

Parameters EPL CPL EP CP

Cr2O3 (%) in chrome


Published on 24 July 2015. Downloaded by UNIVERSITY OF OTAGO on 27/07/2015 06:50:19.

tanned leather before

RSC Advances Accepted Manuscript


6.430.20 6.170.22 5.460.19 5.100.16
leaching (dry weight
basis)
Leaching of Cr2O3 from
chrome tanned leather Solvent Water Water Solvent Water Water
(%)
1.57 1.87 2.17 0.98 1.49 1.3
Cr2O3 (%) in chrome
tanned leather after
6.320.19 6.050.18 5.410.21 5.040.20
leaching (dry weight
basis)
CP Control pickle-based; EP Experimental pickle-based; CPL Control pickle-less; EPL
Experimental pickle-less.

21
RSC Advances Page 22 of 31
View Article Online
DOI: 10.1039/C5RA11740B

Table 4
Organoleptic assessment data of the control (C) and experimental (E) chrome tanned leathers

Parameters EPL CPL EP CP


Published on 24 July 2015. Downloaded by UNIVERSITY OF OTAGO on 27/07/2015 06:50:19.

Color Good Good Excellent Good

RSC Advances Accepted Manuscript


Grain smoothness Excellent Good Excellent Good

Fullness Fuller Good Fuller Good

Wrinkles More Less Less Less

CP Control pickle-based; EP Experimental pickle-based; CPL Control pickle-less; EPL


Experimental pickle-less.

On a scale of 0 to 10, the qualitative descriptors such as excellent, good, average and poor are
weighed as 9, 7 good 8, 4 average 6 and 3, respectively. While the terms such as fuller,
more and less are weighed as 9, 7 more 8 and 4 less 6, respectively. Higher numbers
indicate better properties except wrinkles.

22
Page 23 of 31 RSC Advances
View Article Online
DOI: 10.1039/C5RA11740B

Table 5

Composite liquor analysis for control (C) and experimental (E) chrome tanning

Emission load (kg/ton of raw


Volume of material processed)
Published on 24 July 2015. Downloaded by UNIVERSITY OF OTAGO on 27/07/2015 06:50:19.

COD BOD TS effluent


Samples
(mg/L) (mg/L) (mg/L) (l/ton of raw

RSC Advances Accepted Manuscript


material) COD BOD TS

CP 12950 2950 7378 2463 31.8 7.2 18.2


EP 11150 2320 4296 2450 27.3 5.7 10.5
CPL 17855 4580 8622 1882 33.6 8.6 16.2
EPL 10650 2650 3784 2336 24.8 6.2 8.8
CP Control pickle-based; EP Experimental pickle-based; CPL Control pickle-less; EPL
Experimental pickle-less.

Composite liquors were collected from chrome tanning up to post tanning

23
RSC Advances Page 24 of 31
View Article Online
DOI: 10.1039/C5RA11740B

Table 6
Physical properties of crust leathers

Properties EP CP EPL CPL


Published on 24 July 2015. Downloaded by UNIVERSITY OF OTAGO on 27/07/2015 06:50:19.

Tensile strength (N/mm2) 20.51.5 21.12.0 21.91.8 20.21.6

RSC Advances Accepted Manuscript


Elongation at break (%) 45.31.4 46.31.8 47.72.5 45.32.8
Tear strength (N/mm) 33.01.2 29.41.5 30.21.4 30.92.0
Grain crack strength (kg) 221 241 200.5 222
Distention at grain crack
6.90.3 7.70.4 7.00.1 7.40.2
(mm)

CP Control pickle-based; EP Experimental pickle-based; CPL Control pickle-less; EPL


Experimental pickle-less.

24
Page 25 of 31 RSC Advances
View Article Online
DOI: 10.1039/C5RA11740B

Table 7
Data on recycling of the spent ethanol liquor in the pickle-based chrome tanning process

Second batch Third batch


Parameters First batch
(1st Recycle) (2nd Recycle)
Volume of
spent ethanol
Published on 24 July 2015. Downloaded by UNIVERSITY OF OTAGO on 27/07/2015 06:50:19.

64.7 60 63.2
liquor

RSC Advances Accepted Manuscript


collected (%)
BCS (%)
present in the
total volume 0.71 0.78 0.88
of spent
ethanol liquor
BCS (%) offer 7 6.29 6.22

Fresh ethanol
added (%) 100 35.3 40

Photographic
images of
chrome tanned
leathers

Shrinkage
temperature 106 108 109
(oC)

25
RSC Advances Page 26 of 31
View Article Online
DOI: 10.1039/C5RA11740B

Figure Captions
Fig. 1. Digital images of control and experimental chrome tanned leathers and their respective

process liquors from (a) pickle-less chrome tanning in ethanol medium (b) pickle-less chrome

tanning in water medium (c) pickle-based chrome tanning in ethanol medium and (d) pickle-
Published on 24 July 2015. Downloaded by UNIVERSITY OF OTAGO on 27/07/2015 06:50:19.

based chrome tanning in water medium

RSC Advances Accepted Manuscript


Fig. 2. Scanning electron microscopic images of showing the surface control and experimental

chrome tanned leathers from (a) pickle-based (b) pickle-less chrome tanning in ethanol medium

and (c) pickled-based chrome tanning in water medium

Fig. 3. Scanning electron microscopic images showing he cross section of control and

experimental chrome tanned leathers from (a) pickle-based and (b) pickle-less chrome tanning in

ethanol medium and (c) pickle-based chrome tanning in water medium

Fig. 4. Organoleptic properties of control and experimental crust leathers processed through (a)

pickle-based and (b) pickle-less chrome tanning

26
Published on 24 July 2015. Downloaded by UNIVERSITY OF OTAGO on 27/07/2015 06:50:19.
Page 27 of 31

Fig. 1.

27
RSC Advances
DOI: 10.1039/C5RA11740B
View Article Online

RSC Advances Accepted Manuscript


Published on 24 July 2015. Downloaded by UNIVERSITY OF OTAGO on 27/07/2015 06:50:19.

Fig. 2.

28
RSC Advances
DOI: 10.1039/C5RA11740B
View Article Online

RSC Advances Accepted Manuscript


Page 28 of 31
Published on 24 July 2015. Downloaded by UNIVERSITY OF OTAGO on 27/07/2015 06:50:19.
Page 29 of 31

Fig. 3.

29
RSC Advances
DOI: 10.1039/C5RA11740B
View Article Online

RSC Advances Accepted Manuscript


Published on 24 July 2015. Downloaded by UNIVERSITY OF OTAGO on 27/07/2015 06:50:19.

Fig. 4.

30
RSC Advances
DOI: 10.1039/C5RA11740B
View Article Online

RSC Advances Accepted Manuscript


Page 30 of 31
Page 31 of 31 RSC Advances
View Article Online
DOI: 10.1039/C5RA11740B

Table of Contents Entry


Published on 24 July 2015. Downloaded by UNIVERSITY OF OTAGO on 27/07/2015 06:50:19.

RSC Advances Accepted Manuscript


Waterless chrome tanning in ethanol medium is reported for leather making with comparable
properties and shrinkage temperature, low chromium leaching, high exhaustion along with
possibility of recycling.