WATERLESS WET WHITE TANNING

A PROJECT REPORT

Submitted by

S.SATHIYAMOORTHY(2016306040)

In partial fulfillment for the award of the degree

Of

BACHELOR OF TECHNOLOGY

IN

LEATHER TECHNOLOGY

ALAGAPPA COLLEGE OF TECHNOLOGY

ANNA UNIVERSITY: CHENNAI 600025

OCTOBER 2019
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WATERLESS WET WHITE TANNING

A PROJECT REPORT

Submitted by

S.SATHIYAMOORTHY(2016306040)

In partial fulfillment for the award of the degree

Of

BACHELOR OF TECHNOLOGY

IN

LEATHER TECHNOLOGY

ALAGAPPA COLLEGE OF TECHNOLOGY

ANNA UNIVERSITY: CHENNAI 600025

OCTOBER 2019
 3

ABSTRACT

An approach towards waterless tanning is crucial to address present challenges

faced by humanity such as global warming and the depletion of water resources.
Here, green solvent alternatives to water such as ethanol, ethyl acetate and ethyl
lactate were employed for both pickle-based and pickle-less chrome tanning. The
results show that an ethanol medium appears to be the best solvent for wet white
tanning in terms of color, tanning agents uptake and other bulk properties of
tanned leathers. Extensive studies indicate that wet white tanning in the ethanol
medium leads to a higher exhaustion (87% for pickle-based and 95% for pickle-
less), better chromium content, distribution and shrinkage temperature, and low
tanning agents leaching in tanned leathers compared to water mediated tanning.
Both visual and electron microscopic analyses demonstrate a comparable grain
structure and fiber architecture in tanned and crust leathers. Similarly, the strength
and organoleptic properties of crust leathers are also comparable between ethanol
and water mediated tanning. The process enables the reduction of COD, BOD
and TS loads in the composite liquor by 14–26, 21–28 and 42–46%, respectively.
The leather properties are not altered upon recycling of the tanning agents
containing ethanol liquor up to two times. These results suggest that it is possible
to replace water with ethanol for wet white tanning, which offers great potential
for sustainable solvent recycling.
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TABLE OF CONTENT

CHAPTER NO TITLE PAGE NO

1 ABSTRACT 3

5
2 INTRODUCTION

2.1 Introduction about the project 5

2.2 Scope of the project 7
2.3 Objective 7
2.4 Expected outcomes 8

3 LITERATURE SURVEY 10
3.1 Characteristics 12

4 MATERIALS AND METHODS 9

4.1 Material 14
4.2 Selection of combination system 14
4.3 Receipe 16

5 CONCLUSION 16

6 REFERENCES 17
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CHAPTER 1
INTRODUCTION ABOUT THE PROJECT

1.1. INTRODUCTION

The present environment conscientious world is driving researchers to explore eco-

friendly products and processes. The leather industry, similar to most other potential
polluting industries, is continuing to implement its environmentally friendly
procedures in proportion to the regulatory legislation. The comprehensive concern
on the negative impact of the leather industries on the environment has forced
tanners to pay attention to the processes that would reduce the problems related to
pollution. Alternatives to water based wet white tanning are being sought actively
owing to the stringent regulations. Any alternative tanning system should not only
satisfy environmental criteria but also should be able to match the properties of wet
white tanned leathers. There has been an ongoing search for other metal ions to
replace water based wet white tanning. Various waterless wet white tannages have
been reported in the recent past. The combination tanning of other metal ions with
ethanol, as a waterless approach, has been shown to exhibit better leather
characteristics with much less environmental impact. In the light of total replacement
of water, combination tanning of other metal ions with ethanol as a waterless
approach has been explored in the present study. The alternative tanning system
should not only match the properties of wet white leather but should also add more
value to the leather in terms of special properties imparted by the chosen solvent. In
today's fashion world pastel shades are more sought after colors. Also, the
applications for wet white are increasing, especially in the automotive industry. In
Europe, automobile manufactures insist that their upholstery is made exclusively
from wet white. Various metals, which could produce white leathers are aluminium,
zirconium, zinc, silica. Aluminium and zinc combination has been shown to produce
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leathers with Ts above 90ºC. Zirconium oxychloride based tanning has also been
shown to produce good quality waterless wet white leathers. waterless wet white
pretanning as a technique to reduce water usage has been reported. Wet white in
earlier times referred to pretanning with aluminium salts. Use of silicon dioxide and
sodium silicate for manufacture of waterless wet white leathers have also been
reported. Gluteraldehyde pretannage and modified gluteraldehyde have also been
used for manufacture of waterless wet white leathers. Silica based tanning produces
white leathers hence, the concept of waterless wet white tanning as a potential
alternative to water based wet white tanning is appealing. Silica tannage also
produces leathers with softness and fluffiness because of the gelling nature of silica.
However, the drawbacks associated with the solo tanning with silica are the lack of
desired shrinkage temperature and strength properties in the leathers. Aluminium
tanning produces waterless wet white leather with shrinkage temperature of 80ºC.
Also, aluminium tanned leathers are known to produce rich dyeability. Phosphonium
based tanning salts have been studied in the past. Leathers using THPS have been
found to give Ts of about 90ºC with excellent strength characteristics.

Since tanning contribute to nearly 80% of the total water, technologies are now
focused on tanning methodologies to overcome this problem. In this context, a new
tanning system based on aluminium-silica-phosphonium has been developed as a
water-free wet white approach. This approach not only eliminates water during
tanning but also seeks advantages in avoiding pollutants and gaining environmental
acceptability. In this present investigation, silica in combination with aluminium has
been studied. The leathers obtained were characterized for their physical strength
characteristics, organoleptic properties and the environmental benefits.
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1.2. SCOPE OF THE PROJECT:

Leather industry has to cope with major environmental problems because of the
polluting processes. A world bank report has placed the leather industry in the ninth
place when considering environmental impact. Therefore, increasing the
environmental efficiency in the leather sector is the major aim of leather, auxillary
materials equipment manufacturers. The development of tanning method and new
technologies is required to cope with increasingly higher environmental pressure on
the current tanning methods such as tanning with water. The original contribution of
this work in solving the above problems has involved the use of ethanol.

1.3. OBJECTIVE:

All tanners are facing the same problems of minimizing the environmental and
health impact of their processes when selling into the global market.

Regulatory pressures oblige tanners to make continuous improvements in the

processing operations. The regulatory authorities and consumers are looking more
closely at whether hazardous substances, such as certain preservatives are present in
leather and leather products.

Closer monitoring of this aspect has revealed that leather and leather products
sometimes contain some hazardous substances. After 10 years the whole world
facing the depletion of water scarity. In order to avoid this issue, waterless wet white
leathers are produced by combinations of synthetic tannins, vegetable tannins,
glutaraldehydes and minerals, such as aluminum and zirconium.

Wet white tanning allows making water-free leathers with the same equipment
alternative to ethanol.
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To reduce the water in the wet white tanning to make the waterless wet white leather
with the help of solvent such as ethanol.

1.4. EXPECTED OUTCOME:

The reaction of aluminum and ethanol forms aluminum tri ethoxide, Al(OC2H5)3,
but the reaction is fairly slow at room temperature, particularly if the aluminum is
anodized.

In the presence of any moisture it decomposes into aluminum hydroxide and

ethanol.
The Safety Data Sheet indicates that aluminum tri ethoxide is both flammable and
can cause "severe skin burns and eye damage", but in atmospheric conditions it
likely decomposes as quickly as it forms, so the main adverse effect will be the
corrosion of the aluminum, covering it with a white crust of Al2O3 (I've seen this
happen to an aluminum lid on a container used for ethanol).

UNH has posted a chart that shows that anodized aluminum is resistant to ethanol
attack, but does not state at what temperature, so you may have to experiment to see
if it suitable in your application.
BTW, many other alcohols react in a similar manner, such as isopropanol, which
forms aluminium iso propoxide with aluminum.

Chemical reaction:

Al + C2H5OH Al(OC2H5)

( Ethanol ) (Aluminium tri ethoxide).

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Property of aluminium tri ethoxide (C6H5AlO3):

Appearance: white powder.
Solubility in water: reacts violently.
Better reducing agent.

Advantages of wet white tanning:

Waterless wet-white leathers are lighter in color and can be converted into pastel
shade leathers.

Shrinking temperatures of at least 70°C.

High softness.

Good lightness.

Natural sensation.

Pleasant touch.

Beauty over the time.

High-performance leather can be obtained.

Leather can be burnt without the hazard of chromium (VI) formation.

Disadvantages of wet white tanning:

Slightly higher production cost compared to water based wet white tanning.

Requires more controls.

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CHAPTER 2

2.1 LITERATURE SURVEY:

2.1.1. wet white leather processing: A new combination tanning system,

N.NISHAD FATHIMA et al, JALCA 101 (2), 58-65,2006.

OBSERVATION:

Eco friendly leather (chrome free leather).

TANNING AGENTS: Three separate combinations

viz silica-Al, silica-THPS-Al, silica-THPS.

THPS: Increase the strength properties, shrinkage temperature 90ºc.

SILICA: Produce softness and fullness.

ALUMINIUM: Produce white leather with shrinkage temperature 80ºc. Reduction

of COD by 41% and TS by 67%.

DISADVANTAGES: Slightly higher production.

Require more controls.

2.1.2. New wet white tanning agents and technology, MARIAN crudu et al,
Proceedings of ICAMS, 27-29,2012.

OBSERVATION:

Also eco-friendly leather.

TANNING AGENTS: Titanium replace the chromium (III).

TITANIUM: To increase the environmental efficiency of the leather sector .

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Produce smooth grain full and supple.

Shrinkage temperature – 68-82ºc.

ADVANTAGE: Easy to apply.

Cheap to produce.

2.1.3. Improving the properties of wet white leather characteristics by using

collagen based biopolymer, Bahri basaran et al, XXXIII IULTCS Congress,
nov, 24th-27th, Novo hamburgo/brazil, 2015.

OBSERVATION:

Improving the methods of waste processing to make them more efficient.

Key words: wet white, collagen Hydrolysate, leather, organic polymer.

Wet white Tannages consist of zirconium (IV) and aluminium (III) salts with high
durability and resistance.

Also organic alternatives.

Study with many optimistic results aimed at the improvement of leather performance
criteria through the combination of collagen based biopolymers with tanning agents.

Result: With modified tanning method, imperfections of wet white leather properties
were enhanced.

2.1.4. A comprehensive evaluation of physical and environmental

performances for wet white leather manufacture, Jiabo shi et al , jcp
139,1512-1519,2016.
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OBSERVATION:
TANNING PROCESS: Tannic acid and Laponite Nano clay.

Shrinkage temperature above 86ºc.

ICP-AES measurements indicate that laponite can be evenly and tightly bound
within collagen.

Confirmed by SEM-EDX.LCA-Life Cycle Assessment.

RESULT: Wet white leather have reasonable good physical properties.

Wet white tanning process exhibits reduced environmental impacts in ADP, GWP
and HTP impacts, but higher GWP excluding biogenic carbon and energy
consumption.

2.2. CHARACTERISTICS:

2.2.1 DETERMINATION OF SHRINKAGE TEMPERATURE:

The shrinkage temperature, which is a measure of hydrothermal stability of leather,

was determined using a shrinkage meter.20 Each value reported is an average of
three measurements.

2.2.2. EVALUATION OF ORGANOLEPTIC PROPERTIES:

Crust leathers were assessed for softness, grain smoothness, fullness and general
appearance by tactile evaluation. Experienced tanners rated the leathers in a scale
of 0-10points for each functional property.
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2.2.3. PHYSICAL TESTING OF LEATHER SAMPLES:

The samples for physical testing were obtained as per IULTCS methods.21
The samples were conditioned at 804oF and 65 2 % R.H. for 48 hrs. Physical
properties such as tensile strength, % elongation, tear strength and grain crack
strength were investigated as per standard procedures. 22-24 Each value
reported is an average of four (2 along
the backbone, 2 across the backbone) measurements.

2.2.4. SCANNING ELECTRON MICROSCOPIC ANALYSIS:

Samples from waterless wet white tanned control crust and silica-aluminium tanned
crust leathers were cut from the official sampling position. The specimens were then
coated with gold using Edwards E306 sputter coater. A Leica Cambridge Stereo scan
440 scanning electron microscope was used for the analysis. The micrographs for
the obtained by operating the SEM at an accelerating voltage of 20 KV with
different lower and higher magnification levels.

2.2.5. ANALYSIS OF SPENT TAN LIQUOR:

Spent tan liquors from experimental leather processing were collected and analyzed
for COD and TS (dried at 103-105oCfor 1 hr) as per the standard procedures. From
this emission were calculated by multiplying concentration(mg/Lit) with volume of
effluent (lit) per tonne of raw skins processed. The values reported are average of
three experiments along with their standard deviations.

CHAPTER 3
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MATERIALS AND METHOD:

3.1 MATERIAL:

Wet salted goatskins (5-6 sq. ft area) were chosen as raw materials for waterless wet
white leather production. All chemicals used for leather processing were of
commercial grade without water by using of ethanol.

3.1.1 PROPERTIES OF ETHANOL:

Ethanol is the only hydrocarbon which is soluble in water in all proportions while
ethanoic acid is miscible with water in all proportions. It is soluble in water in all
proportions. It has a distinct smell and burning taste. It burns in air with pale yellow
flame.

Pure ethanol is a flammable, colorless liquid with a boiling point of 78.5° C. Its low
melting point of -114.5° C allows it to be used in antifreeze products. It has a pleasant
odor reminiscent of whiskey. Its density is 789 g/l about 20% less than that of water.

3.2 SELECTION OF COMBINATION SYSTEM:

Two different combination systems were chosen viz. Silica-Aluminium and

Titanium-Aluminium. Selection of percentages of aluminium sulphate and titanium
based agent synthesis (on pelt weight basis) for better shrinkage and leather
characteristics was carried out .All the experiments were carried out on
conventionally processed pickled goatskins.

3.2.1 SILICA-ALUMINIUM COMBINATION TANNING:

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Single pickled goat skins were taken for trial. Pickled skins were treated with varying
amounts (1-2.5%) of Al2O3 with different combinations of ligands ((i) sodium
tartarate and hexamethylene tetramine,(ii) sodium citrate and hexamethylene
tetramine and (iii)sodium tartarate, sodium citrate and hexamethylenetetramine
(HMT)).The ratio of metal : ligand was maintained at 1:0.1. Drum was run for 1 hr.
10% sodium metasilicate(previously neutralized to a pH 4.5 - 5.0) was then added
and the drum run for another 1 hr 30 min. Then, basification was carried out by the
addition of 2% sodium bicarbonate(amount varied from 1.5-3.0% depending on the
%Al2O3 offer) and 15-30% ethanol (percentages based on fleshed weight) in four
instalments at an interval of 15 min. Finally, the drum was run for 1 hr and the pH
was checked to be 3.8-4.0. Then, the leathers were piled for 24 hrs. Next day, the
hydro thermal stability of the waterless wet tanned leathers was measured using a
shrinkage tester.

3.2.2 ALUMINIUM-TITANIUM COMBINATION TANNING:

Single pickled goat skins were taken for trial. Pickled skins were treated with varying
amounts (1-2.5%) of Al2O3 with Titanium.. Drum was run for 1 hr. Then,
basification was carried out by the addition of 2% sodium bicarbonate(amount
varied from 1.5-3.0% depending on the %Al2O3 offer) and 15-30%
ethanol(percentages based on fleshed weight) in four instalments at an interval of 15
min. Finally, the drum was run for 1 hr and the pH was checked to be 3.8-4.0. Then,
the leathers were piled for 24 hrs. Next day, the hydrothermal stability of the
waterless wet tanned leathers was measured using a shrinkage tester.
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TABLE 1
Control waterless wet white tanning process
Solution % Time Remarks

Pickle liquor 50 Check pH 2.8-3

Al2O3 2.5 60 min Check penetration

Ethanol 50 10 min

Sodium formate 1 10 min

Sodium bicarbonate 1 Check pH 3.8-4.0

CHAPTER 4

CONCLUSION:

Anew tanning system without water is the need of the hour for sustainable growth
in the leather industry. A tanning using silica, aluminium, titanium and ethanol has
been explored. The amount of ethanol has been selected as 50%, to get better leather
characteristics. The shrinkage temperature of the leathers obtained from the silica-
aluminium combination is 86oC. A reduction in the COD and TS loads of the
effluent liquor has been observed for a pickle-less combination. Scanning electron
microscopy studies show good fiber coating owing to thepresence of silica. The
strength and tactile properties of the experimental leathers are well above the
stipulated norms.
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CHAPTER 5

REFERENCE:

1. Ward, G. J.; Wet white pretanning- A technique for reducing chrome usage.
JALCA 90, 142, 1995.

2. Wren, S. and Saddington, M.; Wet white- pretanning with the 'Derugan' system.
JALCA 90, 146, 1995.

3.Wolf, G., Breth, M., Carle, J. and Igl, G.; New developments in wet white tanning
technology. JALCA 96, 111, 2001.

4.N.Nishad Fathima, T. Prem Kumar, D. Ravi kumar, J. Raghava Rao and B. Unni
Nair.; wet white leather processing: A new combination tanning process. JALCA,
VOL. 100, 2005.

5. M.M. Taylor, J. Lee, L.P.BUMANLAG, E. Hernandez Balada, and E.M. Brown.;

Treatments to enhance properties of chrome-free (wet white) leather. JALCA, VOL,
105, 2010.

6. GABRIEL Zainescu, DANA CORNA Deselnicu, IOANNIS ioannids, PETRE

VOICU CRUDU.P.; New versatile conversion technology for wet white waste
transformation to biofertilisers. Proceedings of the 4 th Conference on Advanced
Materials and Systems-ICAMS 2012, 71-76,2012.

7. Bahri Basaran1, Aykut Sancaklı2, Yusuf Dilek.; Improving The Properties of

Wet-White Tanned Leather Characteristics By Using Collagen-Based Biopolymer.
XXXIII IULTCS Congress November, 24th – 27th , 2015 Novo Hamburgo/Brazil
1048.
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8. Siwei, yunhang Zeng, Wenhua Zhang, Yanan Wang, Bi shi.; Inverse chrome
tanning technology based on wet white tanned by Al-Zr complex tanning agent. J
Am leather Chem Assoc 110, 114-121, 2015.

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

Waterless tanning: chrome tanning in ethanol and its derivatives. RSC Advances
Issue 82, 2015.

10. Jiabo Shi, Rita Pung, Jun Sang, Wei Lin.; A comprehensive evaluation of
physical and environmental performances for wet-white leather manufacture. JCP
139(2016) 1512-1519.

11. Jiabo Shi, Chunhua Wang, Liyuan Hu, Yuanhang Xiao, Wei Lin.; Novel Wet-
White Tanning Approach Based on Laponite Clay Nanoparticles for Reduced
Formaldehyde Release and Improved Physical Performances. ACS Sustainable
Chem. Eng. 2019,7, 1, 1195-1201.

12. Julian Osgood1, Michel Deville2 and Wolfram Scholz3.; new wet white/chrome
free process offering significant Environmental and physical property advantages
from beam house To crust. XXXV. Congress of IULTCS, 2019.