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Valorization of Tannery Limed Fleshings Through Fat Extraction: An


Approach to Utilize By-Product

Article  in  Waste and Biomass Valorization · June 2017


DOI: 10.1007/s12649-016-9705-z

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Waste Biomass Valor (2017) 8:1219–1224
DOI 10.1007/s12649-016-9705-z

ORIGINAL PAPER

Valorization of Tannery Limed Fleshings Through Fat


Extraction: An Approach to Utilize By-Product
Md. Abul Hashem1 • Md. Shahruk Nur-A-Tomal1

Received: 4 May 2016 / Accepted: 19 September 2016 / Published online: 24 September 2016
Ó Springer Science+Business Media Dordrecht 2016

Abstract The present work is intended to develop a fat also contribute a significant reduction in the environmental
extraction method from the limed fleshings for soap pro- impact of inevitable solid waste and decrease the costs
duction. In leather processing, just after washing, following associated with disposal.
the liming process, swollen pelts (lime treated hide/skin)
have to pass through an operation to remove the remaining Keywords Tannery solid waste  Limed fleshings 
fat and flesh from the flesh side in order to improve the Environment  Fat  By-product  Soap
diffusion of chemicals into pelt is known as fleshing.
Fleshing is the indispensable mechanical operations in
leather processing where substantial amounts of Introduction
inevitable solid waste (termed as fleshings) are produced.
Generally, fleshings are kept indiscriminately nearly the Cleaner production has become a critical issue for the
industrial area as green, which has negative effects on the industrial sectors, especially the leather sector to regulate
environment including human health. It contains a con- environmental obligations. Therefore, tanneries are faced
siderable amount of fat, which could be a great source for with dual obligations: (1) using fewer chemicals more
soap production. To extract fat, firstly collected cowhide effectively, and (2) improving the treatment technologies
fleshings were delimed with boric acid and hydrochloric of all the forms of process residues [1]. The leather sector
acid for 5–6 h. The delimed fleshings were heated in a is one of the most export-oriented sectors of Bangladesh,
water bath to separate fat from its structure. The optimized which plays an important role in the national economy.
extraction conditions were: temperature 75 °C; time 3 h; According to the Export Promotion Bureau, in the fiscal
without agitation. It was estimated that 6.2 % (dry weight) year 2015–2016 leather sector earned US$1.21 billion by
fat was extractable and yearly 638.6 MT fat could be exporting leather, leather products, and footwear [2]. But
extracted only from the cowhide fleshings in Bangladesh. due to generating the vigorous amount of environmental
Finally, soap was prepared from the extracted fat by pollutants, the tannery has been categorized as ‘red’ cate-
saponification using sodium hydroxide. The soap was sol- gory industry [3].
uble in distilled water, which has good lathering and Tannery waste generation, disposal, and management
cleansing power. The process could be optimized for large- are causing serious problems to survive tannery, especially
scale production, which would be allowed to produce a in Bangladesh. Tannery produces a huge amount of envi-
new product for the commercial use. The approach could ronmental pollutants in the form of solid, liquid and gas-
eous besides it consumes substantial amounts of energy.
The approaches of tannery waste management applied are
& Md. Abul Hashem not sufficient; considerable portions of such solid waste are
hashem_518@yahoo.com; mahashem@le.kuet.ac.bd used for landfills [4].
1 Leather processing (tanning) is a complex procedure
Department of Leather Engineering, Khulna University of
Engineering and Technology (KUET), Khulna 9203, comprising of several technological steps to shield the raw
Bangladesh hide/skin against microbiological degradation as well as to

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1220 Waste Biomass Valor (2017) 8:1219–1224

stabilize collagen with defined tanning agents which pro- Fleshings are composed of various constituents, e.g. sub-
duce a significant amount of waste. A group of researchers cutaneous tissue, fat and flesh among them fat content is
reported that every 10 kg of raw hide/skin processing 4–18 % [11] although the fat content varies according to the
converts only 2 kg of raw materials into leather and more type of animal, feeding, climate and flaying method.
than 6 kg is generated as solid wastes [5]. Of course, Many researchers have investigated to utilize fleshings
generation of solid waste is related to the characteristics of to produce feed ingredients [12], compost [13], biogas
the raw material and manufacturing process of hide/skin. [10, 14], and biodiesel [15–17]. Few literatures present for
There are 220 tanneries in Bangladesh; most of them are extraction of fat from the fleshings and using it for soap
located at Hazaribagh, Dhaka. Daily 100 tons solid waste making [18].
is produced from the tannery in the form of trimmings of The objective of this work was to optimize fat extraction
finished leather, shaving dust, hairs, trimmed animal flesh process from the fleshings of cowhide and to utilize the
skin/hide which contaminate the soil and water [6]. Most of extracted fat in new products e.g. soap, glycerin etc. pro-
the tannery solid wastes are generated from pre-tanning duction. The initiative could reduce the pollution load
operations, especially in fleshing operation. generated by the tannery and also produce more commer-
In tannery, firstly raw hide/skin undergoes the operation cially useable products.
so-called unhairing and liming (commonly known as lim-
ing). In conventional liming operation, sodium sulfide and
lime are used to remove keratinous substances (hair, wool, Materials and Methods
epidermis, etc.), interfibrillary proteins (albumins, globu-
lins etc.) [7]. After liming, pelt (lime treated hide/skin) has Materials
to pass through an operation known as ‘Fleshing’. Fleshing
is one of the most indispensable mechanical operations in Cowhide fleshings were collected from SAF Leather
leather processing where substantial amounts of Industries Ltd., Jessore, Bangladesh just after fleshing
inevitable solid waste (termed as fleshings) are produced. operation in a polyethylene bag and brought back to the
The ‘fleshing operation’ involves cutting or removing the laboratory immediately for experimentation. Chemicals
unwanted part from the flesh side of pelt to improve the which are generally used in the tannery were used for the
diffusion of tanning agents and chemical uptake into pelt experiments. Boric acid (commercial grade), hydrochloric
from the flesh side. It is not possible to omit the fleshing acid (commercial grade), sodium hydroxide (HACH, USA)
operation as skipping it causes chemical wastage, as well and sodium chloride (edible) were used to obtain different
as good quality leather, could not be produced. It is action. Reagents which were used to determine total fat,
reported that fleshings are the 50–60 % of total solid iodine value, saponification value, and acid value, were
wastes generated in the tanning industry [8]. purchased from Merck Limited (India).
In Bangladesh, yearly 33.80 thousand tons wet salted
cowhide and 24.80 thousand tons wet salted goatskin are Characterization of Fleshings
taken for leather production in which 10.3 9 103 MT
fleshings from the wet salted cowhide and 9.8 9 103 MT pH, moisture, and total fat content of the collected fleshings
fleshings from the wet salted goatskin are generated during were quantified in the laboratory. Moisture content (%) and
fleshing operation [9]. The produced a huge amount of total fat (%) was determined using standard methods as
fleshings is kept indiscriminately inside or outside the described in literature [19]. The pH was determined fol-
industrial area as green (without treatment). Generally, lowing method as described in literature [9]. Liquid was
tanneries collect fleshings in wheelbarrows and dump collected by squeezing the fleshings; the obtained liquid’s
nearby tannery area. The fleshings are dumped at the western pH was recorded with a pH meter (UPH-314, UNILAB,
part of Hazaribagh near Dhaka-Narayanganj-Demra (DND) USA). Before pH measuring, the pH meter was calibrated
dam. As stated, fleshings contain proteinaceous substances using the standard solutions of pH 4.0, 7.0 and 9.0. To
that are hydrolyzed to amino acids through proteolytic determine the moisture content of the fleshings, about 5 g
bacteria; amino acids are further hydrolyzed by bacteria, fleshings were heated at 103 ± 2 °C in drying oven until
which liberate gaseous ammonia (NH3), hydrogen (H2), constant weight was obtained. The moisture content was
carbon dioxide (CO2), volatile fatty acids (VFAs) etc., that determined by calculating the % ratio of weight difference
are directly merged to the air [10]. The VFAs help to gen- of wet and dried fleshings to the weight of wet fleshings.
erate toxic hydrogen sulfide (H2S) gas from the fleshings. To determine the total fat content in the fleshings, firstly
Individuals of the tannery area are frequently inhaled the the fat was extracted from the fleshings by Soxhlet
liberated gaseous substances and suffering in difficulties. extractor using ethanol as solvent. After extraction of fat
Fleshings also have a negative effect on water and soil. from the fleshings, the mixture of fat and ethanol was

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Waste Biomass Valor (2017) 8:1219–1224 1221

transferred into a distilling flask. The ethanol was evapo- extraction time, and agitation, so that higher amount along
rated from the distilling flask by heating at drying oven with better quality fat could be attained for large scale
until constant weight was obtained. The dry weight of total extraction. The experiments performed for optimization of
fat was calculated by the following Eq. (1). fat extraction are shown in Table 1. The optimized condi-
W1  W2 tions were established by investigating the percentage and
Extracted fatð%Þ ¼  100 ð1Þ the acid value of the extracted fat from the fleshings. The
W3
amount of extracting fat (%) was determined as discussed in
W1 = Weight of the distilling flask with extracted fat after the previous section (characterization of fleshings).
drying; W2 = Weight of the blank distilling flask; W3 = The acid value of extracting fat was determined by
Weight of the fleshings taken in Soxhlet extractor after drying. following ISO EN 3682 standard method. A standard acid–
base titration with a standard solution of 1.0 M potassium
Deliming of Fleshings hydroxide solution was performed to measure the acid
value.
The collected fleshings were washed with water to remove
unbound/free lime. Fleshings were chopped with knife into Preparation of Soap
small size to facilitate the next operation. The fleshings
were delimed with 2 % (w/w) boric acid for about 5–6 h to The extracted fat (20 g) was taken in a beaker (250 mL)
remove chemically bound lime. The pH of delimed flesh- and heated to melt. Then 20 % sodium hydroxide (25 mL)
ings was adjusted to 6–7 by treating with the diluted was poured, the mixture was constantly heated and stirred
hydrochloric acid and further washed with water. on a magnetic stirring hotplate at 80–100 °C temperature to
speed up the saponification process. Because of heating,
Extraction of Fat from Cowhide Fleshings some of the solvent (water) was evaporated, so water was
added to the beaker in order to maintain the same volume.
The delimed fleshings were subjected to heating with water After saponifying fat with sodium hydroxide, the liquid
(water: fleshings = 1:1) in a beaker in water bath for 1–5 h. was become stringy and muddy looking before it was
After clearly separation of the fat from the fleshings, the turned uniformly into a clear mixture of soap and glycerin.
mixture was transferred to a separating funnel and finally the After 6–8 h, the froth no longer rised and large white
fat was separated from the aqueous phase. The residual bubbles popped on the surface, the end of saponification
water, in fat was then distilled off. The extracted fat is shown was determined by ribbon test and taste test [20].
in Fig. 1. The physicochemical parameters such as iodine After completing saponification, the soap solution was
value and saponification value of the extracted fat were poured into saturated sodium chloride (100 mL) solution in
determined by the following DIN 53241/IP 84/81, and ISO a beaker (500 mL) and stirred with a stirring rod. The soap
3657 standard methods respectively. was coagulated into a solid mass and floated on the surface
of the solution. Then beaker was placed into an ice-water
Optimization of Extraction Process bath. The solution was then filtered using a wire screen
(instead of filter paper) to collect soap. The soap was then
Assays were carried out to optimize the extraction process rinsed twice with ice-water (10 mL) to remove the excess
by varying the parameters like water bath temperature, sodium hydroxide. Once the rinsed soap has been drip
dried, it is moved to a paper towel to finish drying. Then
the soap was dried and it was allowed for curing for several
days.

Table 1 Factors of fat extraction from fleshings and its experimental


levels
Temperature (°C) Time (h) Agitation

55 1 Yes
65 2 No
75 3
85 4
95 5
Fig. 1 Extracted cowhide fat

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1222 Waste Biomass Valor (2017) 8:1219–1224

Properties of Soap operation. Therefore, it was necessary to neutralize flesh-


ings by means of deliming to eliminate sodium sulfide and
Determination of Solubility lime. Fleshings contained 9.1 % fat, which designates that
they could be used as raw material for other industries as a
The solubility of the soap in water was examined following source of fat. The simple technique could be employed to
method as described in literature [21]. 1 g soap and 10 mL extract fat from the fleshings.
distilled water were taken into a test tube. Then the soap
and water were mixed well and observations were made to Optimization of Extraction Process
determine the solubility level.
The results obtained from assays to determine the effect of
Determination of pH agitation to extract fat from the fleshings are represented in
Fig. 2. A negative result was perceived with agitation.
The soap (about 1 g) was dissolved in distilled water Agitation increased the percentage of extracted fat, but
(10 mL) in a beaker and the pH of the soap solution was contrarily increased the acid value, i.e. contributed con-
measured by using the pH meter (UPH-314, UNILAB, tamination of free fatty acid which was undesirable. With
USA). agitation leads to degrading fat, thus, significantly acid
value was increased. The best extraction of fat was attained
Determination of Lathering Power without agitation.
Experiments were carried out to determine the optimum
2 mL of distilled water was added into a test tube. An equal time for extraction of fat. Figure 3 discloses the effect of
amount of soap solution was added to test tube and shaken extraction time, which indicates that with the increase of
vigorously by placing a stopper of the tube and generation time the percentage of extracted fat was increased signifi-
of permanent lather and lasting at least in 30 s was cantly to a certain level beyond this small increase, was
observed. encountered and an acid value of extracted fat was
increased expressively. As beyond certain extraction time,
Determination of Cleansing Power the actual little amount of fat was extracted oppositely the
extracted fat gets degraded consequently acid value was
A drop of used brake oil was placed on a separate thin strip increased. According to the analysis outcomes, 3 h was
of filter paper. It was made sure that the strip of filter paper selected as the optimal extraction time.
was fitted in the test tube. Filter paper with oil spot was The water bath temperature had a significant effect on
placed in the tube containing soap in water. The tube was extraction of fat, which is represented in Fig. 4. It is
shaken well and made sure that the filter paper was observed that the acid value of extracting fat was increased
immersed in the solution. After 2 min, the filter paper was noticeably in elevated temperature, which indicates
removed and rinsed with tap water. The observation was degradation of fat is more at a higher temperature. At the
made that whether if the oil of the filter paper strips get same time with increasing temperature, the percentage of
washed out or not. extracting fat was increased extensively to a certain level;

80 Extracted fat (%) 80


Results and Discussion Acid value (mg/g)
70 70
Characteristics of Fleshings
Extracted fat (%)

Acid value (mg/g)

60 60

Table 2 shows the characteristics of the collected fleshings. 50 50

It seems that pH ([12) was highly alkaline because of the 40 40


introduction of lime and sodium sulfide in liming
30 30

20 20
Table 2 Characteristics of untreated cowhide fleshings
10 10
Parameter Value
0 0
pH 12.2 ± 0.1 No Yes
Total fat (%) 9.1 ± 0.2 Agitation
Moisture content (%) 66.3 ± 0.4
Fig. 2 Effect of agitation on fat extraction

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Waste Biomass Valor (2017) 8:1219–1224 1223

Extracted fat (%) 80


Table 3 Properties of the extracted cowhide fat and comparison with
80
Acid value (mg/g) others
70 70
Parameters This study [22] [23]

Acid value (mg/g)


60 60
Extracted fat (%)

Physical state at room temperature Solid – –


50 50 Iodine value (mg I2/g fat) 52.1 ± 0.6 40.86 43.7
Saponification value (mg KOH/g fat) 188.5 ± 0.9 198.63 175.0
40 40
Acid value (mg KOH/g fat) 32.0 ± 0.4 73.96 2.5
30 30

20 20

10 10
Table 4 Properties of the soap
0 0
1 2 3 4 5 Parameters Observation
Extraction time (h) Color Milky white
Solubility in water Soluble
Fig. 3 Effect of time on fat extraction
pH 8–9
Lathering power Good
80 Extracted fat (%) 80 Cleansing Power Good
Acid value (mg/g)
70 70

Researches on this issue could contribute a significant


Acid value (mg/g)
Extracted fat (%)

60 60
valorization of inevitable solid wastes besides reduction of
50 50
its environmental impact.
40 40
Characteristics of Extracted Fat
30 30

20 20 The physicochemical parameters of extracting fat and


10 10 comparison with other researchers’ outcome are shown in
Table 3. The extracting fat was solid in physical state. It
0 0
55 65 75 85 95 seems that the saponification value, iodine value and acid
Temperature (°C) value were satisfactory comparing to others. It was clear
from the characteristics of extracted fat that the extracting
Fig. 4 Effect of temperature on fat extraction fat was suitable for various products e.g. soap.

beyond this level slight increase in the percentage of Properties of the Soap
extracting fat was observed. Based on the experimental
data, temperature 75 °C was considered as optimal The results obtained from various tests performed with the
extraction time. soap are represented in Table 4. The soap was milky white
Since the observations, it could be concluded that the in color. It was soluble in distilled water. The pH of the
best extraction conditions were found: temperature 75 °C; prepared soap was 8–9, which was within the preselected
time 3 h; without agitation. limit. Healthy skin has a pH 5.4–5.9 [24]. The cleaning
ability of soap to neutralize fatty oils for better removal
Estimation of Extracted Fat depends on the alkalinity of the soap. Higher the pH can
damage the antibacterial barrier and lipid lamellae of the
It was calculated that 6.2 % (dry weight) fats were epidermis which results the skin of dryness as well as
extractable at the optimized conditions. It was estimated entering irritants and allergens [25]. The pH was higher
that yearly 638.6 MT fat could be extracted only from the because of incomplete alkali hydrolysis resulting from the
cowhide fleshings. Extraction of fats from the fleshings process of saponification. The pH could be achieved more
could be a potential source for by-product production. satisfactory level by adding fat or oil, glycerin, etc. The
Simple technologies could allow extracting fat as input for soap was good lathering and cleansing power. The results
other processing industries in the form of raw material, reveal that the extracted fat from the cowhide fleshings
which will consent to produce useful end products. were suitable for soap production. Better quality soap could

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