Waste Management 66 (2017) 190–195

Contents lists available at ScienceDirect

Waste Management
journal homepage: www.elsevier.com/locate/wasman

Soap production: A green prospective

Sandra Félix a,⇑, Joana Araújo a, Ana Maria Pires a,b, Ana Cláudia Sousa a
a
Universidade Atlântica – Centro de Estudos, Sociedade, Organizações e Bem-Estar (CESOB), Antiga Fábrica da Pólvora de Barcarena 2730-036 Barcarena, Oeiras, Portugal
b
Faculdade de Ciências da Universidade de Lisboa – Centre for Ecology, Evolution and Environmental Changes (Ce3C), Campo Grande, 1749-016 Lisboa, Portugal

a r t i c l e i n f o a b s t r a c t

Article history: A green prospective based on the reuse of waste materials such as almond shells, orange peel and used
Received 17 September 2016 cooking oil to manufacture soap is presented.
Revised 15 March 2017 In Portugal, thousands of tons of waste are generated from used cooking oil and production of nut
Accepted 20 April 2017
shells’ residues is growing every year. In addition, the high consumption of citrus fruits, oranges in par-
Available online 25 April 2017
ticular, generates large amounts of citrus peel. Therefore, it is necessary to diversify reuse mechanisms of
these wastes, in order to make them back into raw materials. Complying with this trend, this work was
Keywords:
carried out by processing and grinding almond shells, treating used oil, processing orange peels and
Soap production
Environment
extracting limonene, formulating and producing soap, and performing an acceptance study of the final
Waste recycling product. Results validated a high potential of the idea in the field of environmental education, so it can
Applied chemistry be replicated in practical classes. It can also be useful for waste management, and it can support the
Consumer chemistry development of community projects on an ecological approach.
Green chemistry Ó 2017 Elsevier Ltd. All rights reserved.

1. Introduction
This work aimed to obtain a useful, cheap and good quality
green soap, using waste products as major raw materials. Such
studies are of great importance for replication in practical classes,
and inspiring community projects intended to improve recycling
on an ecological approach: on one hand contributing to families’
economy, and on the other hand reducing the environmental
impact of these residues and stimulating the use of healthier prod-
ucts, which can be relevant issues from the public health point of
view.
1.1. Residues, their reuse and recycling
The encounters and mismatches between man and nature have
always been present and have always strongly influenced our lives
and health. Connections, cycles in nature, renewable energy and
ethical issues are already present in environmental projects, how-
ever, due to the imbalance in our world, it becomes increasingly
necessary to explore new perspectives, focusing not only in
environmental education, but also and specially in the concerns
of public health.
Population growth as well as changes in consumption patterns
and lifestyle have been the main drives of an increased waste
production which causes several impacts on environment and
⇑ Corresponding author.
E-mail address: sfelix@uatlantica.pt (S. Félix).
public health (Herva et al., 2014). In the last decades the waste
management became a major issue, and several processes have
been devised for organic waste treatment, such as composting.
However, despite its low economic cost and waste reduction in
landfills, some products cannot be composted (e.g. oils) and others
can inhibit this biological process (e.g. citrus peel) (DR, 2009; Ruiz
and Flotats, 2014).
According to official data, in Portugal each individual consumes
daily ca. 40 g of vegetable oil, leading to the production of great
amounts of residues (INE, 2012). Portuguese legislation establishes
the regime of management for used cooking oils. It also refers that
each year 43–65 thousand tons of cooking oil residues are pro-
duced, mostly from the domestic sector (62%), but also from restau-
rants and hotels (37%) and from the food industry (1%) (DR, 2009).
Despite the European Community politics for energy forecasts that
a large amount of these residues can be collected and converted
into biodiesel (EC, 2009), data provided from the Portuguese Envi-
ronment Agency (APA – Agência Portuguesa do Ambiente) indicates
that only 340 tons of used cooking oil were collected in 2012, and
370 tons were collected in 2013 (APA, 2013, 2014), which is frankly
far from the proposed goals in this area.
Traditionally Portugal has produced and consumed nuts for
centuries, as part of its Mediterranean diet culture. In recent years
nutrition recommendations have also raised nut’s consumption,
resulting in increased residues’ production. Therefore, recycling
these shells is increasingly becoming an important issue (Yang,
2015). Ranking after apples, oranges are the second most produced
and consumed fruit in continental Portugal (OMAIAA, nd; INE,

http://dx.doi.org/10.1016/j.wasman.2017.04.036
0956-053X/Ó 2017 Elsevier Ltd. All rights reserved.
 S. Félix et al. / Waste Management 66 (2017) 190–195
2013). However, and because of its acidity, citrus peel cannot be
used in composting, generating large amounts of non-processed
waste (Ruiz and Flotats, 2014).
In this connection the manufacturing of this kind of products
using otherwise unusable wastes becomes more attractive both
economically and ecologically.
1.2. Oils and saponification
Saponification reaction, also known as the cold process for mak-
ing soap, is the alkaline hydrolysis of triacylglycerols. These esters
are the major constituents of vegetable oils and animal fats; they
can react with a strong mineral base like sodium hydroxide, in
aqueous medium, to produce the sodium salts of the hydrolysed
free fatty acids (the opaque soap) and glycerol (Fig. 1) (Panda,
2003; Hill, 2004; Mabrouk, 2005).
Historically, soap production used to be a method to reuse ani-
mal fats, lard and sebum. Nowadays, most people use industrial
soap but, mainly in poor regions, there are families and communi-
ties that produce their own soap bars (Onyegbado et al., 2002;
Konkol and Rasmussen, 2015). In fact, there are regions where the
access to a simple washing hand soap is not assured, which highly
increases the risk of infections (Francke and Castro, 2013; Madichie,
2016). There is also a growing movement to enhance artisanal pro-
duction of good quality green soap, both because it is considered
better for the skin and for health in general, as well as for reducing
water and carbon footprints (Francke and Castro, 2013).
Nowadays fat sources have become almost exclusively veg-
etable, and include a considerable number of different oils and fats
which, in association with additives, origin soaps with different
characteristics (Grosso, 2016).
Although all animals and vegetables possess a mixture of tria-
cylglycerols and free fatty acids as structural lipids, different spe-
cies, and even different individuals from the same species, have
different lipidic profiles. This means that when vegetable oils are
extracted from a plant, one cannot know the exact ratio triacylglyc-
erols/free fatty acids.
The saponification index of an oil is an important parameter for
the reaction efficiency, which indicates the weight of KOH (potas-
sium hydroxide) in milligrams that is needed to saponify one gram
of that specific oil (Wakita et al., 2014). This index value supports
the decision on a formulation choice in a wide range of possibilities.
1.3. Fragrances and essential oils
An essential oil is a mixture of secondary metabolites from
plants that are responsible for its characteristic odour. It’s a combi-
nation of different aromatic and aliphatic compounds, frequently
terpenes and terpenoids, which composition depends on the plant
species, variety, geographic origin, soil and season (Figueiredo
et al., 2008; Salgueiro et al., 2009).
Current cosmetic products use synthetic fragrances while high
quality cosmetics’ manufacturers choose essential oils. However,
due to their high volatility, organic fixative molecules such as
R1
R2 O OH
O O
OH
NaOH
O + 3 H2O
O HO
O
R3
Fig. 1. Saponification reaction.
191
sucrose, sucrose derivatives, sodium carboxymethyl chitosan,
among others are needed (Jimtaisong and Saewan, 2014).
Following this principle the use of an essential oil is increased
with the use of a further additive which is not essential for soap
cleaning function.
2. Experimental
2.1. Materials and reagents
The recycled waste products used as major raw materials in the
soap formulations were used cooking oil, orange peel and almond
shells.
In some formulations, commercial materials were used, such as
bees wax, olive oil, coconut oil, palm oil and soya lecithin.
Some reagents were also used, namely: ethanol (C2H5OH abso-
lute, Merck), potassium hydroxide (KOH, p.a., Merck), sodium chlo-
ride (NaCl, p.a., Sharlau), sodium hydroxide (NaOH, pellets, p.a.,
Riedel-de Häen). An agate mill was used to grind the almond shells.
2.2. Almond shells treatment
Almond shells were involved in a strong plastic bag and
smashed with a hammer. After soaking overnight, the resulting
pieces were washed several times with tap water, until clear water
was obtained, and after that dried at 60 °C. After thoroughly dried
(2–3 days), shells were finely ground using an agate mill and the
resulting powder was sifted through a 210 mm sieve to remove
the bulkiest grains.
2.3. Cooking oil treatment
Treatment of used cooking oil involves three phases: filtration,
for the removing of particulate matter; washing, for the extrac-
tion of non-visible particles in suspension; and deodorization,
for the removal of molecules that give the oil some odour
(Araújo et al., 2013).
Although there were no visible particles in suspension, the used
cooking oil was filtered under vacuum for removing eventual par-
ticulate matter. A volume of 100 mL of filtered oil was washed
twice using 100 mL of warm (50 °C) brine solution (10 % NaCl),
in a 250 mL separation funnel. In each operation, the aqueous
phase was removed after 1 h separating. Washed oil was then
poured in a beaker and deodorized by agitation with almond shells
powder for another hour. This procedure was performed by first
using 3 g of powder, which was filtered after this, and then
repeated using 2 g of powder.
2.4. Determination of the oil saponification index
Saponification index was determined both on the used cooking
oil and on the olive oil. In each case, 1 g of oil was rigorously
weighed in a 100 mL round bottom flask. After the addition of
25 mL of KOH alcoholic solution, the mixture was refluxed for
O O O
+ - + -
+ -
+ Na O
+ Na O + Na O
R1 R2 R3
192 S. Félix et al. / Waste Management 66 (2017) 190–195

1 h, and after that was cooled and titrated with 0.5 M HCl in the distilled to being a mixture containing essential oil and water,
presence of phenolphthalein. Blanks were performed using 25 ml and was collected for 2 h.
of KOH alcoholic solution and each assay was performed three The orange essential oil was separated from the water using a
times (Wakita et al., 2014). separation funnel and then stored in a stoppered glass flask.

2.5. Orange essential oil extraction 2.6. Colorants

Orange essential oil was extracted from orange peels by distil-
lation. We took orange peel and removed its internal white part.
The external orange peel was then dried and finely ground; 100 g
were placed in a 1000 mL round bottom flask and suspended in
300 mL of deionized water. The mixture was refluxed and
After the extraction of essential oil, the orange peel was once
more dried in the oven and finely ground, and sifted through a
210 mm sieve. The orange peel powder obtained was used in some
of the formulations as a colorant. Palm oil was also used in some
formulations, giving the soap its natural orange colour (see Fig. 2).

Fig. 2. Orange peel processing. (a) Fresh peels. (b) Dry peels. (c) Ground dry peel. (d) Dry peel, after essential oil extraction. (e1) Orange peel fragments 212 mm. (e2) Orange
peel powder <212 mm.

Table 1
Ingredients and amounts used in the different formulations.

Formulation Cooking oil Olive oil Palm oil Coconut oil Fresh cream Bees wax Soya lecithin Water NaOH
1 30 g – – – – – – 11.4 g 4.05 g
(100%)
2 15 g 15 g – – – – – 11.4 g 4.06 g
(50%) (50%)
3 18 g 7.5 g 4.5 g – – – – 11.4 g 4.08 g
(60%) (25%) (15%)
4 18 g 7.5 g – 4.5 g – – – 11.4 g 4.27 g
(60%) (25%) (15%)
5 15 g 7.5 g – 7.5 g – – – 11.4 g 4.41 g
(50%) (25%) (25%)
6 18 g 7.5 g – – – 4.5 g – 11.4 g 3.56 g
(60%) (25%) (15%)
7 15 g 7.5 g 4.5 g – – 3.0 g – 11.4 g 3.69 g
(50%) (25%) (15%) (10%)
8 18 g 7.5 g – – 4.5 g – – 11.4 g 3.56 g
(60%) (25%) (15%)
9 15 g 7.5 g 4.5 g – 3.0 g – – 11.4 g 3.96 g
(50%) (25%) (15%) (10%)
10 15 g 6.0 g 4.5 g 4.5 g – – – 11.4 g 4.30 g
(50%) (20%) (15%) (15%)
11 15 g 7.5 g 6.0 g – 1.5 g – 11.4 g 4.24 g
(50%) (25%) (20%) (5%)
12 15 g – 7.5 g 7.5 g – 0.9 g – 11.4 g 4.26 g
(48.4%) (24.3%) (24.3%) (3%)
10.1 15 g 6.0 g 4.5 g 4.5 g – 1.8 g – 11.4 g 4.30 g
(47%) (19%) (14%) (14%) (6%)
10.2 15 g 6.0 g 4.5 g 4.5 g – – 1.8 g 11.4 g* 4.30 g
(47%) (19%) (14%) (14%) (6%)
10.3 15 g 6.0 g 4.5 g 4.5 g – – 1.8 g 11.4 g 4.30 g
(47%) (19%) (14%) (14%) (6%)
10.4 15 g 6.0 g 4.5 g 4.5 g – 0.9 g 0.9 g 11.4 g 4.30 g
(47%) (19%) (14%) (14%) (3%) (3%)
*
Water distilled during the extraction process of limonene.
 S. Félix et al. / Waste Management 66 (2017) 190–195 193

2.7. Saponification
2.7.1. General procedure
The oils were rigorously weighed in a beaker (Table 1) and
slightly heated up to complete homogenization. Solid NaOH was
weighed and dissolved in deionized water (or water from essential
oil extraction). When both solutions reached the temperature of
37 °C, the NaOH solution was carefully added to the oils’ solution,
and the mixture was then stirred until it was visibly thickening.
Soya lecithin, when used, was previously hydrated in deionized
water for 1 h. After placing in the moulds, the soaps dried for at
least 48 h, before unmoulding. Maturation processes took around
two weeks, depending on the formulation.
2.7.2. Formulations
Reagents (mass, in grams) used in each formulation are discrim-
inated on Table 1, where oils and additives mass percentages (over
the total mas of oils and additives) are also shown. The soap chosen
for the consumers’ study was that obtained with formulation 10,
using orange essential oil (3% in mass) as the fragrance additive.
3. Results and discussion
washing time optimization. The first one aimed at finding the ideal
waiting time for the separation of both phases, resulting that
longer than 2 h period brought no significant improvement. The
second one consisted in comparing the use of deionized water or
brine solution for the washing process. Brine solution option
achieved total separation on both phases (96%) after 1 h in contrast
with deionized water that required 16 h for the same result.
Despite having been washed, the oil still presented a frying
odour, making the deodorization step strongly important. This
can be done using nuts’ shells, which are porous materials and
can adsorb those molecules with an unpleasant odour. In this par-
ticular case, almond shells powder has been used.
3.2. Determination of saponification index
The used cooking oil was a mixture of sunflower and corn oils, with
unknown exact composition. Therefore, saponification index esti-
mates the amount of free fatty acids present in the oil. For used cook-
ing oil the value was 196.3 mg (KOH)/g (oil), and for olive oil it was
201.9 mg (KOH)/g (oil). As the saponification agent used was NaOH,
the conversion of those values resulted, respectively, in 140.2 mg
(NaOH)/g (used cooking oil) and 144.2 mg (NaOH)/g (olive oil).

3.1. Cooking oil treatment 3.3. Soap formulations

Washing oil with deionized water revealed to be a lengthy pro- Different formulations were tested in order to determine a bet-
cess (Araújo et al., 2013). Therefore, two studies were made for ter one for an efficient and pleasant soap for daily use. Table 2

Table 2
Different soap formulations and respective description.

Formulation description Photo Formulation description Photo

1. Exclusively using recycled cooking 7. Although it was easily shaped
oil, the soap obtained exudes compared to the previous, this
during the maturation process, formulation also led to the
conducting to an unattractive production of non-uniform soap.
appearance

2. This soap presented a uniform 8. This soap was externally hard, but
consistency. However, the amount internally pasty and it also presented
of olive oil used conducts to a an unpleasant odour
longer maturation process

3. Despite the uniform consistency, 9. This formulation produced a soap

palm oil gave a natural orange that was slightly more consistent
coloration, which became than the previous. However, it was
heterogeneous during the still not hard enough and the odour
maturation process was also unpleasant

4. This formulation had a nice 10. This formulation gave birth to

consistency, and a pleasant nice soaps, with the right consistency
appearance but a harder soap and pleasant texture and aroma. This
along maturation process formulation was the selected one

5. This formulation showed similar 11. Reducing the proportion of bees

time of maturation and final wax, this formulation was easily
appearance as formulation 4, shaped compared to nr. 7. Soap
being just slightly harder presented good consistency and a
pleasant appearance

6. This soap showed a reduced 12. This formulation was the only one
maturation time. However, not containing olive oil, presenting a
because bees wax makes the pasty consistency in the early days.
mixture solid too quickly, it was Soya lecithin provided a very uniform
difficult to place it evenly into the appearance to the soap
moulds
194 S. Félix et al. / Waste Management 66 (2017) 190–195

Table 3
Study of the effect of additives in the basis formulation.

Formulation Additive Description Photo

10.1 Bees wax Bees wax
makes the
mixture
solidify too
quickly, being
difficult to put
evenly into the
moulds
10.2 Soya Nice Fig. 3. Soap obtained with formulation 2.
lecithin consistency
Water and
distilled appearance Table 4
during Soap production costs.
limonene
extraction Product Packaging Unit Used Real
price amount cost
10.3 Soya Soap with a
lecithin non-uniform Cooking oil washing estimation 1L 2.00€ 250 g 0.54€
consistency Olive oil 1L 2.99€ 250 g 0.32€
and Coconut oil 200 g 5.99€ 100 g 2.25€
unpleasant Palm oil 500 cm3 3.79€ 75 g 0.71€
appearance Sodium hydroxide 1 kg 6.90 € 75 g 0.49€
Ingredients cost 4.31 €
Energy (30% of ingredients) 1.29 €
10.4 Soya Nice
lecithin consistency
Bees wax and
uniformity,
but with
from the hands after washing. Regarding the hands’ sensation after
unpleasant washing, 31 individuals (77.5%) classified it as pleasant. The least
appearance classified criteria were aroma and foam formation; with 17 indi-
viduals (42.5%) considering it having a pleasant aroma and 14
(35.0%) a tolerable aroma. Only one person (2.5%) referred an
unpleasant aroma for the tested soap. Considering its foam, 18
resumes different formulations tested, their respective description
individuals (45.0%) indicated low or insufficient foam, while 12
and a photo of each obtained soap.
(30.0%) assumed it as sufficient.
Although formulations 2 and 10 were highlighted by their
higher quality, for consumer acceptance study only formulation
10 was considered, due to its shorter maturation time (two weeks). 3.6. Soap cost
Furthermore, formulation 10 combined a better balance concern-
ing production cost, maturation process, washing power, smooth- A simple study has been made in order to estimate the costs
ness, removing ease and hydration. associated to the soap production. Table 4 shows the cost of the
Nevertheless, some further assays using emollient and thicken- commercial raw materials used to produce a batch of 65 soaps,
ing additives were performed with formulation 10. Table 3 pre- using formulation 10, as well as an estimation of the respective
sents these results, which reveal no advantage added from cost of energy.
emollient or thickening agents’ use. From these data, we can estimate that the production of 65
soaps costs around 5.60€, which means that each soap costs about
3.4. Colorants 0.09€. Labor cost is not considered, once this project’s aim was not
to produce a soap to be placed on the market, thus this would not
Orange peel powder was tested as a colorant (at 3%) with for- be really a cost.
mulation 2. These additive’s particles have larger size and higher
density, when compared to other components, which causes it to 4. Conclusions
have low dispersion capacity. This formulation led to a non-
homogeneous soap because the orange peel showed a strong ten- This experience promotes ecological knowledge improvement
dency to settle at the bottom of the mould (Fig. 3). Therefore, by using all the referred waste materials for manufacturing an
although a slightly orange coloration was observed when using everyday soap. The use of almond shells, apart fixing the oil odour,
this additive, it was not present in the final formulation. can act as an exfoliating agent, whereby they can remain in the
soap. In what concerns the soap aroma, an efficient use of the
3.5. Soap evaluation orange essential oil would require the addition of a fixative.
Though not essential, while it does not alter its effectiveness, the
In order to evaluate the soap’s acceptance (formulation 10, addition of this natural fragrance may increase the acceptability
orange essential oil added), anonymous surveys were answered of the soap.
by school community individuals. Inclusion criteria were being Artisanal soaps have become fashionable nowadays, however
over 18 years old, using the soap for hand washing for at least three they are generally considered superior quality goods, produced
consecutive days, and answering all survey questions. Forty ques- with fine raw materials, and therefore expensive. On the contrary,
tionnaires were validated, within which 33 individuals (82.5%) this study shows that by using cooking oil residues, as well as olive
expressed their pleasure to continue using this soap, attributing oil and nuts’ shells which are relatively abundant in Portugal and
it the highest rating for all parameters. Pointing up the good con- other Mediterranean regions, a good quality and cheap green soap
sistency, good cleaning performance, and being easily removed can be produced.
 S. Félix et al. / Waste Management 66 (2017) 190–195
We point out that this work revealed a high acceptance by the
school community, enabling its replication in practical classes with
successful results.
The release of this idea to the community will contribute to the
increment of environmental awareness and scientific literacy. Its
feasibility is reasonable, nevertheless it should be accompanied
by technical support. Therefore, it may be a starting point to
develop community projects that convey recycling and ecological
approach to environmental issues, as well as public health and
local economy.
Acknowledgments
The authors thank all participants who accepted to answer the
questionnaire, as well as Eugénia Esteves and Sara Costa for kindly
reviewing this manuscript.
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