Evaluation of the Production of Oxalic Acid from Some Solid Industrial

Wastes in Nigeria
Theresa. I Edewor-Kuponiyi; Omotayo. S Amuda
Department of Pure and Applied Chemistry,
Ladoke Akintola University of Technology, Ogbomoso, Nigeria.
ibitheresa@yahoo.com
Abstract A variety of methods exist for the disposing of solid agro-industrial
wastes generated during the processing of agricultural commodities. These include
land application, composting, open burning and placement in a land fill. But agroindustry is an important source of methane which is obtained from the wastewater
and the solid organic wastes. Other important chemicals such as potassium
hydroxide and oxalic acid can be obtained from this industry. Cocoa pods, palm
bunches, and plantain peels were processed for the production of KOH which was
used for the isolation of oxalic acid from saw dust. A total average weight of 2.81 X
1011 tons per annum of KOH can be generated from these agro-industrial wastes
which can be used to produce 0.56 X 106 tons of oxalic acid per annum.
Key Words Oxalic acid; KOH; Saw dust; Cocoa pods; palm bunches; plantain
peels

Introduction

The term agricultural residues refer to wastes obtained from agriculture produce. They consist of
unutilized excesses or residues from processing of raw agricultural products such as cocoa, plantain,
banana, palm bunches, etc. Here the residues referred to are those end-products of production and
consumption that have not been used, recycled or salvaged. They are the non-product flows of material
and energy whose economic values at the present level of knowledge are less than the cost of
collection and transformation for use, and they are therefore discarded as wastes (Taiwo et al., 2001).
A large percentage of the wastes generated in Nigeria are from agriculture (Edewor et al., 1990).
The generation of residues from agriculture is a function of many factors. The quantity and quality of
the residues will depend upon the type of raw materials, the production processes, the product mix, the
production rate, the production output specifications, the prices of inputs and product, the regulations
affecting product quality and use, and any constraints imposed upon discharge of residues. The
residues generated are materials and energy. The material residues may be gaseous, liquid or solid or a
combination of forms. In some industrialized countries these wastes have been converted into some
useful products for the improvement of energy output and farm products. Other products such as gas,
oil and char have also been obtained (Guw et al., 2001). In Nigeria, these agricultural residues are
obtained in large quantities from cocoa, plantain, banana, palm bunches plantations and there is
indiscriminate dumping and burning of these residues leading to the release of probable harmful
volatile compounds into the atmosphere, soil and water (Edewor et al., 1985).

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Edewor-Kuponiyi and Amuda

Due to industrialization the traditional balance between agriculture and rural industry was disrupted as
a result of increased specialization in the production of primary commodities that are further processed
in the metropolitan countries. In Nigeria there is high percentage of small land owners who use labour
intensive traditional farming techniques resulting in high post-harvest losses. These losses are due to
inadequate storage facilities and practices; generation of enormous quantities of agricultural residues
that are inadequately utilized, either because they are widely dispersed and readily available, or
because there is a lack of technological information on how to use them. Another industrial waste that
is produced in large quantity in Nigeria is saw dust. The saw mills are constantly producing saw dust
which are burnt continually thereby releasing some harmful gases (e.g. carbon monoxide) into the
environment. Therefore this present study is evaluating the possible utilization of these agricultural
residues and saw dust in the production of useful chemicals such as oxalic acid; which is useful as
reducing agents for photography, bleaching, and rust removal. It is widely used as a purifying agent in
pharmaceutical industry, precipitating agent in rare-earth metal processing, bleaching agent in textile
and wood industry, rust-remover for metal treatment, grinding agent, waste water treatment, acid rinse
in laundries and removing scale from automobile radiators (Kovacs et al., 2004). In discussing the
evaluation, attempts will be made to investigate the forest or wood reserve in Nigeria. The
approximate quantities of saw dust and agro-industrial wastes (palm bunches, cocoa pods and plantain
peels) needed to produce a certain quantity of oxalic acid per annum in Nigeria.

Materials and method

2.1

Sample collection and preparation

The materials used are Saw dust, plantain peels, cocoa pods, palm bunches. Saw dust was collected
from the saw mill at Ojo, Lagos state, Nigeria The saw dust was filtered using a mesh size 0.001mm in
order to obtain very fine powder while the solid agricultural wastes (plantain peels, palm bunches and
cocoa pods) were collected in groups of five from five different locations in Lagos, Ogun and Ondo
States, Nigeria. The agricultural waste materials were washed thoroughly with tap water to get rid of
sand and dirt. The types of solid wastes, their codes and locations of collection are given in Table 1.
All chemicals were obtained from sigma chemicals, London and were used as supplied.
Table 1: Agro-industrial wastes samples, codes and location of collection
Wastes samples
Cocoa pods

Palm bunches

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Sample code

Location

State

CP1

Ota

Ogun

CP2

Ifo

Ogun

CP3

Yewa

Ogun

CP4

Idare

Ondo

CP5

Okitipupa

Ondo

PB1

Ipokia

Ogun

PB2

Ifekowajo

Ogun

PB3

Lagos mainland

Lagos

PB4

Badagry

Lagos

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Wastes samples

International Journal of Basic and Applied Science,

Vol. 02, No. 01, July 2013, pp. 91-97

Sample code

Plantain peels

2.2

Location

State

PB5

Yewa

Ogun

PP1

Lagos mainland

Lagos

PP2

Ikeja

Lagos

PP3

Mushin

Lagos

PP4

Yewa

Ogun

PP5

Ipokia

Ogun

Ash content

Standard method for determination of ash content was employed. 500g each of the washed and dried
wastes materials were taken from each group and placed in an oven to ash at a temperature of about
550oC. The average weight percentages of the ashes obtained for each sample are shown in Table 2.
2.3

Preparation of the basic solution

Each ash was successively extracted with distilled water until the extract obtained was neutral to
litmus paper. The volume of filtrate obtained from each sample were pulled together and reduced by
heating to 2L (Murov & Stedjee, 2009).
2.4

Molarity of filtrate

Standard solution of potassium hydroxide was prepared and used to standardize the sulfuric acid that
was used to titrate 25 mL of each of the filtrates. The various end points obtained were used to
calculate the molarity of each of the samples (McMurry & Fay, 2010).
2.5

Isolation of oxalic acid

500 g of saw dust was added to the total volume of the filtrates obtained from all the samples. The
mixture was heated gently for 3 hours at a temperature of about 150oC. It was cooled and then 0.5 g of
alkaline KMnO4 was added gradually while stirring the mixture. The mixture was heated for 45
minutes at a temperature of 170oC, later cooled and the resulting brownish residue was dissolved in 2
L of distilled water. The mixture was filtered and 371 g of CaO added to the filtrate. The filtrate was
acidified using 58 mL of aqueous H2SO4, heated for 20 mins and filtered hot. The hot filtrate was
allowed to cool, forming crystals of oxalic acid at the bottom of the flask. The crystals were
recrystalized using ethanol. The pure crystals were dried in the oven and the yield and melting point
determined. The melting point was compared with that of standard oxalic acid (Rigano et al., 2007).
2.6

Thin layer chromatography

A solution of the isolated compound was prepared in water and spotted alongside with a standard
oxalic acid on an already coated Merck silica gel G plate. It was developed using the solvent mixture

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Vol. 02, No. 01, July 2013, pp. 91-97

Edewor-Kuponiyi and Amuda

benzene: acetic acid: water (5: 4: 1; v: v: v). The developed plate was placed in an iodine tank to
visualize the spots (Murov & Stedjee, 2009).

Results

The average weight percent of oxalic acid isolated was 26.89%. The isolated oxalic acid has melting
point of 186-188oC. It gave the same Rf value with the standard (0.45). Table 2 shows the quantity and
molarity of KOH isolated from agro-industrial wastes. Palm bunch gave a highest yield of 58.80%
with a molarity of 0.192 while cocoa pod has the least yield of 40.16%.
Table 2: Average weight of wastes samples, average weight percent and molarities of KOH obtained
from solid agro industrial wastes

Sample

Average dry
weight of
sample (g)

average
weight of
ash (%)

average
KOH/
sample (%)

average
KOH/ ash
(%)

Average
volume of
filtrate (mL)

Average
molarity

Palm bunch

500

29.00

15.80

58.62

2187.50

0.192

Cocoa pod

500

60.75

12.15

40.16

3300.00

0.133

Plantain peel

500

59.38

11.88

53.57

3922.50

0.184

Table 3 shows the average quantity of agro-industrial wastes and saw dust that can be generated per
annum. The average weight percent of oxalic acid isolated from 500 g saw dust using a combination of
the KOH obtained from the agro-industrial wastes is 26.89%.
Table 3: Quantities of some Agro-industrial wastes and saw dust that can be generated per annum in
Nigeria
Sample

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Average quantity produced per annum (tonnes)

Palm bunch

9.00 X 1011

Cocoa pod

10.81 X 1011

Plantain peel

Negligible

Saw dust

2.10 X 106

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Vol. 02, No. 01, July 2013, pp. 91-97

Table 4: Quantity and cost of raw materials imported for the production of 0.8 X10 6 tons of oxalic
acid
*Quantity (X 106 tons)

*Cost (X 106 $)

KOH

1.60

78.88

CaO

1.012

63.80

KMnO4

0.004

0.28

H2SO4

2.14

1.54

Raw materials

*: Sigma-aldrich: Biochemicals and Reagents for Life Science Research, 2010-1011.

Table 5: Quantity and cost of raw materials imported for the production of 0.8 X10 6 tons of oxalic
acid
Oxalic acid

Cost (X 106 $)

Locally produced

222.82

Imported

78.30

From industrial wastes

00.00

Discussion

Oxalic acid is an important chemical in industries such as laundry, pharmaceutical, hospitals, etc. The
isolation and purification of this chemical from waste agricultural materials and saw dust is very
feasible. The utilization of these waste materials will aid in the reduction of toxic compounds
discharged into the environment and can supplement the quantity of oxalic acid imported into the
country.
In a well run oil mill, it is expected that each 100 tons of Full fruit bunches processed produces about
72-76% of waste at various stages (FAO, 2011). The solid wastes that are generated from the milling
operations are empty fruit bunches, palm kernel shell and palm fibre. These waste if not utilized pose a
disposal problem. Some ways of disposing these wastes are (a) through incineration in a boiler for the
production of process heat and power for the oil production, (b) land fill, (c) compositing and (d) open
burning.
The FAO projection for Nigeria for the year 2010 for the production of palm oil was put at 842 X 106
tons (FAO, 2003). This means that the quantity of waste that would be generated is 48 X 10 11 tons.
This volume of wastes can be used to generate about 1.49784 X 1011 tons of potassium hydroxide.
Cocoa is the leading non-oil foreign exchange earner for Nigeria. Since the abolition of the Nigeria
Cocoa Board the growth rate in this sector has slowed down (Nkang et al., 2007). However, Nigeria
has the potential to produce over 3.0 X 105 tons of cocoa bean per year. The FAO projection for the
year 2010 for Nigeria was put at 3.85 X 105 tons (FAO, 2003). If this quantity of cocoa is produced, it
will generate about 10.81 X 1011 tons of cocoa pods as waste which can be used to generate about
1.313415 X 1011 tons of potassium hydroxide.

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Edewor-Kuponiyi and Amuda

The level of plantain production in Nigeria has been low and inconsistent (FAO, 2003), although it is
becoming a significant economic activity for income generation for both large scale and small holder
farmers especially in the south south zone where it is the primary commodity for investment. This
shows that there is a gradual increase in the waste generated. Although this quantity is insignificant
now, in the near future it can also be included in the production of potassium hydroxide.
Nigerias forests can be divided into two principal categories: woodlands and forests of the savannah
regions (about four-fifths of the countrys forest area). These areas are the primary source of fuel and
poles while the rain forests of the southern humid zone supply almost all domestic timber and lumber
with fuel wood as by-product. Nigeria uses approximately 52.39 Tgdm/yr of fuel wood for the period
20002007. Out of these about 60% is wasted as firewood and charcoal and 40% used for wood based
materials (Bogner et al., 2007). Out of the 40% for the wood based material, 10% comes out as saw
dust which is equivalent to 21 X 106 tons of saw dust that can be generated.
The total quantity of potassium hydroxide that can be generated from palm bunches and cocoa pods is
put at approximately 2.81 X 1011 tons. This is taking into consideration that the potassium hydroxide
obtained from plantain peels is negligible. This quantity of potassium hydroxide if fused with 21 X106
tons of saw dust can generate about 0.56 X 106 tons of oxalic acid. Taking into consideration the cost
of manufacturing and importation of oxalic acid, it was observed that it is more expensive to
manufacture than to import (Table 4) oxalic acid. The oxalic acid produced from the agro-industrial
wastes and saw dust can be used to augment the imported oxalic acid.
The volume and composition of agro-industrial wastes could be reduced if there were technological
means for converting them into some useable products (e.g., oxalic acid), if the value of the
subsequent product were to exceed the costs of conversion, or if it were considered to be sound
governmental policy to encourage recovery and reuse. In addition, waste minimization, recycling and
reuse represent an important and increasing potential for indirect reduction of Green-house Gas
emission. If the residues can be utilized for human benefits, then they can no longer be referred to as
wastes but new resources that can augment already existing limited resources. The utilization of a
portion or all of the wastes offers the possibility of a beneficial use for the residues as opposed to the
current methods of disposal and relocation. Incineration of these wastes produces carbon dioxide
which pollutes the atmosphere, their use as landfill produces methane which is a small contributor to
global greenhouse gas emission.

Conclusion and Recommendation

48 X 1011 tons of palm bunches can be used to generate about 1.50 X 1011 tons of potassium hydroxide
while 10.81 X 1011 tons of waste cocoa pods can be used to generate about 1.31 X 1011 tons of
potassium hydroxide. Combining these quantities of potassium hydroxide with 21 X106 tons of saw
dust can generate about 0.56 X 106 tons of oxalic acid.
Efforts are needed to develop technology and institutional arrangements to utilize better the residue
from agricultural production and saw dust from saw mills. The need is to consider these residues as
potential resources rather than as undesirable wastes. Thus the better use of residues from agricultural
production and saw mills can help accomplish two important objectives: (a) better utilization of
existing resources to meet human needs, and (b) reduction of potential environmental problems caused
by such residues.

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Vol. 02, No. 01, July 2013, pp. 91-97

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