UTILIZATION OF RICE HUSK ASH AS A MAGNETIC NANOCOMPOSITE ADSORBENT

FOR THE REMOVAL OF LEAD (II) IN WASTEWATER

TITLE PAGE

JAMES MATTHEW PAZ LIMPIN

SUBMITTED TO THE FACULTY OF

DEPARTMENT OF CHEMICAL ENGINEERING
COLLEGE OF ENGINEERING AND AGRO-INDUSTRIAL TECHNOLOGY
UNIVERSITY OF THE PHILIPPINES LOS BAÑOS
IN PARTIAL FULFILLMENT OF THE
REQUIREMENTS FOR THE
DEGREE OF

BACHELOR OF SCIENCE IN CHEMICAL ENGINEERING

MAY 2019

This thesis manuscript can be accessed by:

By the general public -

Only after the consultation with author or adviser -
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 II. Review of Related Literature

2.1. Lead as a Heavy Metal Waste

Heavy metals are elements which have high atomic weight and density. They

are natural components of the earth’s crust. The various applications of heavy metals in

agriculture, medicine, industry, and in technological development have caused them to be

unnaturally distributed in the environment. The heavy metal contamination has been

associated with increasing ecological damage and health risks. (Tchounwou et al., 2012;

Jaishankar et al., 2014).

Lead is widely used due to its low melting point, high density, high malleability,

and ductility. In 1923, tetraethyl lead was the first mass-produced lead compound in the

U.S. Production from 1923 to 1964 was 266 million to 148 million kilograms (Jameson et

al., 2003). Despite its various uses, lead is known to have a high degree of toxicity along

with arsenic, chromium, cadmium, and mercury. Lead compounds are emitted as a waste

product in the air, water, and soil. The discharge of lead occurs in processes such as mining,

and fossil-fuel burning. Moreover, it is used in the production of batteries, x-ray devices,

metal pipes, fabric dyes, and ammunitions. Even with the reduction of lead use in

producing paints, pipes, and ceramics, lead is still a prevalent heavy metal waste. A study

in the US estimates that 1.52 million metric tons of lead were used in the United States in

2004 wherein 83% of the usage was in lead-battery production. (Tchounwou et al., 2012).

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 2.2 Physicochemical Properties of Lead

Elemental lead is an odorless bluish-gray metal which is naturally found in

small traces. It has an atomic mass of 207.2 gm/mol and a density of 11.34 g/cm3 .

Moreover, it has a melting point of 327.43o C and a boiling point of 1740o C. Lead is a

very soft and highly malleable; it is chemically stable and resistant to corrosion. In addition,

pure lead is insoluble in water (Abadin et al., 2007).

Lead is used in the form of inorganic and organic compounds. Lead oxide (PbO)

is an inorganic compound used in paint, glass, ceramics, rubber, and plastics. Tetramethyl

lead (Pb(CH3 )4 ) is an organic compound used in augmenting fuel as an antiknock agent.

Lead acetate trihydrate (PbC4 H6 O4 ) is used in chrome pigments and varnishes. Lead is

chemically inert in water. However, its reactivity with water increases in the presence of

moist air. Lead acetate is an example of a compound soluble in water; it is commonly used

in hair dyes and sweeteners (Jameson et al., 2003).

2.3. Lead Toxicity

According to Jaishankar (2014), lead is one of the most common heavy metals

found in wastewater. They can enter the environment through human intervention which

includes sewage discharge points, industrial waste waters, pesticides, and disease control

agents in crops. Due to its chemical properties, lead does not decompose easily and can

accumulate in plants via absorption of lead-containing waters; it also accumulates in

animals which consume contaminated plants. In the cellular level, lead binds to protein

sites in place of the other metals needed such as calcium, magnesium, and iron via ionic

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mechanism; thus, it causes cellular malfunction and toxicity. In plants, lead damages the

chlorophyll and suppresses the overall growth for plants.

Lead can enter the human body in various ways. It can be through physical

contact with lead-contaminated water and soil, inhalation of lead-containing particles in

the air, and ingestion of lead present in water and food. In humans, absorbed lead is rapidly

transported into the blood and soft tissues, causing it to quickly circulate in the body

(Tchounwou et al., 2012; Holm et al., 2002). Depending on the duration and exposure, lead

has many negative effects in the body. It may cause morphological changes, inhibition of

enzyme production, and death. Moreover, harmful levels of lead in the body can damage

neurological and renal functions, resulting to brain and kidney damage. It can also damage

the reproductive and endocrine systems (Holm et al., 2002).

2.4. Analysis of Lead in the Philippines

Vegetables, fruits, crops, seafood, meat, and water may contain significant

amounts of lead. According to Molina (2011), heavy metal analyses were performed in fish

samples collected in Laguna de Bay. The fish samples were bangus, tilapia, kanduli, dalag,

and mamaling. Three sampling stations in major lake areas were uitlized during dry and

wet seasons. The study shows that the fish are not suitable for human consumption due to

elevated levels of lead contamination. Industrial, domestic, and agricultural waste pose as

the sources of lead contamination in Laguna de Bay. The fish consumption was associated

with life time cancer risks. For bangus and tilapia, there were 9 and 3 cancer cases per

100,000 populations respectively.

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 In 2009, study on the assessment of heavy metals was conducted in Manila bay.

The monitoring of the waters was done for 6 months from September to February. Results

show that lead, cadmium, and chromium were evident in fish and macroinvertebrates,

particularly in the liver and muscles. In the fish species collected, the lead content in the

liver ranges from 0.23 to 0.67357 mg/kg, which exceeds the 0.4 mg/kg permissible limit.

The amounts of lead may be due to waste waters discharged in the bay (Su et al., 2009).

Heavy metal lead analysis in Filipino staple food were conducted in the Metro

Manila area. Rice varieties and fish samples were collected. The data were analyzed and

compared with the allowable standard limits by the U.S. E.P.A. (U.S. Environmental

Protection Agency). Results show that the Malagkit and the National Food Authority Rice

Brands have lead content which exceed the 0.5 ppm limit in food. Blood tests conducted

in children and adults have toxic amounts greater than 10 𝜇𝑔/𝑑𝐿 (Solidum, 2014). In

addition, a study on tap water analysis in an office in Manila was conducted. According to

Solidum (2012), the tap water samples analyzed in Manila, Philippines have concentrations

of lead greater than the limits set by the U.S. E.P.A. which is 0.015 ppm.

A study on the determination of Lead Concentration in the Angat River Network

in Bulacan was done in 2014-2015. Water samples in the river from various points were

collected and analyzed. Results show that the legal limit at 0.01 ppm for lead in rivers set

by the W.H.O. is exceeded by 30-fold. Lead may be discharged through factories

established along the river (Estrella et al., 2015).

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 2.5. Methods of Removal of Lead

Chemical Precipitation is the formation of the insoluble solid from the solution

by manipulating the composition of the solvent. In removing Lead (II) from aqueous

solutions, calcium hydroxide is added and then acidified with nitric acid which resulted to

a 99.42% removal rate at the optimum conditions (Kavak, 2013).

Ion exchange reaction is where ionic species exchange between positively and

negatively charged components. This is mostly used in obtaining pure forms of different

chemical species from mixtures. In removing lead, calcium nitrate is used to remove lead

(II) in exchange of the calcium (II) ions (Lalmi et al., 2018).

Adsorption involves the transfer of mass wherein the substance is turned into a

solid phase from a liquid phase and is bound by physical or chemical interaction. It is

applied in adsorbing aqueous pollutants. There are two kinds of adsorption: (1) Chemical

adsorption and (2) physical adsorption. Chemical adsorption is a process wherein the

pollutant is transferred into the surface of the adsorbent and adsorbed via film formation or

intra-particle diffusion. Physical adsorption is the process where the adsorbate binds in the

adsorbent surface due to van der Waals forces of attraction (Khulbe and Matsuura, 2018).

An example of physical adsorption is the use of activated carbon as adsorbent.

2.6. Rice Husk Ash as Adsorbent

Activated carbon can be a highly porous substance when treated usually with

acid for increased adsorption performance. It has a good physico-chemical stability and

high sorption capacity. In addition, it has a large surface area which makes it more porous.

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Activated carbon is the most widely used adsorbent for treating wastewater from harmful

heavy metals such as lead, copper, cadmium, and chromium. Rice husk ash is a good

alternative for an activated carbon adsorbent because it is composed of 32% cellulose, 21%

hemicellulose, 22% lignin and 15% ash. Various studies had shown that rice husk is a good

adsorbent for lead (Hanum et al., 2017).

According to a study done by Hanum (2018), the activated carbon synthesized

from rice husk ash yielded 49.33% carbon content and the adsorption capacity of lead was

0.56731 mg/g with a 54.85% removal efficiency. Another study involved the utilization of

rice husk as adsorbent of lead showed that the surface area of raw rice husk is 2.232 𝑚2 /𝑔

which proves its porosity (Sovattei et al., 2013). In Malaysia, the adsorption capacity of

the adsorbent from rice husk ash was studied. It was found that the adsorption efficiency

in adsorbing lead is 71% when the contact time was increased to 70 minutes, and 86%

when the adsorbent dosage was increased (Aliyah, 2012).

Rice is the staple food of the Filipinos and the estimated production of rice hull

is 2 million tons per year and around 20% of the hull is rice husk. The country has 1.2

million hectares of rice-producing lands which feed every Filipino 100 kilograms of rice

on average. The use of rice husk will provide a cheaper alternative and promote the

utilization of biomass waste (Zafar, 2018).

2.7. Magnetic Nanoparticle Composite Adsorbents

The use of magnetite or iron oxide in increasing the recovery of powdered

adsorbents was done in various studies. According to Juang (2017), the activated carbon

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nanocomposites with high surface area were made recoverable by binding the magnetite

nanoparticles to the adsorbent. The magnetite particles are equally distributed to the

surfaces of the powdered adsorbent thus maintaining the high surface area of the activated

carbon. The adsorbing capacity was decreased by 15% due to magnetization, buy the easy

of recovery has shown the potential application to the removal of toxic substances in

wastewaters.

A study in the synthesis of magnetized activated carbon in the removal of

carbamazepine (toxic organic compound) from municipal wastewater has proven cost-

effective and efficient. The results showed that the maximum removal efficiency achieved

is 93% and the maximum sorption capacity was 182.9 𝑚𝑔/𝑔 (Baghdadi et al., 2016).

Another study has shown that the removal of the organic compound ceftriaxone from

wastewater with the use of magnetized activated carbon achieved a maximum removal

efficiency of 97.18%. In addition, further experimental runs using the recovered adsorbent

were done and the removal efficiency loss was less than 10% (Badi et al., 2018).

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