Adamson University

Ermita, Manila
College of Engineering
Chemical Engineering Department

Research Proposal

Nano-Silica Sulfuric Acid Derived from Corn Cob Ash as

a Green Catalyst for Nitration of Phenol

Proponents:

Cuevas, Nicole A.
Dimaculangan, Jayvee E.
Isuan, Kelly A.
Lopez, Judilyn Grace P.
Palad, Ayra Patricia B.

Co-Adviser:
Francis M. Dela Rosa, R.Ch.

Adviser:
Engr. Erison C. Roque

MOR Professor:
Engr. Kendall Paul A. Laureano
 CHAPTER 1
INTRODUCTION

1.1 The Problem and Its Background

Aromatic nitration is well known as one of the reactions in organic synthesis as the nitro

compounds are very useful in various industrial processes. As long as dyes, explosives,

pharmaceuticals, rubber, wood and industrial chemicals continues to exist and be consumed,

“nitro phenol” compounds will remain the biggest known and used group among all chemicals

used in the industry. The nitro phenol compounds are also used in synthesizing organic

compounds (Trivedi, Tallapragada, Branton, & Nayak, 2015 & Balasundram, Sundram, &

Samman, 2006). Usually, nitration reactions suffer from low regioselectivity and over nitration

(L. Y. Chen, Liu, Zhou, & Sun, 2014). In nitration process, a huge amount of H2SO4 is needed

since the reaction slows down due to the water by-product that dilutes the acid. After these

processes, a big quantity of “spent acid” is acquired wherein for “batch reactions” is usually for

disposal and neutralization while for the process which is continuous one are being recycled by

multifaceted techniques. In addition, products which are separated from the acid are often

problematic and requires too much energy which usually involves simple aqueous work- up.

Besides, handling and transport of sulfuric acid is difficult since it is corrosive (Mohammad Ali

Zolfigol, Madrakian, & Ghaemi, 2002). Another serious challenge every country continuously

faces is the problem with agricultural solid wastes. These wastes originate mostly on farming

activities. It includes paddy husk, cassava stalks, corn residues, slaughter house residues etc. If

not given attention and fails to be managed, these wastes may cause forming of shelter for

worms, flies, insects, vermins, rats, rodents, snakes and all forms of disease causing micro-

organisms which might lead to causing pollutions also. Corn is commonly grown all around the

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word and its weight is greater compared to other grains. Its worldwide production is estimated to

be not less than 785 million tonnes (Kelle, Eboatu, Ofoegbu O.3, & Udeozo I.P, 2013).

Consequently, reducing the quantity of H2SO4 required for nitration reactions and any

simplifying of handling measures that is absolutely suitable on cutting danger and for economic

benefits and environment protection is very significant. In continuous application of inorganic

acidic salts on studies it is established that SiO2 gel reacts with chlorosulfonic acid to give “silica

sulfuric acid (SSA)”. Because the hydrochloric acid gas formed can be eliminated from the

reaction vessel immediately, it is interesting to note that it makes the reaction easier and neat

without requiring any complicated process (Mohammad Ali Zolfigol et al., 2002). Silica are

commonly found commercially as “alkoxysilane compounds (i.e such as

tetraethylorthosilicate(TEOS), sodium silicate, and tetramethylorthosilicate)” but these

compounds can have a negative impact on health. Thus, further approaches to find the source of

silica that is safer, cheaper, and more environmental-friendly is inevitable. Previous researches

reported several sources of silica derived from agricultural waste, such as rice husk, rice straw,

corn cobs, and bagasse. In addition, the method of isolation of silica from agricultural waste, and

its application as a catalyst is also discussed (Permatasari, Sucahya, Bayu, & Nandiyanto, 2000).

Though studies have stated and proven that rice hull ash (RHA) has the most silica content

among other agricultural wastes, there already are other existing uses of RHA such as for

cement, steel, ceramic, and refractory production. Therefore, finding an agricultural waste

containing silica would be significant so the use of RHA cannot be furthermore be divided

(Goswami, Sahadev, & Rankawat, 2016; Kumar, Sangwan, V, & Bidra, 2013; Mohanta, Kumar,

& Parkash, 2012; Obilade, 2014).

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 As an existing study has proven that silica derived from rice hull can be used for

sonochemical synthesis of silica sulfuric acid catalyst for acetylation of alcohols and phenols,

this research aims to modify it by using corn cob in place of rice hull and the catalyst produced

be used for nitration of phenol.

1.2 Objectives of the Study

The overall aim of this study is to produce a green catalyst from Philippine white corn cob

and use it for nitration of phenol. Furthermore, there were other objectives made along the

process of the research:

1.2.1 To synthesize silica nanoparticles from the silica

1.2.2. To characterize the silica nanoparticles and synthesized SSA catalyst

1.2.3. To investigate the catalytic property of SSA using three different parameters such

as amount of catalyst, reaction temperature, and reaction time

1.2.4. To test the reusability of the synthesized catalyst

1.3 Significance of the Study

Due to growing population and increasing consumption of corn and nitrophenol, the study

provides an alternative way of minimizing waste corn cob while at the same time maximizing the

yield of nitration product of phenol. Due to this the following stakeholders will benefit from this

research

 Nitration Industries

Sufficient supply of nitro phenol will be provided with inexpensive, easy to prepare and

environment-friendly catalyst to nitration industries specifically those whose products are dyes,

explosives, pharmaceuticals, rubbers, woods and industrial chemicals. Also, its application will

3
be beneficial in lessening the dependency of chemical industry to commercially available silica

and it will help them to have a faster and higher production of nitro phenol.

 Corn Industries

For this research, corn cob is the main raw material for silica extraction. With this, it gives

corn cob a substantial use more than being just a waste. Also, the corn consuming industry will

benefit from it by earning back and reducing their expense through selling the waste corn cobs.

Along with this, the waste corn cob produced will be minimized.

 Future Researchers

The future researchers will benefit from this study because they can get adequate information

from this and can use it as basis that will help them to conduct further study about the research.

1.4 Theoretical Framework

1.4.1 Nitration Reaction Mechanism

Nitration is an example of electrophilic substitution in which nitro group is introduce to

organic chemical compound. Nitration mechanism first involves the formation of nitronium ion

(NO3+). It is formed when sulfuric acid protonates nitric acid and then dissociates.

Figure 1. Protonation of Nitric Acid to form Nitronium Ion

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 Nitronium ion serves as electrophile and reacts with benzene to form arenium ion.

Formation of ortho-nitrophenol and para-nitrophenol occurs when nitronium ion loses its

proton.

Figure 2. Nitration of Phenol to Nitro-phenol

1.5 Scope and Limitations

This study will focus mainly on producing a heterogeneous nano-silica sulfuric acid

(SSA) catalyst obtained by sonochemical synthesis where the silica is extracted from corn cob.

The catalyst will only be used for the nitration of phenol. In addition, this study will determine

the amount of ortho and para nitro phenol products. This will also be done only on a small scale.

This study will only consider three parameters such as amount of catalyst, reaction temperature

and reaction time that will determine the optimum yield for the nitration of phenol. Moreover,

this paper will also determine the characteristics of the silica nanoparticle using only “XRD, FT-

IR and SEM-EDX”. The characteristic of the synthesized SSA will be determined only by using

“FT-IR”.

This research will use the specific waste substrate Philippine white corn cob. Moreover,

the yield of products produced using the synthesized catalyst to that of commercially available

5
one will be compared. The amount of reaction products and percentage selectivity will be

monitored by “GC-FID” analysis.

1.6 Definition of Terms

Calcination – burning at high temperature of the corn cob to remove its moisture content

Green catalyst – a catalyst that acquires most of the 12 Principles of Green Chemistry

Nitro-phenol – the product formed from the nitration of phenol. It can be an ortho or para

directing depending on its structure.

Silica sulfuric acid (SSA) – a solid acid catalyst used in nitration reaction of phenol.

Sonochemical synthesis – a synthesis wherein it uses sound waves to produce the silica

nanoparticles

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 CHAPTER 2

REVIEW OF RELATED LITERATURE

2.1 Nitration

Nitration is simply defined as the introduction of the nitro functionality, -NO2, into a

molecule most often by the electrophilic action of the nitronium ion (NO2+) (Firth, 2001).

2.1.1 Phases of Nitration Reaction

2.1.1a Liquid Phase Nitration

Based from the study of Kuba et al., 2007, the conversion of toluene improved in a

smaller scale using zeolite beta catalyst during acetyl nitrate nitration which is a kind of liquid

phase process and a continuous one than during non-catalyzed homogenous reaction. Zeolite

beta contains a less reactive substrate called chlorobenzene. In the reaction, “zeolite beta”

performed efficiently as a catalyst. Acetyl nitrate, possessing a well-established process of

liquid-phase nitration, is formed by combining concentrated HNO3and “acetic acid anhydride”

(C4H6O3) together in an exothermic reaction. Having an edge of being a nitrating agent which is

a highly reactive one, it has also a downside of being an explosive when the temperatures exceed

at 60 degrees Celsius and must be carefully handled during its formation and reaction. It can

nitrate aromatic molecules with almost full conversion. “2,4-dinitrotoluene”, when develops

selectivity happens best when used by “zeolite beta” by a homogeneous one. This is based from

the studies on 2-nitrotoluene and toluene nitration (Kuba, Prins, & Pirngruber, 2007).

In nitration using the catalyst “acetyl nitrate” which is happening in a liquid phase. Usage

of “acidic zeolite beta” as the catalyst considering that the other non-protic zeolites and

aluminum salts are less active. Reaction rate is influenced by H+ and its concentration since

7
hydrogen ion is the only counter ion which is active. The activity of zeolite beta catalyst is

indirectly affected by other cations aside from H+ for the reason that these cations are only used

for hydrogen ion during the reaction. Production of too much “acetic acid or acetic acid

anhydride” through the help of “diluted nitric acid” is the main reason why catalyst was

deactivated in this system. We conducted the experiment in an uninterrupted reaction mode for it

is presented that the nitration of toluene with acetyl nitrate is a rapid reaction that needs short

contact time (Kuba et al., 2007).

2.1.1b Vapor Phase Nitration

Regioselective nitration will be produced hopefully in a gas phase nitration because of

the layered structure of the clay which will be carried out in due process (Bharadwaj, Boruah, &

Gogoi, 2014).

An important advantage offered by gas phase “nitration of aromatic compounds” is the

elimination of the phase of separation of the reaction product from the mixture catalyst, as well

as a considerable increase in selectivity in the formation of a monosubstituted nitration product.

The reaction tested in the present project is the gas phase “nitration of aromatic compounds”,

using the azeotropic solution of HNO3. This method is the most promising for the production of

benzene with a boiling temperature of less than 200 °C. The use of nitric oxides as nitrating

agents, allowing the continuous realization of the process (for example, Kyodai nitration

process), imposes a considerable increase in the complexity of the reaction system setup.

Furthermore, NOx are considerably less reactive, with inert nitrogen oxide (I) as a side product.

The fact that cheap, azeotropic nitric acid is used as the nitrating agent in the search for effective

and stable catalytic nitration systems opens the perspective of process industrialization for this

method

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 Monosubstituted nitration product, the selectivity in its formation has a considerable

increase and phase of the separation of the mixture catalyst to the reaction product is eliminated.

The present method of a gas phase nitration of aromatic compounds using azeotropic solution of

nitric acid which is the most promising with a temperature of not greater than 200oC. Complexity

of the reaction system setup and continuous realization of the process makes the use of nitric

oxides at nitrating agents. Moreover, Using inert nitrogen oxide (I) as a side product, NOx are

considerably less reactive and the fact that in the search for effective and stable catalytic nitration

systems, that cheap azeotropic nitric acid is used as the nitrating agent opens up the perspective

of process of industrialization for this method (Koskin, Mishakov, & Vedyagin, 2016).

2.1.2 Uses of Nitration

Nitrogenous functionality can be introduced in a convenient way by nitration; which is

particularly beneficial for the preparation of heterocyclic compounds that finds uses in

pharmaceutical products including NO synthase inhibitors, vasodilators beta blockers and so on

like imidazoles, indazoles and indoles (Firth, 2001).

Explosives, dyes, pharmaceuticals, plastics and perfumes are the handy products from the

nitrated aromatic compounds (Khder & Ahmed, 2009).

The production of a wide range of chemicals from dyes, pesticides to pharmaceuticals

and drugs are some of the applications of nitrobenzaldehydes. These can be used in the

production of cardiovascular drugs and benzodiazepines. Aside from this, it was also found that

2-nitrobenzaldeyde is a photo removable protecting group for several functionalities that is why

a huge interest for compounds recently prepared from 2-nitrobenzaldehyde exists but the chance

of acquiring it directly from benzaldehyde is very minimal because the most favored position

9
during nitration is the meta one (3-nitrobenzaldehyde) (Russo, Onotri, Marotta, Andreozzi, & Di

Somma, 2016).

Great opportunities from nitro group and its influence on benzene ring activity makes

nitroaromatic compounds extensively used in chemical industry as they are the intermediates for

the process of making dyes, medicines, explosives even pesticides. “Nitro-ortho-xylene” like “3-

nitro-orthoxylene (3-NOX)” and “4-nitro-ortho-xylene (4-NOX)” are the most frequently used

“nitrocompounds” in manufacturing as these are the materials used for the starting of a “large-

scale production” of pharmaceuticals like mefenemic acid for 3-NOX and riboflavin from 4-

NOX (Adamiak, Kalinowska-Alichnewicz, Maksimowski, & Skupiński, 2011).

Nitrobenzaldehyde was used cancer therapy which is photodynamic by Gdovin to a time

where it only requires the flash of an ultraviolet light that causes the injected fluid kill cancer

cells. Doing the procedure on cancer cells which are drug resistant are the things his doing to

level up his research, thus making the therapy as powerful and as useful as possible and starting

to a make a nanoparticle which kills “metastasized cancer cells” if put to the body. This

nanoparticle is activated by a wavelength of light that can pass harmlessly to the different parts

of the body like skin, bone and flesh can pass by the light without harming it and still activates

the nanoparticle (University of Texas, 2016).

2.1.3 Catalysts in Nitration Reaction

2.1.3a Homogenous Catalysts

Based from the study of Bernasconi et al., due to high yields even when the reaction time

which is short s finished and in the absence of a “solid catalyst”, the “homogeneous reaction”

which is a nonselective one must be put into consideration since it can mask the “solid acid”

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behavior, make the zeolite catalyzed nitration of the zeolite be more selective to the “intrinsic 4-

NT”. 48 wt% HF was used to treat the catalyst recovered from the reaction in order to break the

framework of the zeolite and analyze the products of the reaction which can be found in the

pores. The results show that product composition of the liquid phase is same as that of ZSM-5,

BEA, and USY which means that both of the products diffuse through the pores while the two

mordenite samples have notable change in the product composition. H-MOR hasn’t produce any

product inside the pores while H-MOR(74), a dealuminated sample, products can be found in the

pores while its “selectivity” showed that the products was outside and inside the pores. The

dimensionality of the channel system is 1-dimensional probably causes difficulty of diffusion in

untreated samples while the scenario was the opposite in the forming a “secondary mesoporous

system” of “toluene” and “nitro toluene” wherein they diffuse freely. However, in “liquid phase”

and in the pores, only BEA shows para-selectivity which suggests that heterogeneous catalyzed

nitration contributes higher than homogenous nonselective reaction which is proven by the fact

that the reaction with USY, mordenite, ZSM-5 and in the blank reaction, (0.5-1%) of α-NT was

detected, while BEA has a different case. Heterogeneous catalyzed reactions dominates over

homogeneous one which causes the absence of the by-product in BEA, it seems too slow to go

against “homogeneous nitration” which is an unselective one (Bernasconi, Pirngruber, & Prins,

2004).

2.1.3b Heterogeneous Catalysts

Some benefits of heterogeneous catalysis over homogeneous catalysis are a) reusability,

b) separation of reaction mixture is easy, c) handling is safer and easier and d) active sites are

well dispersed thus making them more important than the other. Among heterogeneous catalysis,

solid acid is safer than highly corrosive mineral acids thus it is likely to use in large scale

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industrial processes and for this, the widely used and most important nitro-derivatives and

industrial reaction which is used by some materials as a chemical feedstock is the “nitration” of

“organic compounds”. Solid acid catalysis takes place by making the solid acid adsorb the

mineral acid (Bharadwaj et al., 2014).

Some solid acid catalysts were used to investigate the nitration of 2-nitrotoluene and

toluene with acetyl nitrate. All catalyst showed good “para-selectivity” but high yields were only

observed in BEA during the nitration 2-nitrotoluene while only showed zeolite BEA enhanced

para-selectivity during toluene nitration. Only with zeolite heterogeneous catalysis competes

with “homogeneous nitration” in “liquid phase” successfully. The reaction of an acetyl nitrate

complex which is surface bound and arene showed high “para-selectivity” of BEA and not by the

“transition-state selectivity” which is a classical one and is proven by measurements from NMR

and displayed that the formation of zeolite BEA is a specific property (Bernasconi et al., 2004).

Having a solid acid catalyst, we checked the parameters for the catalytic activity based

from the study of Khder and Ahmed. First is about the effect of WO3 content. At first, the

conversion was very small because the reaction was carried out without catalyst which suggests

the effect of catalysts on the selectivity and conversion. Increase of the catalytic activity was

shown by adding the catalyst. Ortho isomer was formed when maximum is reached which is

caused by a function of the extent of WO3. Calcination temperature is inversely proportional to

the catalytic activity while the “nitration activity” is directly proportional to the acidity of the

catalysis because of the “sulfate treatment”. Increase in the catalytic activity can also be caused

by the increase of “surface acidity” specifically “Bronsted acidity”. Next is the effect of reaction

time. It was shown that the temperature of the reaction is directly proportional to phenol

conversion, therefore to amount of phenol as well and usually conversions are lower than

12
reactions. Next is the reaction time. After of 1 hr. gradual increase of the phenol conversion, no

more increase of conversion noticed. Thus, as the time increases, the conversion of phenol

increases due to increase in formation of nitronium ions. The selectivity to ortho-nitrophenol

doesn’t affect significantly. Next is the mechanism of the reaction. The catalytic activity has a

straightforward connection with the Bronsted acidity which was showed when both catalytic

activity and Bronsted acidity decreased in the increase of WO3 content. Last is the reusability

study. It is showed that filtration and washing gradually losses the catalyst therefore decreasing

its catalytic activity as the number of usage increases (Khder & Ahmed, 2009).

2.2 Synthesis Methods of Silica (SiO2) Nanoparticles

2.2.1Hydrothermal

In the field of biomedical and biotechnical, the application of pore and size of

mesoporous silica nanoparticles (MSNs) is vital. Various synthesis strategies were done in order

to prepare spherical MSNs. This includes the Stober method, dilute solution route, the use of

double surfactant system, quenching technique, high yield synthesis method by adding

triethanolamine (TEA), usage of co-solvents and many more. Among those mentioned methods,

it is potent and less intricate to use techniques that restrain particle growth such as synthesis

under dilute conditions or usage of quenchers. In Imas and co-workers journal, they use F127 (a

nonionic surfactant) to minimize the growth of particles and obtain about 20 nanometer diameter

as the particle size of MSNs. But among these methods, the most challenging part is to produce

uniform particles that has under 50 nm diameter. When tetraethyl orthosilicate (TEOS) is used as

source of silica production of MSNs happens in a formaldehyde/water solution and used

cetyltrimethlammonium bromide (CTAB) as template and the basic catalyst is NH4OH, the

MSNs yield is about 90%. This preparation technique is easy and steady (Gu et al., 2012).

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 2.2.2 Sol-Gel

Sol gel process remained the most popular among the other techniques synthesizing silica

nanoparticles (SNPs) for its capacity to control size, distribution, and morphology particles

through systematic monitoring of the parameters of the reaction. This process provided low

temperature method that applies for purely or both inorganic as well as organic materials (Singh

et al., 2014). Sol gel technique synthesis comprises the simultaneous hydrolysis and

condensation reaction of the metal alkoxide. Its advantage from the other methods is low

temperature synthesis and control of the reaction kinetics by changing the composition of

chemicals (Dubey, Rajesh, & More, 2015) . Sol gel method is easy and efficient for SNPs with

uniform sizes. Lately, Rao et al. succeeded in producing particles with varying size ranging from

20 to 460 nm by a simple sol gel method while Rahman et al. found that disperse SNPs ranging

from 20 to 34 nm can be synthesized in the presence of a unsubstantial amount of NH4Br. Kim

et al., noted that adding electrolytes can reduce particle size to 17.5 nm. Though SNPs of

different sizes can be prepared by sol gel method, those lesser than 15 nm are not disperse but

agglomerated. The SNPs of 4 nm size are in colloidal form silica. When these colloidal silicas

are dried to powders, the nanoparticles are hard-agglomerated particles. This makes the synthesis

of disperse amorphous SNPs not exceeding 15 nm a challenge that needs to be addressed(Guo et

al., 2016).

2.2.3 Microwave

“Microwave-induced plasma CVD (MWPCVD)” is a new technique synthesizing

nanoparticles, and has many pleasing features compared to the other methods. The silica size of

the nanoparticles from this technique is comparably undersized than the others. But despite the

attention given to technical aspects, the scaling up from laboratories to industrial plants became a

14
problem with this technique. And so, systematic investigations were needed for the “MWPCVD

reactor” with support of theories of thermodynamics, chemical kinetics, as well as particle

dynamics for the synthesis of SNPs (Hong, Ding, & Zheng, 2004). Advantages of this

synthesizing technique are a lower reaction temperature, ambient pressure operation, constant

temperature field. This technique also applies for synthesis of amorphous materials like

amorphous metals and amorphous carbon nanostructures. The chance of agglomerate formation

in nano powders was lessen because of the low temperatures characteristic of MW plasma (Chau

& Kao, 2009). In the hydrothermal method, microwave was recently introduced and resulted to a

decrease in time needed to heat it during synthesis process due to speedy kinetics of

crystallization and to the original and unstable phase’s formation. Up to now, microwave

hydrothermal process was being developed either by batch or semi-batch process. Yet, looking

into larger scale, the abiding production and collection procedures can submit to industrial scale

production of inorganic materials with smaller capacity than the usual processing. This work

gives a nonstop process of silica nano powders and its equipment(Bondioli, Bonamartini Corradi,

Ferrari, & Leonelli, 2008).

2.2.4 Sonochemical

Sonochemistry or ultrasound-using chemical synthesis and its modified processes have in

recent past increased interest. Researchers have shown that different kinds of colloidal particle

combine in the nanometer like “Au, Pt, Fe and CdS”. These particles are created by ultrasonic

caused by the reduction of solutions. For aqueous solution, hydrogen and hydroxyl radicals were

produced from aqueous solutions under ultrasonic conditions. Studies have reported that there is

a possibility of increasing the rate of nucleation and growth for more preferred size dispersion

characteristics. This method allows to improve the shape and size of silica particle obtained by

15
molar ratio change of deionized water and ammonium hydroxide in the reaction. “Scanning

electron microscopy” confirmed the optimal manipulation of silica particles’ size and

shape.(Kim, Lee, & Kim, 2016).

2.2.5 Laser Ablation

Most NP synthesis techniques such as physical vapor deposition, precipitation,

solvothermal/hydrothermal methods and sol gel methods are costly and complex and offer only

finite control over particle size and size evenness. In the past few years, solid containing

solutions pulsed-laser ablation has attracted interest due to its versatility and inexpensiveness

demonstrated recently the bulk synthesis of NPs by laser ablation, yielding ceramic NPs on a

scale of several grams. The study indicates the potential feasibility of laser ablation for large-

scale synthesis applications. A one-step method was developed to produce silica NPs from

sugarbeet bagasse using laser ablation. NPs obtained by laser ablation were smaller (38–190 nm)

than those prepared by NaOH treatment. Silica NPs thus produced have less adverse effect on C.

vulgaris growth than chemically produced NPs. The results obtained may aid the development of

environmentally friendly and economically attractive alternatives to current NP production

methods. (San et al., 2014)

2.3 Sources of SiO2

2.3.1 Pure Chemical Sources

2.3.1a Printed Circuit Board Waste

With the continuous advancement and increase consumption of products on a daily basis

in the electronic industry it is anticipated a multiplying mass of electronic wastes over the

preceding decades. Based on an environmental program of UN’s alert bulletin year 2005, million

tons of e-wastes are collected yearly with an approximation of annual 4% increase rate. Though

16
there is minusculization of e-devices like on phones already, it still doesn’t prevent rising of

waste onslaught, as the effect has been compensated by buildup in sales especially in developing

countries. These e-wastes are consists of thousands different substances.

The platform where the microelectronic components are mounted is called printed circuit

board. It is used as a support of the electronic components. Waste PCB contains metallic and

non-metallic fraction. The non-metallics are treated with acids then thermal treatment aiming to

get high purity porous silica. The as-prepared silica is as good as the industrially sold samples

(Bazargan, Bwegendaho, Barford, & McKay, 2014).

2.3.1b Raw Powder Glass

Raw powder glass is an unrecyclable waste following the conventional procedure and

proven to be a flexible silica resource for zeolite synthesis. The silica source is dissolved easier.

Introducing Fe3+ to the zeolite network for high silica containing “MFI zeolite” appraises it as a

capable supply of double cations. A multi-use pure silica “MEL zeolite Silicalite-2” attained

using “tetrabutylammonium hydroxide” as the structure leading agent and hydrofluoric acid as

the mineralizing mediator (Vinaches, Alves, Melo, & Pergher, 2016).

2.3.2 Biogenic Sources

2.3.2a Rice Husk

Rice husk, a by-product of rice milling industry, representing 20 % of the weight of the

rice has silica as its main inorganic component. Silica extraction from it is a growing trend in the

respiratory diseases if inhaled by human. Thus, recycling waste and recreating it into something

with greater value can be beneficial to the environment and also a promising resource

(Permatasari et al., 2000).According to Alvarez et al.,temperatures that are higher than 700℃

causes transformation of silica from amorphous to crystalline structure. Hence, the silica will be

17
coming from the employed rice husk ash from the separators with 650 - 690°C temperature

limits. Five bunches of rice husk ashes each having 50 g were used processed for 5 hours. In line

with the results reported by Bogeshwaran et al., around 60% silica exracted from the rice husk

ashes (Thakkar, Makwana, Mohanty, Shah, & Singh, 2016)

2.3.2b Rice Straw

Rice straw is available in large quantities and does not have commercial importance that

is one of the agricultural waste rich in silica. The silica contest rice straw has is larger compared

to other plants. But the ash constituents depend on the type of rice, climatic, and geographical

conditions where it is grown (Permatasari et al., 2000).

Table 1 in Kurokochi and Sato journalwith title “Effect of surface structure, wax and

silica on the properties of binderless board made from rice straw” shows that when particle size

decreases the amount of silica in ash increases. Ash and silica constituents are relatively high in

bigger particles. It is easier to break down into smaller pieces through grinding the leaf part

compared to the stem part. Also, silica content content is higher in leaf part. Hence, silica

comstituents becomes high for fine particles. It is effective and efficient to do dedusting in wheat

and ricestraws fireboards in order to remove the fine particles but it is unknown of how much

silica contents is lost. Greater than 90% is the silica content in ash(Kurokochi & Sato, 2015).

2.3.2c Sugarcane Bagasse

Sugarcane bagasse (SCB) is a deposit produced in large masses by sugar industries. In

general, for every ton of sugarcane, 280 kg of bagasse is generated. Yet, the utilization of this

bagasse is limited and is primarily used as fuel to sugar mill (Permatasari et al., 2000).

According to Worthanakul et al., the SCB ash has silica content composition of around

89.04%. While another study of Baharudin and Santhanan claims that SCB ash is composed of

18
70.97% of silica after pyrolysis under controlled temperature of 600°C for 4 hours (Norsuraya,

Fazlena, & Norhasyimi, 2016).

2.3.2d Corn Cob

Because of the huge availability of corn, keeping its cob is likely to become more

economical if used as a resource. Presently, these cobs just end up being burned in open spaces

then therefore adds up to environmental pollution and disposal problem. So, considering energy

and resource conservation some burn these cobs under controlled conditions and use the ashes

for abrasive materials, constructions, etc. Because of the ashes’ high surface area, it shows

potential as a catalyst (Velmurugan et al., 2015). More than 60% of silica with small amount of

metals can be found on corn cob. Corn cob ash is acquired in fine powder form by combustion so

further grinding is not anymore needed. It is one of the economical sources of silica(Permatasari

et al., 2000).

With the support of organic acids, precipitated silica can be successful synthesized. But

the highest percentage of sodium silicate that has sodium oxide and silica contents and

precipitated silica is extracted from those cobs soaked in citric acid(Saleem, Rustam, Naqvi,

Jabeen, & Akhtar, 2014)

2.4 Pretreatment of SiO2

Several agricultural wastes such as corn cobs, rice husk, rice straw and bagasse

ash are now being studied as sources of silica. Silica can be extracted from these wastes through

various methods like microbial treatment, chemical treatment and thermal treatment. Before

undergoing to such treatments, those agricultural wastes were subjected to pre-treatment in order

to improve the purity of the silica being extracted and to eliminate impurities. One of the most

common ways of pre-treatment is washing the agricultural waste such as corn cob and sugarcane

19
bagasse ash with water and drying it for 24 hours and calcining it at certain temperatures such as

550 ℃, 650 ℃ and 750 ℃ for given hours , for perlite, it was calcined at 800℃ for 3 hours

(Srivastava, Shringi, Devra, & Rani, 2013). For agricultural waste like rice straw, it has

undergone a similar heat pre-treatment method wherein rice straw between 20-50 cm was cut

into 2-3 cm length and washed using tap water and placed in an electric oven at 60℃ until dry

(Wattanasiriwech, Wattanasiriwech, & Svasti, 2010). Also, there is a kind of pre-treatment

wherein these agricultural wastes particularly the corn cob were soaked in 25% of three different

organic acids namely “citric acid, acetic acid, and oxalic acid” and combined solution of acetic

acid and citric acid for a day after being washed and sundried (Saleem, Rustam, Naqvi, Jabeen,

& Akhtar, 2014). Another known pre-treatment method is the acid-leaching treatment wherein

agricultural wastes like sugarcane bagasse (Affandi, Setyawan, Winardi, Purwanto, & Balgis,

2009)and rice husk (Norsuraya et al., 2016)were washed with hydrochloric acid. Also, there is an

alkali-acid leaching wherein rice husk was first treated with diluted hydrochloric acid obtaining a

residue which will soon be treated with 10wt% NaOH. According to (Indian Journals), HCl in

the stages of acid leaching can effectively done at concentration of 1 M for removal of metal

with a surface area and the pore volume generated is also good. It also stated that the process of

acid leaching in rice husks before burning produce silica powder with a large surface area.

However, if the acid leaching stage is carried out after the combustion process, the surface area

of the silica is not so high.After these various initial steps in pre-treating the agricultural wastes,

white fibrous ash was obtained and put in deionized water and stirred for hours and then filtered

using Whatman paper no.41. This residue is considered as the clean agricultural waste ash (Non,

Chemicals, & Glycol, 2015). Some ash was subjected to further drying and/or heating at certain

temperatures for several hours like sugarcane bagasse ash that was heated at 40℃ for a day after

20
being filtered (Norsuraya et al., 2016) , the paddy husk ash was burnt at 700℃ for 6 hours (Sci,

2013)and some like corn cob ash were burned inside a programmable furnace 700℃ at a rate of

5℃/min (Shim, Velmurugan, & Oh, 2015).

2.5 Silica Sulfuric Acid (SSA)

2.5.1 Preparation

In many organic reactions, SSA is one of the most commonly used catalyst. It became as

a substitute for sulfuric acid (H2SO4) due to its heterogeneous characteristic compared to the

latter which is homogenous in phase.

SSA catalyst can be prepared in many ways. It can be done by using the method of

soaking and drying but commonly it was formulated by reacting silica gel with chlorosulfonic

acid (HSO3Cl). Based on the study of Manna et al., 2015, Soak and dry method was used to

create the SSA catalyst. The SiO2 gel was separated in the solution of diethyl ether [(C2H5)2O]

then the concentrated H2SO4 was added drop wise to the SiO2 gel detached in (C2H5)2O. At least

ten minutes was allotted for the stirring of the mixture after it goes to the oven where it is dried.

A dry powder was obtained and it was heated in order to acquire the catalyst. The catalyst

formed is brown in color and put inside an argon-filled glovebox. The amount of H+ in the SSA

may be determined by acid-base titration (Shaterian, Ghashang, & Feyzi, 2008). A domestic

microwave can be used also to dry the silica gel and subsequently irradiation may be carried out

for optimized time (Eshghi & Hassankhani, 2007).

Many literatures show that SSA catalyst was prepared by the reaction of silica gel with

HSO3Cl(Gaikwad, Haridas, Sayyed, & Farooqui, 2013; Journal et al., 2015; Lasemi, 2016; Li et

al., 2008; Mirmohamadi, Seraji, Shahtaheri, Lahmi, & Ghasemkhani, 2004; Mohammadpoor-

baltork, 2012; Rajendran & Karthikeyan, 2011; Wang, Lu, & Wu, 2011). Some studies

21
performed this reaction by first providing a suction flask with dropping funnel at constant

pressure. This is where the HSO3Cl can be contained. A gas inlet tube was also provided for the

hydrochloric acid (HCl) that will form above the absorbing solution. The SiO2 gel was put into

the suction flask and constant dropwise addition of HSO3Cl at room temperature will be done.

is(Mohammadpoor-baltork, 2012; Rajendran & Karthikeyan, 2011). The white powder formed

after reacting silica gel with HSO3Cl was filtered and the resulting powder were dried at room

temperature (Lasemi, 2016). Using mortar and pestle in grounding silica gel and H2SO4 was also

presented. The residue obtained on this process was heated to furnish SSA as a free flowing

powder (Pourmousavi & Zinati, 2009).

2.6 Acid Catalyzed Reactions

Many liquids and solutions were used as a catalyst for the hydrocarbon conversion. It can

be either heterogeneous or homogenous. Liquid acid catalyst is considered to be homogenous in

nature. This provides some advantages which includes good catalytic activity at low temperature

like producing a high selectivity, cheaper cost, and easy to use. On the other hand, the bad things

about using this catalyst are that the separation of products are difficult to perform, it can’t be

used again and therefore it became waste after it is used in the reaction which imposed a great

concern in our environment. Aside from that, H2SO4 is also difficult to regenerate, concentrate

and purify. These are the reasons why many studies used other catalyst to substitute for

H2SO4.Aside from sulfuric acid, there are still many liquid acid catalysts used in industrial

processes. Some of these are hydrofluoric acid (HF), aluminum trichloride (AlCl3) and

hydrochloric acid (HCl).

Another type of acid catalyst is the solid acid catalyst. This catalystis almost perfect due

to its characteristic that it can be completely recovered from the products of reaction by using

22
only basic operations like filtration and evaporation. The main distinction for solid acid catalyst

is its higher surface area and therefore relatively small size powders. The main drawback when it

comes to solid acid catalyst is its deactivation by coking which is the reason why the

carbonaceous products are produce that destroy the acidic site of the catalyst and causes the

covering of the surface of catalyst. Due to this, reactivation process can be made to overcome

this problem about coking. The study shows that by burning the coke particles through the use of

air or pure oxygen the reactivation process can be made. However, this process of regeneration

or reactivation by burning is somehow exothermic in nature which resulted to an increase in

temperature at the catalyst surface. That is the reason why it needs to be subsequently stabilized

in order for the catalyst to overcome this treatment and provide no significant damage like

surface area loss and sintering. Sometimes, hydrogenation was used as a regeneration process if

the particles involved are noble metals that catalyzes the reactivation reaction (Busca, Kennedy,

& Genova, 2007).

2.6.1 SSA Catalyzed Reactions

2.6.1a Nitration Reaction

SSA catalyst which is an example of solid acid catalyst is commonly used for the organic

reactions like nitration of aromatic compounds. Studies show that the product of nitration play a

significantpart specifically in the plastic and medicinal industry. This is the main reason why

many researches developed this kind of catalyst in order not only to lessen the disadvantages

provided by using liquid acid catalyst but also to improve the yield of the products formed.

Commonly, nitration reaction is done on solvent free conditions (Mohammad Ali Zolfigol et al.,

2004).The main benefits of using SSA as a catalyst for nitration reaction are: First, the catalytic

activity of SSA can be changed based on how the aromatic substrate reacts. Second, the reaction

23
can be done at room temperature and lastly it is easier to formulate and handle compared to

“clay-supported copper nitrate (claycop)” and“clay-supported ferric nitrite (clayfen)” which are

another type of commonly used catalyst for nitration reaction (Begari, Singh, Nookaraju, &

Kumar, 2014; Haghnazari, Karami, Ghodrati, & Maleki, 2011).

2.6.1b Other Reactions

Fischer Esterification Reaction which is a powerful tool for the creation of various

synthetically significant esters which acts as the precursors in synthesizing industrially and

medically important compounds employed SSA as a catalyst because of its reusable properties.

Ionic liquid in the filtrate was separated from unreacted starting materials by decantation or

filtration. It was dried to remove the water and SSA was reused(Manna, Roy, & Sharma, 2015).

Facile reaction involving activated carbonyl compounds also practiced the use of SSA as a

catalyst. This reaction plays an important role as a precursor in the pharmaceutical industry and

as a building block for the production of organic semiconductors. Filtration was also applied to

separate SSA from the product(Azizian, Karimi, Kazemizadeh, Mohammadi, &

Mohammadizadeh, 2005). The synthesis of benzimidazole derivatives also employed this type of

catalyst. Benzimidazole derivatives are important active compounds that show important role

against viruses such as HIV and many more. After each run, chloroform (CHCl3) was added and

the products undergo filtration, the solvent evaporated and the residue which is the catalyst was

rinsed with CHCl3 and reused (Sadeghi & Ghasemi Nejad, 2013). Most of the time, SSA was

used as a catalyst for the acetylation of alcohols and phenols (Salavati-Niasari & Javidi, 2012).

Other important reactions that employ SSA as catalyst areone-pot condensation, hydrolysis,

Biginelli reaction, Ritter reaction, Beckmann rearrangement of ketones, Aza-Michael Addition

24
Reaction and many more (W. Chen, Qin, & Jin, 2007; Eshghi et al., 2007; Gaikwad et al., 2013;

Li et al., 2008; Reddy, Thirupathi, & Patil, 2009; Sadeghi & Ghasemi Nejad, 2013).

2.7 Characterization of SiO2 Nanoparticles and SSA

The characterization of nanoparticles for in depth knowledge of their morphology and

other properties has been determined by different methods and techniques. These includes “X-

Ray Diffraction (XRD), Fourier Transform Infrared (FT-IR), Scanning Electron Microscope

(SEM) and Transmission Electron Microscope (TEM)”(Hussain, 2014).

2.7.1 “X-Ray Diffraction (XRD)”

XRD is a characterization technique able to determine the crystalline structures of

nanoparticles. It is useful for studying chemical composition, crystal structures and phase. The

interaction of x-ray beams with crystal form diffraction pattern that analyze the material and its

phase. The diffraction pattern contains information about the size of crystalline, symmetry of

unit cell and growth orientation (Ashrafi, Davoodnia, & Tavakoli-hoseini, 2013; Hussain, 2014;

Joshi, Bhattacharyya, & Ali, 2008; Salavati-Niasari & Javidi, 2012; Zahmatkesh, Ranjbar, &

Rostami, 2015). In Zahmatkesh et al., journal entitled “Nano Silica Sulfuric Acid: a Mild and

Efficient Catalyst for Tetrahydropyranylation of Alcohols and Phenols” the XRD of silica

nanopraticles and nano-SSA shows that the peak positions are almost identical except that the

intensity peak of nano-SSA increased.

2.7.2 “Fourier Transform Infrared Spectroscopy (FT-IR)”

FT-IR is use to detect the functional group and structural features of nanoparticles by

measuring the infrared intensity over wavelength of light. It is related with the vibrational energy

of atoms in materials. IR spectra contains the overall size and shape estimation (Mecozzi,

25
Pietroletti, & Monakhova, 2016; Salavati-Niasari & Javidi, 2012). In Zahmatkesh et., al journal

entitled “Nano Silica Sulfuric Acid: a Mild and Efficient Catalyst for Tetrahydropyranylation of

Alcohols and Phenols” the IR spectra of silica nanoparticles obtained for the Si-O-Si symmetric

and asymmetric band is in 1815 cm-1 and 1000-1200 cm-1 respectively. For functionalized

silica to silica sulfuric acidSO stretching band is at 813-886 cm-1 and S=O stretching at 1172cm-

1.

2.7.3 “Transmission Electron Microscopy (TEM)”

TEM is a technique for analysis of materials including chemical composition and crystal

or surface structure information. It works at a high energy electron source of around 200KeV.

TEM has much improved resolution and magnification compared to SEM but it has

disadvantages such as its difficulty to operate and time consuming(Hussain, 2014; Liebig et al.,

2016). In Zolfigol et al., journal entitled “Synthesis, characterization and catalytic properties of

monodispersed nano-sphere silica sulfuric acid” the TEM data obtained that the diameter of

spherical nano-SSA is about 60 to 90 nanometer.

2.7.4 “Scanning Electron Microscopy (SEM)”

In identifying the entire appearance of nanoparticles SEM is applied. It helps in

identifying different properties like quality, shape diameter, density, length, thickness and

orientation of nanoparticles. It uses beam of electrons in order to make image. The beams of

electrons leave the electromagnetic lenses and strike the sample's surface. The detector collects

the ejected electrons and converts it into signals. SEM has the capability of capturing image with

magnification range from 20X up to 30 000X with spatial resolution of 50-100 nm and electron

acceleration voltage in the range of 5-20 KV(Hussain, 2014; Omrani et al., 2016). The SEM

image of nano-SSA in Ashrafi et., al journal entitled “A Fast, Highly Efficient, and Green

26
Protocol for Synthesis of Biscoumarins Catalyzed by Silica Sulfuric Acid Nanoparticles as a

Reusable Catalyst” analysis shows that the particle size is about 28-32 nanometer.

2.8 Characterization of Products of Nitration

“Gas Chromatography” is an analytical technique to quantify content of components in

sample. It works by injecting the sample solution into the instrument. A gas stream often used

are Helium and Nitrogen transport the sample in a separation tube called column. The sample

will then be separated. The detector measures the quantity of components that exit the column

(Ashrafi et al., 2014).

In the journal “Regioselective nitration of phenol over solid acid catalysts” by

M.Dongare, S.Dagade and V.Kadam, the gas chromatograph shows that by using Mo/SiO2

catalyst the conversion of phenol is 48 % with orto-nitrophenol selectivity of 70 % and para-

nitrophenol of 17 %. The ortho para ratio is 4.11.

27
 CHAPTER 3

METHODOLOGY

3.1 Materials

Philippine white corn cobs will becollected from Lemery, Batangas.Distilled water will

be obtained from the Chemistry Laboratory of Adamson University, to be used for the removal

of dirt and other contaminants present in corn cob waste. Among chemicals used in this study

include 1.0 M hydrochloric acid (HCl), 3N sodium hydroxide (NaOH), 1.0 M nitric acid

(HNO3), chloroform, ethanol, silica gel, phenol, o-phenol, p-phenol, acetone, diethyl ether and

chlorosulfonic acid. All of these reagents will be acquired from the Chemistry Laboratory of

Adamson University except for silica gel, o-phenol, p-phenol that will be bought commercially

to Bambang, Manila.

3.2 Equipment

3.2.1 Major Equipment

3.2.1.1 “Gas Chromatography Flame Ionization Detector (GC-FID)”

Perkin Elmer GC-FID will be used to test the purity and quantify the products of the

aromatic nitration of phenol. This will be obtained from the Chemistry Laboratory of Adamson

University.

Figure 3. GC-FID Schematic

28
 3.2.1.2“Ultrasonic Generator (Sonicator)”

Probe-Type Cole Parmer Sonicator which operates at 20kilohertz (kHz) and an

extremeoutput of 750 Watts (W) will be used for the ultrasonic irradiation. This will be acquired

from Chemistry Laboratory of Adamson University

Figure 4. Probe-Type Sonicator Diagram

3.2.1.3 “X-Ray Diffraction (XRD)”

This will be practiced for the characterization of the SiO2 nanoparticle. This will be

obtained from the UP National Institute of Geological Sciences.

Figure 5. Schematic of X-Ray Diffraction

29
 3.2.1.4 “Scanning Electron Microscopy with Energy Dispersive X-Ray

Spectroscopy (SEM-EDX)”

This will also be used for the characterization of SiO2 nanoparticle. This will be obtained

from the De La Salle University – Manila.

Figure 6. Schematic of SEM-EDX

3.2.1.5“Fourier Transform Infrared Spectroscopy (FT-IR)”

This will also be used for the characterization of SiO2 nanoparticle and that of

functionalized SiO2 nanoparticle. This will be obtained from the Chemistry Laboratory of

Adamson University.

Figure 7. Schematic of FT-IR

30
 3.2.1.6 Thermometer

This will also be obtained from Chemistry Laboratory of Adamson University and will

also be used to monitor the temperature.

3.2.1.7 Furnace

This will be used for burning the cleaned pure corn cob at controlled temperatures.

3.2.2 Minor Equipment

3.2.2.1 Weighing Scale

This will be used to weigh the total corn cobs collected.

3.2.2.2 Analytical Balance

This will be used to weigh part of the sample.

3.2.2.3 Filter Paper

This will be used to separate the resulting powder of corn cob ash from the HNO3

solution.

3.2.2.4 Buchner Funnel

This will be used as a support for the filter paper for separating the residue of corn cob

ash from the HNO3 solution. This will be used also to separate the catalyst from the product of

nitration.

3.2.3 Glasswares

The glass wares to be used upon doing the experiment are the following: 250 mL

graduated cylinder, 400 mL beakers, 10-15 mL test tubes, 150-250 mL round bottomed flask, 25

mL pipette, 500 mL reagent bottles, glass rod and watch glass.

31
3.3 Experimental Procedure

3.3.1 Synthesis of Silica Nanoparticles

The method suggested by Salavati-Niasari and Javidi, 2012 is adapted to synthesize nano

silica particles from calcined corn cob ash. The corn cob will be washed with distilled water for

several time to eliminate dirt and contaminants present in it. It will be dried for 24 hours. An

appropriate amount of cleaned corn cob will be calcined at 650℃ for 2 hours. Corn cob ash will

be pretreated by the use of 1.0M HNO3 solution and stirred for about 18 hours at room

temperature to remove the metal oxide from the corn cob ash and extract the silica. The powder

that will be formed is washed at least three times with the use of ethanol (C2H5OH). Afterwards,

this will be dry at 80℃ for at least 3 hours under vacuum and will be categorized as SiO2

extracted. To promote purification of silica, 5.0 grams of the SiO2 extracted will be mixed with

2.0 g NaOH and heated at 600℃ for 1 hour. The ensuing powder will be dissolved in 50.0 mL

distilled water and the solution will be filtered using filter paper. The residue will be washed

with 30 mL boiling water. The remaining liquid is sodium silicate (Na2SiO3). For preparation of

SiO2 nano particles, while 10 mL of the Na2SiO3 solution will be irradiated with the use of

sonicator, a solution of HCl (1.0M) will be added dropwise to the Na2SiO3 solution. The powder

that will be formed shall undergo filtration and washing at least three times with C2H5OH and

distilled water. Subsequently it must be dry again at 80 ℃ for at least 3 hours under void

conditions. The powder that is already dried will be heated at 750℃ for at least 2 hours.

3.3.2 Characterization of SiO2 nanoparticle

3.3.2.1 “X-Ray Diffraction (XRD)”

This characterization technique will be done after producing SiO2 nanoparticles. It will be used

to show and investigate the crystalline properties of the nanoparticles formed.

32
 3.3.2.2 “Scanning Electron Microscopy with Energy Dispersive X-ray

spectroscopy (SEM-EDX)”

This analysis will be done after producing the SiO2 nanoparticles. On using this technique

the images of nanoparticle formed and its elemental composition will be analyzed.

3.3.2.3 “Fourier Transform Infrared Spectroscopy (FT-IR)”

This will be done after producing the SiO2 nanoparticles. On this technique, the “stretching

bands of SO2 with Si-O-Si” will be known.

3.3.3 Synthesis of SSA

Chlorosulfonic acid (ClSO3H) will be added dropwise to the mixture of 2 grams of silica nano

particles and 15 mL chloroform at 0℃ during 2 hours. After the complete addition, the mixture

will be mixed for 2 hours until HCl gas evolution will stop. The ensuing powder will be filtered

and washed three times using C2H5OH and distilled water. The washed powder will be dried at

room temperature to acquire the SSA nano particles.

3.3.4 Catalyst Characterization

3.3.4.1 “Fourier Transform Infrared Spectroscopy (FT-IR)”

This technique will be performed after synthesizing the SSA. The stretching bands of SO2

with Si-O-Si in the SSA will be known.

3.3.4.2 Catalytic Activity

The activity of SSA catalyst will be tested for the “phenolic nitration using nitric acid

(HNO3)” and acetone as a solvent. Using a round bottomed flask with a stirring mixture of 10mL

acetone and 1mol phenol at varying temperature starting from 25℃ to 80℃, 1M HNO3 and a

varying amount of catalyst starting from 0.1 g – 0.4 g will be added. The reaction mixture will be

33
stirred for a varying reaction time starting from 1 hour – 2.5 hours. Afterwards, the mixture will

be filtered and the products will be characterized off-line by GC-FID.

3.3.4.2a Amount of catalyst

The amount of catalyst that will be used in nitration of phenol will vary while keeping the

other parameters constant. 0.1 – 0.4 gram using an increment of 0.1 gram of SSA catalyst will be

the extent that will be used for this procedure.

3.3.4.2b Reaction Temperature

The reaction will be carried out in the reaction temperatures starting from 25℃ up to 80℃

in the presence of SSA catalyst.

3.3.4.2c Reaction Time

The reaction will be followed at different times starting from 30 minutes up to 2 hours in

the presence of SSA catalyst.

3.3.5Reusability of catalyst

The collaboration of three parameters that will give the optimum yield will be used for

this procedure. The catalyst will be separated by the use of filtration and will be washed using

acetone or diethyl ether and must be dry at temperature not lower than 180℃ for at least 2 hours.

Afterwards it will be used again in nitration of phenol. The maximum yield that will be obtained

after reusing the catalyst will be investigated.

3.3.6 Comparison of Synthesized Catalyst to Commercial Catalyst

The yield that will produce by synthesized catalyst will be compared to commercially

available catalyst. The combination of three parameters that will give the optimum yield in 3.3.4

will be compared by using the same combination of parameters for the reaction using the

34
commercially available catalyst. The yield will be obtained using equation 3.1. Also, the

selectivity will be calculated using equation 3.2.

𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑦𝑖𝑒𝑙𝑑 = 𝑚𝑎𝑥𝑖𝑚𝑢𝑚 𝑦𝑖𝑒𝑙𝑑 𝑜𝑏𝑡𝑎𝑖𝑛𝑒𝑑 𝑢𝑠𝑖𝑛𝑔 𝑠𝑡𝑜𝑖𝑐ℎ𝑖𝑜𝑚𝑒𝑡𝑟𝑖𝑐 𝑐𝑎𝑙𝑐𝑢𝑙𝑎𝑡𝑖𝑜𝑛𝑠 (𝟑. 𝟏)

𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑑𝑒𝑠𝑖𝑟𝑒𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡

𝑆𝑒𝑙𝑒𝑐𝑡𝑖𝑣𝑖𝑡𝑦 = (𝟑. 𝟐)
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑢𝑛𝑑𝑒𝑠𝑖𝑟𝑒𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡

3.3.7 Characterization of Products of Nitration

3.3.7.1 “Gas Chromatography Flame Ionization Detector (GC-FID)”

The reaction products and its corresponding yield will be determined through the use of

GC-FID. The percentage selectivity for the products formed will be known by the use of this

instrument.

35
 3.4 Process Flow Chart Corn Cob
650℃

Corn Cob Ash

HNO3

SiO2 extracted

NaOH

Na2SiO600℃
3
HCl
)))))

Si(OH)4
750℃

SiO2 nanoparticle Characterization

ClSO3H

Characterization 600℃
SiO2-OSO3H (SSA)
Application XRD SEM-EDX FT-IR

Nitration Reaction
Catalytic
FT-IR
Activity

600℃
Nitration of Phenol

Amount of Catalyst Reaction Temperature Reaction Time

Optimized Yield (Characterized by GC-FID)

36 Reusability of
Catalyst
3.5 Experimental Design

Amount of T (℃) % yield

Catalyst 0.5 h 1h 1.5h 2h
T.Y O P T.Y O P T.Y O P T.Y O P
25 ℃
40 ℃
0.1 g 60 ℃
80 ℃
25 ℃
0.2 g 40 ℃
60 ℃
80 ℃

25 ℃
0.3 g 40 ℃
60 ℃
80 ℃
25 ℃
0.4 g 40 ℃
60 ℃
80 ℃
Note:

*Experiments are done in duplicates

Total experiments = 128

Legend:
T.Y = Total Yield
O = Yield of ortho-nitro phenol
P = Yield of para-nitro phenol

37
 3.6 Sampling Method 25℃ 0.5hour, 1 hour, 1.5hours & 2hours

0.1 gram 40℃ 0.5hour, 1hour, 1.5hours & 2 hours

60℃ 0.5hour, 1hour, 1.5hours & 2hours

80℃ 0.5hour, 1hour, 1.5hours & 2hours

25℃ 0.5 hour, 1hour, 1.5hours & 2hours

0.2 gram 40℃ 0.5hour, 1hour, 1.5 hours & 2 hours

60℃ 0.5hour, 1hour, 1.5hours & 2hours

80℃ 0.5hour, 1hour, 1.5hours & 2hours

Amount of Catalyst

25℃ 0.5hour, 1hour, 1.5hours & 2hours

0.3 gram 40℃ 0.5hour, 1hour, 1.5hours & 2hours

60℃ 0.5hour, 1hour, 1.5hours & 2hours

80℃ 0.5hour, 1hour, 1.5hours & 2hours

25℃ 0.5 hour, 1hour, 1.5hours & 2hours

0.4 gram 40℃ 0.5 hour, 1hour, 1.5hours & 2hours

60℃ 0.5 hour, 1hour, 1.5hours & 2hours

80℃ 0.5 hour, 1hour, 1.5hours & 2hours

38
3.7 Statistical Treatment

This study wants to determine the combination of three parameters which are the“amount of

catalyst, temperature and time” that will give the optimum yield for the nitration of phenol. Due

to this, the statistical treatment that we will use is the Box-Behnken method which is designed

for the determination of the optimum yield that contains 3 factors. The statistical treatment will

be performed using the design expert software.

39
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