THE EFFECT OF COPPER LOADING ON THE SELECTIVE NOx REDUCTION

OF GYPSUM-REINFORCED ZEOLITE COMPOSITE

______________

A Project Study Proposal

Presented to the Faculty

Of the Chemical Engineering Department
School of Engineering and Architecture
Saint Louis University

______________

In Partial Fulfillment
Of the Requirements for the Degree
Bachelor of Science in Chemical Engineering

______________

by:

Engr. Melissa May Muoz-Boado, MSEnE

Norween Vince P. Alibuyog
Rudolph John C. Barcellano
John Vincent B. Cario
Marcel Roy B. Domalanta
Frances Kaye E. Magaoay
Margaret P. Mat-an
Elaiza Ann A. Rosario
Christine Joy P. Viduya
Antonino N. Villarey

December 2017
 TABLE OF CONTENTS

TITLE PAGE .................................................................................................. i

INDORSEMENT .................................................................................................. ii

TABLE OF CONTENTS ....................................................................................... iii

List of Figures ................................................................................................. iv

Chapter 1

THE PROBLEM AND ITS SETTING .................................................................... 1

BACKGROUND OF THE STUDY ..................................................................... 1

THEORETICAL AND CONCEPTUAL FRAMEWORK....................................... 6

PARADIGM OF THE STUDY ......................................................................... 12

STATEMENT OF THE PROBLEM .................................................................. 12

SCOPE AND DELIMITATION ......................................................................... 14

CONSTRAINTS OF THE STUDY ................................................................... 14

SIGNIFICANCE OF THE STUDY ................................................................... 15

OPERATIONAL DEFINITION OF TERMS ...................................................... 16

Chapter 2

RESEARCH DESIGN AND METHODOLOGY ................................................... 19

RESEARCH DESIGN...................................................................................... 19

DATA GATHERING TOOLS ........................................................................... 19

DATA GATHERING PROCEDURE................................................................. 20

Materials ...................................................................................................... 20

Ion Exchange .............................................................................................. 20

 TREATMENT OF DATA .................................................................................. 21

Chapter 3

REVIEW OF RELATED LITERATURE ............................................................... 22

REFERENCES ............................................................................................... 32
 List of Figures

Figure 1.1 The development of the three dimensional structure of zeolite with
high Si/Al ratio (Devadas, 2006)

Figure 1.2 Input-Process-Output

 Chapter 1

THE PROBLEM AND ITS SETTING

This chapter explains the foundation for this study and was pushed through

due to the increasing issues of air pollution. With the aid of the previous studies,

books and journals about zeolites, gypsum, and emission reduction processes

were used to support this research which aims to investigate the mechanisms of

Nitrogen Oxides adsorption on to a gypsum-reinforced zeolite composite.

1.1 BACKGROUND OF THE STUDY

It has been a great dilemma to people the pollution caused by unseen

particles by the naked eye. This pollution is primarily caused by the suspension of

small particles in air that results from the incomplete combustion of fuel. The

combustion process produces various products that are considered to be harmful

to human health. Air pollution is the side-effect of the increasing industrialization

and urbanization. The sources of pollution may be stationary, mobile, or area.

Mainly, air pollution affects the people through their cardiovascular system which

leads to lung disease, heart disease, and increase the risk of cancer. The World

Health Organization (WHO) estimates that air pollution causes 3.12 million

premature deaths worldwide - 1.15 million due to urban outdoor air pollution and

1.97 million due to indoor air pollution (WHO, 2009). Air pollutants range from

different products such as PM (particulate matter), CO2, VOCs (volatile organic

compounds), HCs (unburnt hydrocarbons), SOx (oxides of sulfur), and NOx

(oxides of nitrogen).

1
 Nitrogen Oxide, which is the yield of the interaction between the Nitrogen

and Oxygen gases in air. These Nitrogen Oxides contribute to the formation of the

Particulate Matters and the ground level ozone, which are both associated with

adverse health effects such as irritating the lungs, causing bronchitis and

pneumonia, and lowering resistance to respiratory infections (Liu, Berg, &

Schauer, 2008). These small particles, at high levels of exposure, find their way

into the respiratory system of the human body and start causing inflammation of

the passage of air; and with prolonged exposure can cause decrease of functional

activity of the lungs as a whole and increase risk on respiratory conditions and

allergens (WHO Working Group, 2003). For the past years, according to World

Health Organization one of the primary reasons of fatality nowadays is smoke

inhalation. Moreover, these also affect the ecosystem as a whole because they

are both precursors of greenhouse gases since it is capable of reacting with other

elements in the atmosphere thus contributing to acid rain and ozone formation.

The reduction of NOX from the exhaust of internal combustion engines or industrial

boilers is one of the most urgent issues needing to be solved since the serious

effects of N2O not only health problem but also lead to the destruction of the

ozonosphere and are a leading factor in the greenhouse effect. With this,

legislation requires that the emission of NOx in different industries is strictly limited.

Nowadays, one of the largest contributors of all pollution is related to

burning of fossil fuels. Gasoline/Diesel is the primary fuel utilized in the internal

combustion engine and approximately 11 million tonnes of gasoline/Diesel is

2
consumed in 1986 to 2012 in the Philippines according to United States Energy

Information Administration. Oxides of nitrogen (NOx) is one of the main ingredients

involved in the formation of ground level ozone, which have an impact on the

climate as well. These acidic gases are primary sources for atmospheric pollution

and are believed to be causing increasingly serious environmental problems

mainly Nitrogen (NOx) which plays a major role in formation of urban

photochemical smog, acid rain and eutrophication of soil and water along with half

of all of hydrocarbons and carbon monoxide that are consumed is associated with

burning of fossil fuels. Furthermore, Recent studies show define ultrafine and

nanoscale particulate matter to demonstrate the undesirable contaminants in air

pose serious health threats to human beings by contributing to a broad range of

health issues including inflammation of the airways at high levels, decrease lung

function, increase the risk of respiratory conditions such as asthma, bronchitis,

emphysema increases the response to allergens. Particulate concentrations

emitted into the atmosphere from both stationary and mobile combustion sources,

including fossil fuel combustion in heating and thermal power plants, petroleum

reneries and simultaneous exposure to such local traffic emissions contribute

substantially to exceeding the critical levels and critical loads in the area, thus

public awareness pertaining to various health implication should disseminate.

It has been known that vehicles with diesel engine are very attractive not

only because of the low-priced fuel and their NOX emission has always been low

relative to gasoline-engine, however ambient urban concentrations of NOx in the

3
Philippines have drastically increased in NOx concentration systematically higher

than the calculated in recent years, hence, serious threats creates harm to human

population as well as depletion of ozone layer which consequently needed for NOx

reduction. The focus of this article is concerned with the reduction of Nitrogen

Oxides, which contributes climate change due to high temperature of exhaust in

engines.

Nitrogen oxides (NO, NO2) are considered to be the major source of air

pollution and contribute a lot to photochemical smog, acid rain, ozone depletion

and greenhouse effect. NOx (95%) are mainly produce from the transportations

(49%) and power plants (46%) (Z.S. Wei et al., 2007). The emission of various

nitrogen oxides into our atmosphere occurs on a massive scale. Worldwide, over

30 million tons of NOx are vented to the earth's atmosphere each year (J.N. Armor,

1995).

The latest National Emissions Inventory in 2015 by source showed that 65%

of air pollution comes from mobile sources, 21% from stationary sources, and 14%

coming from area sources. Emissions from mobile sources contribute significantly

to total emissions of particulate matters (PM), volatile organic compounds (VOC),

carbon monoxide (CO), and nitrogen oxides (NOx). According to the report of

Environmental Management Bureau, Region IV-A and NCR are the most

contributors for NOx emission in the Philippines in 2015 thus methods of NOx

reduction is becoming a great concern.

There are three catalytic methods used for the reduction of NOx from engine

exhaust namely, (i) non-selective reduction, (ii) selective reduction and

4
(iii) decomposition (Traa, Burger, & Weitkamp, 1999). For the past researches,

selective catalytic reduction was the method used for the reduction of NO x since

the other methods were not able to control NOX emissions in oxygen-rich exhaust

gas. Additionally, SCR systems are tolerant to higher sulfur content and have

recently been adapted by several engine manufacturers for use in mobile emission

sources to meet stringent NOx regulations (Liu, Berg, & Schauer, 2008).

Technologies such as different monolith modifications and zeolite modifications

have been studied for efficient SCR of NOx.

Natural zeolites exist geologically as crystals of volcanic and sedimentary

rocks of low temperature under normal conditions. Microscopically, it contains

pores or cavity channels of relatively small uniform size and of high internal surface

area which makes its capable of selective entrapment of foreign molecules. It is

why zeolites are frequently regarded as molecular sieves, with its application

extends to commercial and industrial applications in ion-exchange, filtration,

adsorption, and other separation processes. Zeolites offer unique physicochemical

properties such as pore structures of molecular scale, ion exchange capacities,

strong surface acidity and a unique internal surface topology (Anpo et al., 1996).

Structurally, zeolites are crystalline polymers based on a three-dimensional

arrangement of tetrahedra (SiO4 or AlO4) connected through their oxygen atoms

to form subunits and finally large lattices by repeating identical building blocks (unit

cells). Each zeolite type can be easily obtained over a wide range of compositions

directly by synthesis and/or after various post synthesis

5
treatments. Moreover, various compounds can be introduced or even synthesized

within the zeolite pores (Gilson & Guisnet, 2015; Bonenfant, Kharoune, Niquette,

Mimeault, & Hausler, 2008; Hardie, Garnett, Fallick, Rowland, & Ostle, 2005).

The focus of this study is concerned with the reduction of NOx, which arises

from the fixing of atmospheric nitrogen due to the high temperature which exist in

engines. Similar to Vanadium, Titanium, Tungsten and other common oxides,

zeolites are considered as catalysts for selective catalytic reduction (SCR). They

are able to oxidize unburnt hydrocarbons (HC) and PM, and possibly reduce NOx

from gasoline-engine exhaust (Boado & Caldona, 2017). Zeolite catalyst

specifically Mordenite (MOR) and Heulandite (HEU) reinforced with gypsum and

copper as an additional material is to be used in order to analyze the effect of this

system to the NOx-containing exhaust produced by gasoline engines

1.2 THEORETICAL AND CONCEPTUAL FRAMEWORK

NOx REDUCTION

NOx are one of the main pollutants generated from both mobile and

stationary sources that can affect human health and harm the environment (Zhang,

2001). The last twenty years have observed a reduction of approximately 95% in

NOx generated from diesel engines after installing the NOx reduction technologies

(Deka, 2013). All over the world, environmental regulations are strict about

reducing NOx in order to have a clean environment to live in (Sjocall,

6
2006). NOx reduction can be categorized as combustion modifications and post-

combustion process. Combustion modifications reduce NOx formation during

combustion process and post-combustion processes, which reduce NOx formation

after it has been formed (Sadan, 2014).Post-combustion process include

technologies such as Selective catalytic reduction (SCR) and Selective non-

catalytic reduction (SNCR) in which the former will be employed.

SCR

The SCR technology is used since the end of the 1960s with different

catalysts. It is considered nowadays as the most effective method of the leading

post combustion abatement technologies for NOx removal in stationary

applications such as chemical industries (Abbasian, 2012; Zhang, 2001). In this

study, however, this process will be applied in the reduction of NOx emissions from

diesel-engine vehicles. Advantages of this process is that it is one of the most

effective NOx abatement techniques, operating temperature ranges from 300 to

400 based on catalyst type (for this case V2O5 is used), maximizes NOx reduction

and minimizes ammonia slip which is dependent on NH3 to NOx ratio, NOx removal

efficiency could reach up to 90% (Abbasian, 2012) and catalysts are made from

zeolites, precious and base metals. (Sadan, 2014).

SCR process depend on the following major points, which are the

concentration of oxygen, the inhibition of ammonia, the ratio of ammonia to NOx,

and the temperature of the process. The process chemistry can be summarized

by the following reactions. There are two desired reactions and two undesired

7
reactions that could have an inverse effect on the process. The overall SCR

reactions are as following Equations (1) & (2) (Abbasian, 2012):

3
xNO + yNH3 +(43 y x)O2 = (x + y)N2 + 2yH2O (1)

3
xNO2 + yNH3 +(43 y x)O2 = (x + y)N2 + 2yH2O (2)

Selective reaction Equations (3) & (4) (Khanh-Quang Tran, 2008) (R. Bonzi L. L.,

2010):

4NO + 43 + 2 42 + 62 (3)

22 + 43 32+ 62 (4)

Non-selective reaction Equations (5) & (6) (Khanh-Quang Tran, 2008):

43 + 5242 + 62 (5)

32 + 4322 + 62 (6)

The temperature of the process is the main factor that decides upon the

favorability of the undesired reactions.

ZEOLITE PROPERTIES THAT POINT TO SCR

Natural zeolites were used in this study, namely Heulandite (HEU) and

MOR (MOR) as one of the catalyst for SCR because of their abundance in the

country. The catalysts distinct properties; uniform dispersion, amount of

exchangeable cations in their voids, and breadth of pores prove them to have

varied applications in separation processes. Microscopically, they possess pores

8
or channels which are of relatively small and uniform size and high internal surface

area making them capable of selectively trapping other foreign molecules. It is for

this reason that zeolites are frequently referred to as molecular sieves (R.

Barrer,1973; M. Guisnet, J.P. Gilson (Eds.),2002). Another distinct characteristic

of catalytic zeolites is their silicon-to-aluminum ratio (Si/Al). Their Si/Al ratio is of

utmost importance as it indicates their stability toward chemical attack, high

temperature, and moisture (V. Petranovski, V. Gurin, N. Bogdanchikova, A. Licea-

Claverie, Y. Sugi, E. Stoyanov, 2002; N. Zilkova, M. Bejblova, B. Gil, S.I. Zones,

A.W. Burton, C.-Y. Chen, Z. Musilova-Pavlackova, G. Kosova, J. Cejka, 2009).

HEU and MOR have Si/Al ratio of 4and 5, respectively.

Figure 1.1 The development of the three dimensional structure of zeolite with

high i/Al ratio (Devadas, 2006)

The structure of aluminosilicate is negatively charged which attracts the

residing positive cations. Within this framework, are linked cavities or network of

open pore with a restricting regular uniform arrangement. These pores adjust and

adsorb those that are smaller in diameter and exclude the larger molecules as a

result of its molecular sieving property. The spaces are interconnected and form

9
long wide channels of varying size depending on the mineral, which allows the

easy movement of the resident ions and molecules into and out of the structure.

These channels are evenly distributed throughout the grains of the zeolite. The

voids present within the structure are enough to permit the passage of the

adsorbed molecules through it and the penetration further into the interior structure

zeolite active sites where the SCR can take place. Zeolites have distinct qualities

that prove them to have varied applications in separation processes. These are

uniform dispersion, amount of exchangeable cations in their voids, breadth of

pores, and silicon to aluminium ratios. Moreover, these characteristics can be

modified and tuned accordingly. For efficient use of zeolite, it is necessary to

develop a major matrix component which will allow the free passage of gas

molecule into the depth of the material and would open the input channel. Just like

the popular oxides of vanadium, titanium, and tungsten, zeolites are also

considered as SCR catalysts (T.C. Watling, Y. Lopez, J.D. Pless, B. Sukumar, W.

Klink, P. Markatou, 2013; G. Neri, G. Rizzo, S. Galvagno, A. Donato, M.G.

Musolino, R. Pietropaolo, 2003; H. An, P.J. McGinn, 2006.Z. Zhang, Y. Zhang, Z.

Wang, X. Gao, 2010; K. Kamatani, K. Higuchi, Y. Yamamoto, S. Arai, N. Tanaka,

M. Ogura, 2015;W.M. Vatauk, W.L. Klotz, R.L. Stallings, 1999;S. Biswas, V.

Verma, J.J. Schauer, C. Sioutas,2009 ) such that they may be able to reduce NOx

and oxidize unburnt hydrocarbons (Boado & Caldona, 2017).

10
GYPSUM-REINFORCED ZEOLITE

It is to be noted that owing to their porosity and density, pure zeolites are

mechanically prone to rupture such that they may not be able to withstand the

effect of the exhaust flow rate. In this regard, gypsum, a low-cost binder material,

is added as reinforcement to make the resulting material denser and more

compact. The stable crystal lattice of the gypsum material works hand in hand with

the fine fractions of the zeolite to provide advanced surface for ion exchange.

Gypsum has a stable monoclinic crystal lattice and sorption capacities (W.A.

Felsing, A.D. Potter,1930; A. Colombo, M. Bortoli, H. Knoppel, E. Pecchio, H.

Vissers,1993) and are larger-sized than that of the zeolite, which without blocking

the channels to the zeolite, provides advanced surface for a reaction to take place

(F. Heinzelmann, Q.L. Yu, B.M. Rumiantsev, H.J.H. Brouwers, 2012; H. Li, 2014).

ZEOLITE MODIFICATION: COPPER LOADING

Metal-based zeolites are one of the main types of catalysts involved in NOx

SCR process and are usually used for temperatures higher than 400-600C.

Copper-based zeolites have been examined thoroughly because these materials

were the first metal zeolites found to be active in SCR. Using hydrocarbon and

ammonia as reducing agent can cause the copper loaded zeolite to be active. This

is widely used compared to V2O5 due to its high activity in higher temperature. It is

also cheaper compared to V2O5 and can remove NOx and SOx simultaneously with

high activity (Sadan, 2014).

11
 1.3 PARADIGM OF THE STUDY

Figure 1.2 presents the general flow of the research study from the input to

process to output recovery. The input starts with the production of gypsum-

reinforced zeolite composites arranged in a fixed bed.

OUTPUT
PROCESS
INPUT

Producton of FTIR and XRF analysis Established

gypsum-reinforced and characterizaton properties of GRZC
zeolite composites of GRZC advantageous in NOx
adsorption

Exhaust gas from Adsorption of NOx adsorption

gasoline engine Nitrogen Oxides by capacity of the
source. Selective Catalytic composite
Reduction

Figure 1.2 Input-Process-Output

The initial input of the study requires the passage of NOX through the GRZC

as a fixed bed for adsorption to occur. GRZC is expected to adsorb which makes

the output NOX concentration be lower than that of the input concentration. The

pore size diameter, pore volume and surface area of the GRZC are used to

substantiate that the adsorption will at least be possible but more importantly,

effective. The comparison of the pore size diameter of the composite and the

typical NOX diameter will be confirmed.

1.4 STATEMENT OF THE PROBLEM

The study aims to quantify the SCR capability of gypsum-reinforced zeolite

composite (GRZC), that is pure and copper loaded. The composite aims to

12
significantly reduce the concentration NOx from the emission of a controlled

gasoline engine source. Specifically, it intends to answer the following questions:

1. What is the extent of copper loading in the GRZC samples?

a. 30:70 Cu-GRZC

b. 60:40 Cu-GRZC

c. 90:10 Cu-GRZC

Hypothesis: It is hypothesized that the 90:10 Cu-GRZC would have

the highest degree of extent in Cu-loading while the 30:70 ratio would

have the lowest degree of extent in Cu-loading in terms of elemental

composition of materials by using X-Ray Fluorescence Analysis.

2. What is the percentage decrease in NOx emission when the exhaust is

intercepted with various GRZC samples?

a. 30:70 GRZC

b. 60:40 GRZC

c. 90:10 GRZC

d. 30:70 Cu-GRZC

e. 60:40 Cu-GRZC

f. 90:10 Cu-GRZC

Hypothesis: It is expected to have high NOx conversion of 90:10 Cu-

GRZC, mainly because of the high copper content, in terms of wt. %

and dispersion, of the prepared various GRZC samples.

13
 3. Is there a significant difference in the NOx reduction capability of bare

GRZC versus copper-loaded GRZC?

Hypothesis: There is a significant difference in the capability of bare

GRZC & Cu-GRZC in the reduction of NOx emission due to the

conditions such as Cu- Loading concentration in the precursor solution,

temperature, Si/Al ratio and the behavior of the catalyst during the NOx

removal process

1.5 SCOPE AND DELIMITATION

There are different types of air pollutants; volatile organic compounds

(VOCs), carbon monoxide (CO), nitrogen oxides (NO x), sulfur dioxide (SOx),

particulate matter (PM), and lead. However, this research only focuses on the

ability of zeolite to lessen the emission of NOx in the atmosphere.

Zeolites are natural minerals that are mined in many parts of the world; most

zeolites used commercially are produced synthetically. There are currently around

40 types of naturally occurring zeolites found in nature (Auerbach et al, 2003).

However, for this study, the researches opted to use. The zeolites will be

purchased at Mangatarem, Pangasinan, for it is readily available at SAILE

Industries Philippines.

Preparation of catalyst is as very important stage because it affects the

activity of the catalyst during SCR reactions. Copper-zeolites, especially Cu-ZSM-

5, are being studied to use them as NOx removal catalysts (Broeke & Saleh, 2014).

14
There are several different methods to prepare copper-zeolite catalyst but the

researchers will only use wet ion exchange method.

1.6 CONSTRAINTS OF THE STUDY

The actual composition of the natural zeolites may vary and cannot be

controlled by the researchers. What is definite, are its major components HEU

and MOR.

14
 1.7 SIGNIFICANCE OF THE STUDY

According to the World Health Organization Air pollution is contamination

of the indoor or outdoor environment by any chemical, physical or biological agent

that modifies the natural characteristics of the atmosphere. Pollutants in the air

are a ubiquitous problem and it is not necessarily visible and coming in one source.

The air that surrounds us contains damaging components to both the environment

and to our very own health. These components varies from particulate matter (PM),

volatile organic compounds (VOCs), unburnt hydrocarbons (HCs), carbon dioxide

(), ground level ozone (O3), and oxides of sulfur and nitrogen (SOx and NOx).

Human health can be affected either having acute or chronic effects that damages

the different organs and systems in the body. (Kampa & Castanas, 2008).

The problem arises in handling the airborne pollutants as it affects the whole

ecosystem even from a microsource such as the car engine. In expense to higher

fuel efficiency in automotive applications, emissions of nitrogen oxides (NOx) is a

rising concern. Nitrogen oxides can be seen as a reddish-brown layer in the urban

air that contribute to the formation of harmful ground level ozone as well as the

production of acid rain. This study aims to investigates how NOx can be

sequestered using an improved zeolite-gypsum composite imparted in an

emissions control device (ECD). Zeolites are aluminosilicate crystalline materials

that compose of uniform pore sizes found in its lattice structure. Both synthetic and

natural zeolites potential arises in its capability of SCR of ammonia and nitrogen

oxides (NOx).

15
 In respect to the rising issue of air pollution and its increase in concentration,

more demanding emission standards are being proposed worldwide. The

production of an ECD will predominantly focus on the transportation sector

emissions. Transportation vehicles have unquestionable detrimental effects on the

public health and as more Filipinos rely on mobile transport there is undeniable

increase in airborne pollutants. The ordinary Filipino, with his attention focused on

making a decent living, cannot be expected to easily replace his vehicle just so to

adhere to clean air regulations. The resulting ECD that utilizes a low-cost solid

sorbent is thought to provide people with an alternative solution to effectively

control vehicular emissions.

1.8 OPERATIONAL DEFINITION OF TERMS

Adsorbent A material that has the capability to extract certain substances from

gases, liquids, or solids by adhesion to its surface without changing its physical

properties.

Adsorption It is the ability to adhere of atoms, ions, or molecules from a gas,

liquid, or dissolved solid to a surface thus creating a film on the surface. Gypsum

An abundant mineral which is chemically known as calcium sulfate dihydrate

gypsum contains calcium, sulfur bound to oxygen, and water.

Heulandite, HEU also known as Hydrated Calcium Sodium Aluminum Silicate is

one of the most common and one of the most well-known members of the Zeolite

Group with a chemical formula of (Ca,Na)2-3Al3(Al,Si)2Si13O3612H2O

16
MOR, MOR also known as hydrated calcium sodium potassium aluminum

silicate. MOR is one of the rarer, but still somewhat more widespread, members

of the zeolites group of minerals. It has the chemical formula of (Ca, Na 2,

K2)Al2Si10O247H2O

Pore size This gives an indication of the median or mean size of the pores on a

membrane surface.

Pore volume It is defined as the ratio of a porous materials air volume to a

porous materials total volume.

Surface area This is the sum of all the areas of all the shapes that cover the

surface of the object.

Emission it is defined as the discharge of gas from the tail pipe of the gasoline

engine source.

Nitrogen Oxide (NOx) Nitrogen oxides can be seen as a reddish-brown layer in

the urban air that contribute to the formation of harmful ground level ozone as well

as the production of acid rain.

Zeolite Zeolites are hydrated microporous aluminosilicate minerals that are

capable of selective ion exchange. They can adsorb molecules on their large

internal area, provided they can pass through the windows. They can be a solid

acid catalyst.

Selective Catalytic Reduction Selective Catalytic Reduction, also called SCR,

is used to describe a chemical reaction in which harmful nitrogen oxides (NOx) in

exhaust gas are converted into water (H2O) and nitrogen (N2).

17
Reduction Reduction specifically refers to the chemical reaction that NOx

undergoes, although it is directly related to a decrease in amount.

18
 Chapter 2

RESEARCH DESIGN AND METHODOLOGY

2.1 RESEARCH DESIGN

In the determination of the adsorption of NOx of the ZGC, an experimental

approach was employed.

2.2 DATA GATHERING TOOLS

Instrumental Analysis. X-ray Fluorescence (XRF) Spectroscopy at the Mining

Engineering Department of Saint Louis University will be conducted for the bare

and modified composites.

2.2.1 FTIR SPECTROSCOPY

FTIR spectra provide highly specific spectroscopic fingerprints of microorganisms

allowing an accurate identification at both species and sub-species levels. This

approach represents an analytical, non-destructive, and dynamic method to

investigate the specific spectroscopic fingerprints of GRZC. It is based on the

vibrational excitation of molecular bonds by absorption of infrared light energy. (M.

Taha, et. al., 2013)

2.2.2 XRF

X Ray Fluorescence Analysis is an analytical technique to determine the

elemental composition of materials. This analysis will be used in order to determine

the extent of copper-loading onto the composite

19
2.2.3 NOx GAS ANALYZER

NOx gas analyzer will be used to determine the varying levels of NO, NOx, and

NO2 and keep the concentration at lower levels.

2.3 DATA GATHERING PROCEDURE

Materials. Natural zeolite occurring in granulates mainly consisting of HEU and

MOR are taken from SAILE Industries Philippines, operating in Mangatarem,

Pangasinan. These will be modified using 1-N Hydrochloric Acid (HCl), 0.1-M

Sodium Chloride (NaCl), and 0.5-M Copper Sulfate (CuSO4) solutions from the

Chemical Engineering Laboratories of Saint Louis University.

Ion-Exchange. Raw zeolite granules will be will washed with deionized water (Z)

to remove residual fine particles and then dried in an oven for 1 hour at 110C.

Dried zeolite samples will be soaked in HCl solution for 1 hour. After soaking, HCl

treated samples (HZ) will be will washed with deionized water to remove Cl- ions,

using litmus paper as its indicator. Subsequently, the samples will be dried again

in an oven for 1 hour at 110C. In preparation for copper ion-exchange, Na+, as

the displaceable ion, will be loaded in by immersing the zeolite samples in NaCl

solution. The samples will be then will washed using deionized water until no color

change in the blue litmus paper will be observed and then dried, just like in the

previous steps, to secure Na+ ions. Na+ treated zeolite (NaZ) will be loaded with

Cu2+ ions using CuSO4 solution. The mixture will be first stirred for 1 hour at 60C.

After which, it will be soaked for 2 hours. To remove the sulfur, samples will be will

washed once by distilled water. Calcination of the zeolite is the final modification

step for copper-exchanged

20
zeolite (CuZ). The drying process will be done at 400C for 5 hours. The calcined

samples will be separated into three parts to which the will be reinforced with

gypsum, individually. The reinforcement of individual samples will be 30, 60 and

90% of Zeolite to which the adding of gypsum depends on the current mass of the

Zeolite. The individual samples will be then fashioned into discs, with a proportion

of 10 grams of samples 5 mL of water.

2.4 TREATMENT OF DATA

The paired sample t-test, sometimes called the dependent sample t-test,

will be used to determine statistically the difference between the performances of

Non-Copper loaded and Copper-loaded zeolite composites. By means of the FTIR,

the researchers will be able to determine the successful incorporation of copper

into the composite. XRF shall be used to quantify the amount of copper, thus the

approximate number of active sites responsible for NOx reduction.

21
 Chapter 3

REVIEW OF RELATED LITERATURE

Zeolite Framework

According to Garnett, Fallick, Rowland, and Ostle and further studies of

Bonenfant, Kharoune, Niquette, Mimeault and Hausler, Zeolites are a subclass of

tectosilicates that possess a framework formed by a three dimensional assembly

of tetrahedral consisting of silicon tetroxide (SiO4) and Aluminum Oxide

(AlO4).Their aluminosilicate tetrahedral assembly result to high internal surface

area and thus point them as good adsorbents (Bonenfant, et al., 2008); (Hardie,

Garnett, Fallick, Rowland, Ostle, & Flowers, 2011).

According to Clean Air Technology Center of the U.S. Environmental

Protection Agency, zeolite has a natural porosity because it has a crystal structure

with windows, cages, and supercages. The windows are how the molecules reach

the cages and supercages to be adsorbed or catalyzed. The cages are the smaller

cells in the crystal structure. The supercages are cells in the crystal structure that

are larger than cages and may even contain cages. The natural zeolites are limited

in their window size (pore size) and are all hydrophilic (having an affinity for

water). Generally, the higher the silicon to aluminum ratio, the more hydrophobic

the zeolite is. Hydrophobic zeolite must be synthesized, for it does not occur in

nature. Synthesis is important because it allows scientists and engineers to (1)

predict the properties of the zeolite, (2) make a zeolite with a larger pore size,

and (3) make hydrophobic zeolite. (Clean Air Technology Center (MD-12), 1998).

22
Gypsum

Gypsum is used as a main component due to its availability, low energy

consumption in obtaining the material and manufacturability in processing. NOx

first reaches the developed surface area of the porous gypsum material. Then NOx

passes into the depth of the binder due to its high intergranular pores. It will further

penetrate into the micro porous structure of the zeolite due to the gradient diffusion

forces. The molecules of the NOx are adsorbed mainly due to dipole interactions

and some will experience a partial ion exchange.

Characterization of Supported Metal Zeolites

According to the study of Sadan, in the span of 20 years, much research

has been carried out concerning zeolite catalysts for the NHR3R-SCR reaction.

Different zeolite materials, such as MOR, MFI, Y, BEA, FER loaded with various

metals, i.e. Cu, Co, Fe and Pt, have been investigated. Especially, copper-based

zeolites have been examined thoroughly because these materials were the first

metal zeolites found to be active in SCR (Sadan, 2014)

Former studies of the catalytic activity of Fe-loaded zeolite and Cu-loaded

zeolite used to decompose NOx by SCR were conducted by May Nwe Win, Tin

Tin Aye, Kyaw Myo Naing, Nyunt Wynn, and Maung Maung Htay. The Fe and Cu

containing zeolites were prepared by solid state ion-exchange method under

ambient pressure and at the temperature of 600C whereby characterized by XRD,

FT-IR and SEM methods. The XRD data revealed that zeolite is composed

23
of sodium, aluminum silicate hydrate and Supported metal zeolites are totally

different from normal zeolite. The results show Cu-ZSM-5 was the best catalytic

absorber having 87% conversion of the NOx molecule with the corresponding

optimum amount of catalyst (1.0 0.5) g working under the reactor space volume

of 30 cm3 at ambient temperature (30-32)C compared to Fe-ZSM-5 and H-ZSM-

5 (May, Tin, Kyaw, Nyunt, & Maung, 2005).

Zeolite and Gypsum Combinations

There have been previous studies concerning a blend of zeolites and

gypsum. Orlov et. al. suggested the use porous gypsum-zeolite material (PGZM)

in adsorbing indoor pollutants through molecular sieve effect. Their experiment

showed longer saturation time of the PGZM as compared to other sorbents and

that the increased temperature as a sign of the exothermic reaction between

ammonia and the material as it was adsorbed (Orlov, Yu, Rumiantsev, & Brouwers,

2012). In the other study, a zeolite-gypsum composite (ZGC) was tested in its

capability of reducing PM from emissions, particularly that of diesel-run vehicles.

The results showed a significant decrease in exhaust gas opacity which is

attributed to the oxidation of PM in the composite (Munoz-Boado & Caldona,

2017). The ZGC is simply a 2:1 mixture of natural zeolite to commercial gypsum.

The proponents of this project intend to build upon the idea on an improved ZGC

where the zeolites are chemically modified and then combine it with foamed

gypsum. Foamed gypsum makes the product less dense and more porous. This

can be achieved by gas foaming agents such as potassium alum,

24
sodium lauryl sulfate, and ammonium bicarbonate, or employ air entrainment

methods as explored by Colak (Colak, 2000).

The adhesion of the zeolite matrix and the porous gypsum is formed by the

needle-like contact point of the gypsum protruding to the surface of the zeolite.

Gypsum crystals and the surface of the zeolites are located at different angles.

Gypsum contains a considerable larger particulate size compared to that of the

zeolite. The contact point minimizes the blocking of the zeolite input channels.

These in turn will allow the access of the adsorbed molecule of the NOx to

penetrate the thickness of the depth to provide a high sorption property of the

gypsum zeolite material.

The stable crystal lattice of the gypsum material works hand in hand with

the fine fractions of the zeolite to provide advanced surface for ion exchange. The

composite themselves has the control over their molecular sieves property.

Copper loading of Zeolite Composite

De La Torre et al. observed that the most active species in NOx reduction

using a zeolite composite was Cu2+. The experiment concluded that higher metal

loading decreased the maximum NOx conversion as well as having enhanced

selectivity to N2O (De La Torre, Ayo, & Velasco, 2012). High NOx reduction

catalysis was also analyzed by Effinov et al. by using Copper-mordenites (Effinov,

Petranoskii, Marzke, Pestryakov, Hernandez, & Chavez, 2004). The effect of

copper loaded gypsum-reinforced zeolite composite is to be employed in

25
this research to determine if a higher performance selective NOx reduction can be

achieved.

Abdallah M. Hasna conducted new development of zeolite supported metal

catalysts Cu-ZSM5(158) catalyst using electrical heating element reactor for

better decomposition of nitrogen oxides. The results illustrated a consistent source

data for the reduction of NOx in a microreactor for the Cu-ZSM5 (158), at

temperatures of 350, 400 and 450 C. The maximum conversion of 64.32 % was

obtained at the highest contact time and the highest temperature of 450C with

respect to first order kinetics following the Arrhenius equation. The purpose of

Abdallah is to illustrate the conversion calculation process at various temperatures

and contact times using zeolite supported metal catalysts Cu-ZSM5(158) catalyst

(Hasna, 2009).

Selective Catalytic Reduction

NOx gases are formed during combustion at high temperatures. Nitric

Oxide/ nitrogen monoxide (NO), Nitrogen dioxide (NO2), and Nitrous oxide (N2O)

are considered as the main representatives of the NOx group. NO and N 2O are

odourless and colourless but NO2 can be seen as a reddish brown layer in the

air.

According to Sadan, Low NOx burners, Over Fire Air, Re-burning, Flue gas

recirculation, and selective non-catalytic reduction, although commercially used,

has low efficiencies. A good candidate for NOx reduction would be SCR

Technology (Sadan, 2014). As reported by Cavenati, Grande and Rodrigues, the

26
maximum amount of Nitrogen and Carbon Dioxide in a quality-pipeline cannot

exceed 4% and 2% respectively (Cavenati, Grande, & Rodrigues, 2004).

According to Yvonne Traa, Beate Burger, Jens Weitkamp, there are three

catalytic methods for removing NOx from engine exhaust gases which are usually

classified into three, (i) non-selective reduction, (ii) selective reduction and (iii)

decomposition. An example for non-selective reduction would be the three-way

catalytic converters used for the purification of emissions from spark ignition

engines. However, the traditional three-way catalyst does not control NOx

emissions in oxygen-rich exhaust gas (Traa, Burger, & Weitkamp, 1999). The

study of Sadan, found that the SCR process is considered nowadays as the most

effective method of the leading post combustion abatement technologies for NOx

removal in stationary applications such as chemical industries (Abbasian, 2012);

(Zhang, 2001). Moreover, based on the results obtained by Sadan, it was expected

to have high NOx conversion, mainly because of the high copper content, in terms

of %wt, of the prepared catalysts. Thus, in this study the SCR paired with copper

loaded gypsum-reinforced zeolite composite is used in order to reduce NOx

emission produced by gasoline engine vehicles (Sadan, 2014).

SCR is used to describe a chemical reaction in which harmful nitrogen

oxides (NOx) in exhaust gas are converted into water (H2O) and nitrogen (N2). By

using this technology the removal efficiency could reach up to 90% (Abbasian,

2012). The employed temperature ranges from 300 to 400oC based on the catalyst

type. Catalysts used are usually zeolites, base metals and precious metals.

27
 The performance of commercial silicon carbide Cu/zeolite by coating it on a

diesel particulate filter was analyzed by Millo et al. It was observed that there was

an increased conversion at temperatures higher than 250C until a maximum thus

NOx conversion is a function of temperature. The maximum conversion was

achieved at equimolar concentrations of NO2/NOx ratio. The consumption of NO2

for its oxidation, and the production of NO resulted in passive soot regeneration

(Millo, Rafigh, Fino, & Miceli, 2017). The study of Troconi et al. suggests how to

develop a suitable design and proper dosing to control the process for soot

oxidations interactions with SCR (Troconi, Nova, Marchitti , Koltsakis , Karamitros,

& Maletic, 2015).

The catalyst used for temperatures higher than 400-600oC is the metal

based zeolite catalyst due to its resistance to thermal excursions. The activity of

the catalyst during the SCR reaction is mostly affected by the preparation of

catalyst. The preparation employed in this research is the Wet Ion Exchange (WIE)

which is the most common method in preparing metal-exchanged zeolites. The

copper salt is dissolve considerably with deionized water followed by the addition

of the zeolite composite. The prepared catalysts are added in the water suspension

in a drop-wise manner to the dissolved copper salt under continuous stirring. Wet

ion exchange is a simpler process compared to impregnation. It shows a higher

activity for the abatement of NOx compared to the solid ion exchange. The percent

conversion of NOx reaches to approximately 99.9% approximately. A limitation of

this technique is the difficulty to have full ion exchange and the longer preparation

time (Pieterse, 2004; Yang, 2004).

28
 Zeolite can be used as a molecular sieve because it has a uniform window

(or pore) size. Zeolite is metastable; i.e., it is stable as long as it is at a suitable

temperature and pH. Within this range, it is unaffected by wide swings in

temperature, pressure, and ionizing radiation. Natural zeolite exists as a natural

rock, and these can reach boulder size. However, synthesized zeolite crystals are

always less than a millimeter in size -- because the crystals grow slowly, and we

usually want the zeolite in this century or millennium.

In this study HEU and MOR are used because of their abundance in

the Philippines. MOR is an industrially important zeolite used as a catalyst for

various reactions, viz. hydrocarbon hydrocracking, hydro-isomerization, alkylation,

reforming, and dewaxing, and, also, in the production of dimethyl amines. There

have been lots of articles and patents concerning MOR synthesis in the presence

or absence of organic templates as structure directing agents that tailor pore

openings for some selected catalytic reactions. MORs shape selectivity, acidity

and thermal stability are its unique features. In order to optimize the catalytic

properties of MOR, the zeolite has been subjected to chemical modification using

various procedures, most importantly are the metal-ion incorporation, pore size

engineering and partial dealumination. In this study, the zeolite will be subjected

to metal-ion incorporation. Ion exchange is well suited for zeolite modification,

whereby introduction of different cations modifies the catalytic and sorption

performances of the zeolite. It controls the effective pore size and modifies the

electrostatic field and field gradient in the zeolite, thus generating active sites

inside the framework capable of attracting reactant

29
molecules and prompting their bond distortion and rupture. These are necessary

molecular rearrangement events for the anticipated chemical change to occur.

Activity and shape selectivity of a zeolytic catalyst depend generally on the

dispersity (particle size), structure, morphology, and composition of the

incorporated transition metal ions (TMI) particles, as well as their interactions with

the framework components. A fair TMI dispersion will depend on a proper selection

of the precursor compound and the zeolite material (Mohamed M. Mohamed et al.,

2005)

Clinoptilolite and heulandite are two closely related natural zeolites and

commonly coexist in sedimentary rocks of volcanic origin. The topological

arrangement of the TO4 (T-atom is Si or Al) building blocks in these two minerals

form a network recognized by the International Zeolite Association as HEU.

Although a variety of zeolite samples are described as either heulandite or

clinoptilolite on the basis of chemical parameters and/or thermal behavior, in

several instances the mineral name is assigned based only on the site where the

sample originates. The name heulandite is used for samples in vugs of igneous

rocks, while samples in diagenetically altered vitroclastic sediments are assigned

the name clinoptilolite. Some publications refer to the type of zeolite only based

upon the sample origin and without further analysis. Other authors argue that two

mineral names are not necessary to describe these zeolites and suggest that

silica-rich heulandite could replace the name clinoptilolite .The Structure

Commission of the International Zeolite Association provides the unique HEU

framework type code for the heulandite family of zeolites, without commenting on

30
differences between heulandite and clinoptilolite. The Si/Al ratio reflects the

chemistry of the rigid framework but has no topological content. Zeolite mineral

species are not normally distinguished solely on Si/Al ratio. Indeed, many zeolite

species may possess variable Si/Al ratio and display the same framework

structure. Despite this fact, the subcommittee on zeolites of the International

Mineralogical Association, Commission on New Minerals and Mineral Names, has

supported the identification of heulandite and clinoptilolite based on the Si/Al ratio.

This is an exception based on the established usage of the heulandite and

clinoptilolite names and on the convenience for recognizing a chemical feature.

Therefore, the official definition of heulandite is a zeolite mineral with framework

topology HEU and the ratio Si/Al < 4 and the definition of clinoptilolite is a zeolite

with the same framework topology and Si/A1 P 4.0. (S. Yang et al, 2010)

Zeolite has a specific characteristics represented in void structure and

acidity, where it is used as a heterogeneous catalyst. The void structure could be

central or board types. The acidity has a big influence on the activity of catalysts,

where it is represented in Bronsted and Lewis acid sites. Bronsted acid can donate

protons. On the other hand, Lewis acid can accept a pair of electrons. Bronsted

acid in zeolites may change into Lewis acid under condition of heating (Devadas,

2006).

Synthesis is important because it allows scientists and engineers to (1)

predict the properties of the zeolite, (2) make a zeolite with a larger pore size,

and (3) make hydrophobic zeolite. Hydrophobic zeolite must be synthesized, for it

does not occur in nature (U.S. Environmental Protection Agency, July 1998).

31
References

Abbasian, J. (2012). Dry generable CuO/y-AL2O3 catalyst for simutaneous of SOx

and NOx from flue gas. Applied Catalysis B: Environmental, 297-303.

Bonenfant, D., Hausler, R., Kharoune, L., Kharoune, M., Mimeault, M., Niquette,
P., et al. (2008). CO2 Sequestration Potential of Steel Slags at Ambient
Pressure and Temperature. Industrial & Engineering Chemistry Research,
7610-7616.

Cavenati, S., Grande, C. A., & Rodrigues, A. E. (2004). Adsorption Equilibrium of

Methane, Carbon Dioxide and Nitrogen on Zeolite 13X at High Pressures.
J. Chem. Eng Data 49, 1095-1101.

Clean Air Technology Center (MD-12). (1998). Zeolite, A versatile air pollutant
Adsorber. Research Triangle Park, NC 27711: Office of Air Technology and
Planning Standards, U.S. Environmental Protection Agency.

Colak, A. (2000). Density and Strength Characteristics of Foamed Gypsum.

Cement and Concrete Composites, 193-200.

De La Torre, U., Ayo, B., & Velasco, J. (2012). Cu-Zeolite NH3-SCR Catalysts for
NOx Removal in the combined NSR-SC2 technology. Chemical
Engineering Journal, 10-17.

Effinov, A., Petranoskii, V., Marzke, R., Pestryakov, A., Hernandez, M., & Chavez,
F. (2004). Copper Mortdenite as a de-NOx Catalyst: Role of Variable Silica-
Alumina Ratio and Effects of Adsorbed Water. Proc. XIX Iberoamerican
Symp. on Catalysts.

Hardie, S., Garnett, M., Fallick, A., Rowland, A., Ostle, N., & Flowers, T. (2011).
Abiotic Driver and their interactive effect on the flux and carbon isotope
composition of peat-respired CO2. Soil Biology & Biochemistry 43, 2432-
2440.

Hasna, A. M. (2009). Reduction of NOx Gases using Copper Zeolite Catalyst.

May, N. W., Tin, T. A., Kyaw, M., Nyunt, W., & Maung, M. (2005). Supported Metal
Zeolites as Environmental Catalysts for Reduction of NOx molecules.
Chemistry No. 1, Vol. III.

32
Millo, F., Rafigh, M., Fino, D., & Miceli, P. (2017). Application of a global kinetic
model on an SCR coated on Filter (SCR-F) catalyst for automotive
applications. Fuel, 198, 183-192.

Munoz-Boado, M., & Caldona, E. B. (2017). Gypsum-Reinforced Zeolite

Composite for Particulate Matter Reduction from Vehicular Emissions.
Journal of Environmental Chemical Engineering.

Orlov, A. V., Yu, Q., Rumiantsev, B. M., & Brouwers, H. H. (2012). Indoor air quality
improvement applying novel gypsum based materials. 18th Ibausil,
International Conference on Building Materials (Internationale
Baustofftagung), (pp. 1160-1165). Weimar, Germany.

Sadan, H. M. (2014). Removal of SOx and NOx gases from Stationary Sources
using Copper Zeolite Based Catalyst.

Traa, Y., Burger, B., & Weitkamp, J. (1999). Zeolite-based materials for the
selective catalytic reduction of NOx with Hydrcarbons. Microporous and
Mesoporous Materials, 3-41.

Troconi, E., Nova, I., Marchitti , F., Koltsakis , G., Karamitros, D., & Maletic, B.
(2015). Interaction of NOx Reduction and Soot Oxidation in a DPF with Cu-
Zeolite SCR Coating . Emission Control Science and Technology 1(2), 134-
151.

Zhang, D. K. (2001). Selective Catalytic Reduction of Nitric Oxide over Cu and Co

ion-exchange ZSM-5 Zeolite: the effect of SiO2/Al2O3/ratio and cation
loading. Catalysis Today 68, 161-171.

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