CHAPTER 1 LITERATURE REVIEW OF FLY ASH IN

CHAPTER 1 LITERATURE REVIEW OF FLY ASH IN

U n i i v e r r s i i t t y o f f

P r r e t t o r r i i a e t t d

– L a n d m a n

,

,

A A

(

(

2

0

0

3

)

)

CHAPTER 1

LITERATURE REVIEW OF FLY ASH

IN

Aspects of solid-state chemistry of fly ash and ultramarine pigments

U n i i v e r r s i i t t y o f f

P r r e t t o r r i i a e t t d – L a n d m a n ,

,

A A

(

( 2 0 0 3

)

)

Aspects of solid-state chemistry of fly ash and ultramarine pigments

1. LITERATURE REVIEW OF FLY ASH

1.1. Introduction

Kruger reports that the US Congress has classified fly ash as the sixth most abundant resource in the United States of America.

1

Israel could sell good-quality fly ash, based on imported South African coal, at $20 per tonne in 1999.

2

Yet, few

chemists in South Africa see fly ash as a field worthy of study. What follows aims to highlight the opportunities within the field of fly ash research.

Fly ash is a predominantly inorganic residue obtained from the flue gases of furnaces at pulverised coal power plants. When coal is burnt in pulverized coal boilers, the minerals, entrained in the coal, are thermally transformed into chemical species that are reactive or could be chemically activated, for example by the addition of calcium

hydroxide.

3

The finely divided glass phase, the predominant phase in fly ash, reacts

as a pozzolan, defined by Manz as "...a siliceous and aluminous material that in itself possesses little or no cementitious value but will, in finely divided form and in the presence of moisture, chemically react with calcium hydroxide at ordinary

temperatures to form compounds possessing cementitious properties."

4

Eskom, a major power utility in the Republic of South Africa, is a major producer of fly ash. South African fly ash for use as a cement extender is processed and marketed

by Ash Resources (Pty) Ltd.

5

Worldwide, the cement industry has almost reached its maximum consumption level of fly ash, so too its use as landfill. Sphere-Fill (Pty) Ltd, which sources fly ash from

the Lethabo (a Tswana word, which means "good living" or "happiness"

6

) Power

Station in the Northern Free State of the Republic of South Africa, aims to extend the market for this by-product.

The coal in the Republic of South Africa is high in ash content; therefore, the use of fly ash is an environmentally important issue. Eskom produced approximately

27 megatonnes of fly ash in 2001 of which only 1.2 megatonnes were sold

Chapter 1: Literature Review of Fly Ash

14

U n i i v e r r s i i t t y o f f

P r r e t t o r r i i a e t t d – L a n d m a n ,

,

A A

(

( 2 0 0 3

)

)

Aspects of solid-state chemistry of fly ash and ultramarine pigments

(Table 1-1). Emission control legislation has led to an increasing amount of fly ash in a recovered form (Table 1-2).

7

Table 1-1: Eskom statistics regarding coal consumption and ash production

8

Item 2001 2000 1999 1998 1997

Total electricity sold, GWh 181511 178193 173412 171457 172550

Total electricity for Eskom system 198790 194601 188475 185583 187850

(Stations and purchased), GWh

Total produced by Eskom stations, 189590 189307 181818 183093 187811

GWh (net)

Total available for distribution, GWh 196613 191123 184968 182284 184339 burnt,

Average ash content, %

Particulate emissions, kt

Ash produced, Mt

Ash sold, Mt

94136 92289 88470 87225 90169

28.8 28.6

28.5 29.1 28.4

59.64

66.08

67.08 65.21 83.43

26.5

24.6

24.3 24.7 23.7

1.2

1.1

1.1 1.2 1.1

Table 1-2: Environmental implications of using 1 kW of power

8

Grams per 1 kW of power 2001 2000 1999 1998 1997 1992

Ash emitted

500 500 500 500 500 500

140 130 134 135 126 –

0.3 0.4 0.4 0.4 0.4 1.0

Sphere-Fill (Pty) Ltd markets several size fractions of fly ash. Super-Pozz is a fine fraction of fly ash with a 90 % top cut passing of 11 µm and a 99 % top cut passing of

25 µm.

9

The material safety data sheet reports the specific gravity as 2.25, the

melting point as 1 350 ºC and that Super-Pozz is not classified as a hazardous material.

10

Pozzfill is a coarser grade fly ash, varying in size between 40 and

150 µm.

11

A finer fraction of fly ash is marketed as Plasfill, with a size less than

12 µm.

Chapter 1: Literature Review of Fly Ash

15

U n i i v e r r s i i t t y o f f

P r r e t t o r r i i a e t t d – L a n d m a n ,

,

A A

(

( 2 0 0 3

)

)

Aspects of solid-state chemistry of fly ash and ultramarine pigments

Much of the research into fly ash focuses on the measurement of trace concentrations, and the effects of leaching, by X-ray fluorescence, atomic absorption, inductively coupled plasma-optical emission spectroscopy, gas chromatography - mass spectroscopy and laser ionisation mass spectroscopy. Another field of study is the surface adsorbed dioxins and other pollutant chemicals. These were not treated in this review.

Fly ash can be classified as either cementitious or pozzolanic. The cementitious fly ash is labelled as Class C, with SiO

2

+Al

2

O

3

+Fe

2

O

3

making up at least 50 mass percent.

11,12

In pozzolanic fly ash, Class F, SiO

2

+Al

2

O

3

+Fe

2

O

3

makes up more than

70 mass percent of the composition of the fly ash.

11,12

There are two primary sources of fly ash: fly ash from a pulverised coal power plant

and fly ash from a municipal waste incineration plant.

13

This review focuses on class

F fly ash from a pulverised coal power plant.

1.2. Need for Research into Fly Ash

In 2000, the Journal of Hazardous Materials published a special issue on fly ash, its

characterization and uses.

14

The following comment is made in the preface to that

special issue:

Of the hundreds of millions of metric tons of fly ash that are produced annually on a worldwide basis, only a small portion e.g., 20% to 40% of the fly ash is re-used for productive purposes, such as an additive or stabilizer in cement. The remaining amount of fly ash produced annually must either be disposed in controlled landfills or waste containment facilities, or stockpiled for future use or disposal. As a result of the cost associated with disposing these vast quantities of fly ash, a significant economical incentive exists for developing new and innovative, yet environmentally safe, applications for the utilization of coal fly ash.

14

In an article discussing the beneficiation of fly ash, Kruger

11

urges researchers

... to a better understanding of the fundamental characteristics of ash; for example, to what degree do surface characteristics control the reactivity, and what beneficiation techniques are applicable to maximize a particular characteristic? Can fly ash be

Chapter 1: Literature Review of Fly Ash

16

U n i i v e r r s i i t t y o f f

P r r e t t o r r i i a e t t d – L a n d m a n ,

,

A A

(

( 2 0 0 3

)

)

Aspects of solid-state chemistry of fly ash and ultramarine pigments beneficiated to enrich it as a pre-concentration step for the recovery of gallium? Is a particular fraction more suited to producing slow-release fertilizers? How can beneficiation play a role in selecting a portion of fly ash more appropriate to geopolymerization? Knowledge of the needs in the market-place and the symbiotic relation between research and product development is paramount in creating these

new opportunities for fly ash.

11

Scheetz and Earle

12

comment on the use of fly ash in America. Only 27.4 % of the ash produced in 1996 was used in non-landfill applications (confirmed by Hower and others

7

). Scheetz and Earle 12 challenge researchers with the following remark:

...[Fly ash] was imparted with an excess energy, either chemical or stored surface energy, which can be utilized to participate in chemical reactions, if properly activated.

The challenge for the scientific community is to exploit these resources, as low tech

materials, to solve large-volume societal-environmental needs.

12

Malhotra and others

15

report on the use of fly ash in America

in 2002. They estimate that only 30 % of the fly ash produced is used. Two thirds is used in the concrete industry, which has reached a maximum consumption figure. Malhotra and others

15

challenge researchers to find low cost but high volume applications of fly ash, and to convert ashes into value- added products.

15

Foner and others

2

emphasize the role of developing new applications of fly ash in

1999, by pointing out that Israel would produce 1.3 megatonnes of coal ash per annum by 2001 and that only 0.6 megatonnes could be used by the cement

industry.

2

Nathan and others

16

estimated the figures as 1.2 megatonnes and

0.8 megatonnes respectively by 2000.

In the United Kingdom approximately 50 % of the fly ash produced is used,

17

and in

India only 6 %.

18

1.3. Characteristics of Fly Ash

Fly ash is a diverse substance. The characteristics of fly ash differ depending on the source of the coal used in the power plant and the method of combustion.

3,12,19

Cenospheres, hollow spherical particles as part of fly ash, are believed to be formed

Chapter 1: Literature Review of Fly Ash

17

U n i i v e r r s i i t t y o f f

P r r e t t o r r i i a e t t d – L a n d m a n ,

,

A A

(

( 2 0 0 3

)

)

Aspects of solid-state chemistry of fly ash and ultramarine pigments by the expansion of CO

2

and H

2

O gas, evolved from minerals within the coal being burnt.

20

The predominant forces are, however, the pressure and surface tension on

the melts,

20

as well as gravity. The predominantly spherical microscopic structure of

fine fly ash is related to the equilibrium of the forces on the molten inorganic particle as it is forced up the furnace or smoke stack against gravity. The molten inorganic particles cool down rapidly, maintaining their equilibrium shape. A similar situation is found in spherical drops of water falling from a faucet.

Because cenospheres are hollow, they have a low bulk density. The percentage cenospheres increase with the ash content in the coal, and decrease with the concentration of Fe

2

O

3

.

21

This indicates that Fe

2

O

3

is concentrated in the higher density fraction of fly ash,

21

which is to be expected from the high density of Fe

2

O

3

(5.25 g/cm

3

)

22

and Fe

3

O

4

(5.17 g/cm

3

).

22

The iron species should not contribute significantly to the infrared spectra.

21

The inorganic material entrained over years in the coal melt during the combustion of coal in the furnace, and with some, but limited, fusing of the molten particles.

19

Some

of the vaporized low boiling elements, for example alkali metal salts, coalesce to form submicron particles.

19

Some of the vaporised compounds, most notably the

polynuclear aromatic hydrocarbons and polycyclic aromatic hydrocarbons, adsorb onto the surface of the fly ash particles.

19

The surface of fly ash particles is,

therefore, commonly enriched in carbon, potassium, sodium, calcium and

magnesium.

19

Fly ash has, as mentioned before, a characteristic spherical microscopic structure

(Figure 1-1). This microscopic structure is, in fact, so beautiful that a scanning

electron microscope photograph of fly ash was published on the cover of Science magazine, 7 May 1976, vol 192, no 4239; and again on 19 December 1980, vol 210, no 4476.

Chapter 1: Literature Review of Fly Ash

18

U n i i v e r r s i i t t y o f f

P r r e t t o r r i i a e t t d – L a n d m a n ,

,

A A

(

( 2 0 0 3

)

)

Aspects of solid-state chemistry of fly ash and ultramarine pigments

Figure 1-1: The predominantly spherical microscopic structure of fly ash

Fly ash can be approximated as an aluminosilicate and can be used like other minerals. The amorphous aluminosilicate nature of fly ash makes the chemical structure of fly ash difficult to characterise, but also very versatile, since the glassy phase reacts first before the crystalline phase, and also goes into solution first.

X-ray diffraction is mainly used to describe the mineralogy of fly ash. The mineralogy of fly ash is closely related to the minerals entrained in the coal and several different

minerals have been identified as part of fly ash (Table 1-3). The main phases are

glass, mullite, quartz, magnetite, haematite

19,23

and anhydrite. Methods of quantifying

these minerals, and therefore the glass content, have been developed.

47

The

samples analysed, showed similar mineralogy (Figure 1-2). The mullite present in fly

ash forms by the decomposition of kaolinite

62

which is entrained in the coal.

Chapter 1: Literature Review of Fly Ash

19

U n i i v e r r s i i t t y o f f

P r r e t t o r r i i a e t t d – L a n d m a n ,

,

A A

(

( 2 0 0 3

)

)

Aspects of solid-state chemistry of fly ash and ultramarine pigments

Table 1-3: X-ray diffraction mineralogy of fly ash

Glass

2,3,7,24-52

Quartz

2,3,7,16,24-34,36-72

Mullite

2,3,16,24,27-55,60,61,64-74

Sillimanite

38,67,68

Haematite

3,16,24,26,28-32,34,37-39,44, 46,47,55,60-

62, 66,70,71,73,75

Magnetite

3, 16,24,27-30,32-34,38,39,44-47,55,62,

66,71,76

Anhydrite

2,26,29-31,39,47,60,63,77

Gehlenite

26,34,63

Cristobalite

3,28,45,46,52

Lime

2,3,26,28,29,31,39,16,62,63

Bassanite

26,63

3,16,26,28,30,37,39,52,55,63

Mica

3,26,39,63

Amorphous Ca-Al-Fe silicates

16

Merwinite

31

Enstatite

70,72

Amorphous Al-Fe silicates

16

Illite

65

Calcium Silicate

44

The magnetite referred to in Table 1-3 should be classified as ferrite, due to the

different rates of substitution of Fe

2+

and Fe

3+

by other ions, for example vanadium,

chromium, manganese, cobalt, nickel and zinc.

42,71

Spinels containing mainly iron,

and some chromium and nickel impart magnetic properties to approximately 39 % of

the particles (more so in the finer fractions).

78

This leads to the concentration of these

elements in these fractions, and makes fly ash a valuable "ore" for these elements.

Although fly ash contains many potentially toxic trace elements (Table 1-4), leaching

tests have shown that these are stable within the aluminosilicate matrix.

27,79,80

Accordingly fly ash is not classified as a hazardous waste in America.

27

The only

element that might pose a problem is hexavalent chromium.

2

The Ministry of the

Chapter 1: Literature Review of Fly Ash

20

U n i i v e r r s i i t t y o f f

P r r e t t o r r i i a e t t d – L a n d m a n ,

,

A A

(

( 2 0 0 3

)

)

Aspects of solid-state chemistry of fly ash and ultramarine pigments

Environment of Israel, however, considers the use of fly ash as landfill potentially harmful, and forbids its use as landfill,

2

possibly in reaction to the greater leaching

test results of Nathan and others

16

for arsenic, selenium and chromium. The leaching

behaviour is influenced by several factors;

79,81

therefore results can be expected to

vary for fly ash samples from different sources.

2.5

2.0

1.5

M

Q

M

M

Q

M

M

M

M

M M

M

M

M

M

1.0

M

Q

M

M

0.5

M

Q

M

M

M

M

M

M

M M M

0.0

4 14 24 34 44 54 64

2

θ

Figure 1-2: The mineralogy of fly ash; M: mullite, Q: quartz

Several atomic force microscopy studies on fly ash have been done.

45,46,82,83

Fine fly

ash has a spherical microscopic structure (Figure 1-1). Not all particles are spherical

(Figure 1-1). The size distribution can also be assessed by investigation of the

micrographs. The present micrographs are similar to those in literature.

19,20,24,26,33,35,38,39,46,50,53,54,72,75-77, 83-108

Quantitative work by energy dispersive X-ray

analyses indicates the heterogeneous nature of the fly ash particles.

19,20,40,53,54,71,

83,96,100-105

The infrared spectra of fly ash have also been reported

41,45,46,53,54,104,109

but these

results differ from the infrared spectra for fly ash used in our studies (Figure 1-3).

Mollah and others

46

assign the bands in their spectra. The band at 1080 cm

-1

is assigned to the antisymmetric stretching vibration of Si-O-Si and the band at

Chapter 1: Literature Review of Fly Ash

21

U n i i v e r r s i i t t y o f f

P r r e t t o r r i i a e t t d – L a n d m a n ,

,

A A

(

( 2 0 0 3

)

)

Aspects of solid-state chemistry of fly ash and ultramarine pigments

792 cm

-1

to the corresponding symmetric vibration.

46

The band at 1135 cm

-1

is tentatively assigned to the antisymmetric stretching vibration of Si-O-Al and the band at 700 cm

-1

to the symmetric Si-O-Al stretching vibration.

46

The band at 481 cm

-1

is

assigned to the O-Si-O bending vibration.

46

The shoulder at 950 cm

-1

is assigned to a non-bridging oxygen ion band, Si-O-Na.

46

The bands at 800 and 481 cm

-1

are assigned to the presence of cristobalite, and the band at 700 cm

-1

to the presence of mullite.

46

Table 1-4: XRF determined composition of fly ash and Kaolin

(g/100g)

a

Fly Kaolin

b

Compound Mass (g/100g)

a

Fly ash Kaolin

b

SiO

2

Al

2

O

3

CaO

Fe

2

O

3

TiO

2

MgO

K

2

O

P

2

O

5

SO

3

SrO

BaO

Na

2

O

ZrO

2

Cr

2

O

3

V

2

O

5

50.9(7) 45.53(9) MnO

37.1(6) 37.3(2) ZnO

4.5(3) 0.0331(5) La

2

O

3

3.0(2) 0.647(3) NiO

1.8(1) 0.852(3) As

2

O

3

0.8(3) 0.286(3) PbO

0.62(4) 0.949(4) Y

2

O

3

0.48(4) 0.1519(5) CeO

2

0.2(2)

c

0.0198(5) Ga

2

O

3

0.15(2) 0.01944(6) CuO

0.11(5)

Rb

2

O

0.058(9) 0.049(3) Nb

2

O

5

0.055(9) 0.00470(9) Sc

2

O

3

0.052(5) 0.0074(6) Ag

2

O

0.039(8) 0.0195(3) MoO

3

0.038(8)

0.024(4) 0.0035(3)

0.018

d

0.017(4) 0.0014(6)

0.016

d

0.0009(7)

0.015(2) 0.0108(2)

0.014(5) 0.00573(8)

0.012(9)

0.012(3) 0.0110(2)

0.010(3) 0.0008(5)

0.01

d

0.0192(2)

0.007(2) 0.0095(6)

0.006

d

0.0043(2)

0.005

d

0.0005(2) 0.0002(2) a. The data represents the average of four XRF analyses on fly ash and fly ash treated at 1 000 ºC with the standard deviation indicated in brackets, that is 50.9(7) implies 50.9 ± 0.7 g/100g sample. b. The data represents the average of four XRF analyses on Kaolin, content found in Kaolin but not in fly ash is omitted, for example uranium. c. The uncertainty in the value of SO

3

is related to the heat treatment of the samples and the analysis method. d. The compound occurred only once in the set of four repeat analyses.

Chapter 1: Literature Review of Fly Ash

22

U n i i v e r r s i i t t y o f f

P r r e t t o r r i i a e t t d – L a n d m a n ,

,

A A

(

( 2 0 0 3

)

)

Aspects of solid-state chemistry of fly ash and ultramarine pigments

1.2

1

0.8

0.6

0.4

0.2

0

2400 1900 1400

Wavenumber / cm

-1

900 400

Figure 1-3: Infrared spectrum of fly ash

The pH of a suspension of 10 g of fly ash in 200 ml of water is 11.473 ± 0.009 after

10 minutes of agitation. After treating the fly ash at 1 000 ºC, the pH under similar conditions only reaches 8.28 ± 0.03, a statistically different pH, even at the 99.99 % confidence level. This possibly indicates that some of the alkali and alkaline-earth salts on the surface of the particles decomposed to their respective oxides, and were not free to go into solution. Ding and others

74

identify Ca

2+

, K

+

and Na

+

as the soluble constituents of fly ash and find that a suspension of fly ash in water gives a pH of

12.2, in agreement with the present study as well as the work of Foner and others.

2

Bayat

31

observes similar trends in pH development over time, to a maximum of

approximately 12.5, although some fly ash samples gave peak values as low as 9.7 and 10.4. Bayat

31

further determines, through leaching experiments, that sodium and

potassium are almost entirely in their free ionic states, whereas calcium and magnesium are only predominantly in their free ionic states. Hydroxides and sulphates are also common in the fly ash suspensions.

31

Further investigation needs to be done on the characterisation of fly ash, since the validity of any result regarding fly ash for one batch would need to be tested for other batches. Furthermore, fly ash can be studied in its different fractions. Fly ash can be

Chapter 1: Literature Review of Fly Ash

23

U n i i v e r r s i i t t y o f f

P r r e t t o r r i i a e t t d – L a n d m a n ,

,

A A

(

( 2 0 0 3

)

)

Aspects of solid-state chemistry of fly ash and ultramarine pigments separated based on particle size, magnetic characteristics, and density. The order of these fractionation steps can be swapped around, possibly yielding different results.

45

1.4. Past Applications of Fly Ash

Many patents are claimed for the use and beneficiation of fly ash. The classification of fly ash is not discussed, and is reviewed by Kruger.

11

The most important use of fly

ash is in the cement industry, where the presence of fly ash adds strength to concrete. The minerals in South African fly ash are not hydraulic, that is the minerals

do not add strength to cement.

110

The glass phase is believed to react with lime

released from cement while the cement is curing.

110

This pozzolanic reaction adds strength to the cement.

110

In general fly ash reduces the water consumption of

cement, increases the setting time, reduces the heat of hydration and adds long-term strength to cement products, for example concrete.

3

The unreactivity of the mineral or

crystalline phases in fly ash is also evident during zeolite formation.

24,73,77

The unreactivity of the crystalline material in fly ash in terms of cement strength development does not mean that these parts of the fly ash particles are unreactive in all situations, nor does it imply that these minerals prevent the glassy phases from reacting.

Different applications of fly ash are tabulated below (Tables 1-5 to 1-8). The focus is on the period January 1980 to August 2003. In compiling the list of applications, applications regarding cement and concrete have largely been ignored, as well as non-coal based fly ash, for example municipal solid waste incineration ash.

Helmuth

19

and Wesche

23

review the use of fly ash in cement, giving background on

the characteristics of fly ash. Solid stabilisation of waste products has not been included either.

111

Fly ash is used as cement extender, or filler in the manufacture of building material

such as panels and boards (Table 1-5), and is also added to gypsum boards.

Fly ash retains water, which makes it a good soil amender. Boron and selenium enrichment seems to be the most detrimental aspect of fly ash amended soils. In

these applications, fly ash is often mixed with sewage sludge (Table 1-5). The

Chapter 1: Literature Review of Fly Ash

24

U n i i v e r r s i i t t y o f f

P r r e t t o r r i i a e t t d – L a n d m a n ,

,

A A

(

( 2 0 0 3

)

)

Aspects of solid-state chemistry of fly ash and ultramarine pigments possibility exists that the high levels of boron and selenium originate from the sewage sludge rather than from the fly ash. An extension of these soil amendment applications is the formation of artificial reefs.

80,112,113

Polymers are expensive chemical species. To make up volume without using unnecessary amounts of polymer other inexpensive materials are added, known as fillers. Functional fillers are fillers that add extra quality to the final plastic, for example colour, fire retardancy, or UV stability. Fly ash has the potential to be a good

functional filler (Table 1-5), due to its spherical microscopic structure (Figure 1-1).

Cu-coated cenosphere particles are used in conducting polymers for EMI-shielding applications.

105

The mullite and quartz in the non-magnetic fraction of fly ash could be a valuable

resource in the ceramics industry (Table 1-5). The use of fly ash in frictional or brake

material for the automotive industry is a high technology application of the hardness of fly ash.

15

Some transition metals are concentrated in the magnetic fraction of fly

ash and can, therefore, be extracted from this concentrated matrix (Table 1-6).

102

Minerals essential to humans and animals can also be recovered from fly ash.

114

Ferrospheres exist in fly ash

84

and have found direct use as part of copier toner.

115-118

Fly ash is used as an adsorbent for organic wastes (Table 1-7). Whether this

adsorbent nature of fly ash can be ascribed to the porous nature of the silicates or to the activated carbon particles embedded on the surface of the fly ash particle is still a matter for debate. To remove SO x

from gas streams, fly ash is usually mixed with

Ca(OH)

2

(Table 1-7). Fly ash is also used for the removal of heavy metals from aqueous samples (Table 1-7). This property of fly ash is dramatically enhanced by

the formation of zeolites from fly ash (Table 1-8). The zeolites formed from fly ash

(Table 1-8) cover a substantial range of the known structures for zeolites, and have

been reviewed by Querol and others.

119

Smith,

120

Suib,

121

and Cundy and Cox

122

review the structure of these, and other, zeolites. Mullite is the least reactive component in fly ash during the formation of zeolites,

24,73,77

while the glass phase reacts first. Hollman and others

86

emphasize that the formation of the zeolite takes

place on the surface of the fly ash particles. This leads to an impure product. In a

Chapter 1: Literature Review of Fly Ash

25

U n i i v e r r s i i t t y o f f

P r r e t t o r r i i a e t t d – L a n d m a n ,

,

A A

(

( 2 0 0 3

)

)

Aspects of solid-state chemistry of fly ash and ultramarine pigments two-step synthesis, designed to separate the silica-rich leached fraction from the fly

ash, 85 g of pure zeolite can be produced from 1 kg of fly ash.

86

Table 1-5: Applications in which fly ash acts as an additive

Building Industry

Cement and Concrete

1,2,4,11,12,17,19,23,

31,123-126

Grout

Roof Tiles

12,128-131

Bricks

11,12,30,1,123-125,131,133-135

Patches on Roads

12,133,136,137

Panels and boards

2,12,131,133,138-144

Soil Beneficiation

1,30,31,44,124,125,132,145-163

Sewage treatment

164,165

Landfill

12,124,133,166-168

Soil stabilization

169-171

Soil stabilization for roads

175

Fertiliser or composting

30,49,177-181

Coagulation and sludge conditioning agents

97,172,176

Filler Material

182-184

Foams

11

Polyisocyanurate or polyurethane foam

185,186

Phenolic resole foam

187

Polyurethane foam

189

Polyester-polyurethane hybrid resin foams

188

Polypropylene

191,192

PVC

193

Epoxy resin

105,194

Polyester

195

Resins

11

Polyurethane

197

Mineral foam

199

Rigid shaped articles based on fly ash and resin

196

High temperature

11

Mineral wool

124,133,208

Fibre reinforced fly ash

107,200

Insulating Material

125

Low temperature applications.

2,201,202,203

Ceramic Material

11,18,30,69,108,132,133,204-207

Coated cellular glass pellet

209

Glass-ceramics

70,72,124,133,210-212

Chapter 1: Literature Review of Fly Ash

26

U n i i v e r r s i i t t y o f f

P r r e t t o r r i i a e t t d – L a n d m a n ,

,

A A

(

( 2 0 0 3

)

)

Aspects of solid-state chemistry of fly ash and ultramarine pigments

Table 1-6: Applications in which fly ash acts as a metal and metal oxide source

1,31,133,214

Iron

34,53,97,215-226

Germanium

228,229

Lead and Zinc

231

Antimony

232

Vanadium

227,232,234

Aluminium

53,75,97,215,222-226,234-238

Uranium

31,222

Selenium

234

Thorium

222

Table 1-7: Applications in which fly ash acts as an adsorbent

Adsorbent for Organic wastes

173

Chlorophenols

240

Phenol

241,242

o-xylene

243

Toluene

244

Oil and tar

242

Adsorbent for Inorganic Wastes

12,31,170,173,245,246

SO x

41,50,53,65,89-94,98,247-255

NO

x

250,252,253

Nitrates

256

Cadmium

24,28,77,145,259-261

Selenium

262,263

Mercury

264-266

Radium

267

Strontium

61

Zinc

24,28,77,86,269

Chromium

246,259,271

Nickel

24,28,77,86,259,269,273

Fluoride

275

Chapter 1: Literature Review of Fly Ash

27

U n i i v e r r s i i t t y o f f

P r r e t t o r r i i a e t t d – L a n d m a n ,

,

A A

(

( 2 0 0 3

)

)

Aspects of solid-state chemistry of fly ash and ultramarine pigments

Fly ash is used to aid in the oxidation of Na

2

S

276

and organic material

277

in

wastewater, and of H

2

S and ethanethiol in gas streams.

278

This catalytic effect can

also be used in other areas of chemistry, such as catalyst support, for example in the

selective catalytic reduction of NO.

279

Fly ash is used as carbon monoxide disproportionating catalyst, useful in the production of hydrogen and methane,

280

and for hydrocracking.

281

Fly ash is composited with aluminium,

103,282,283

tin,

282

zinc,

282

and sulphur,

284

by

melting the elements in the presence of the fly ash. A less high technology and a

malodorous application is the manufacture of cat litter.

285

Table 1-8: Applications in which fly ash acts as starting material for zeolite synthesis

145

Zeolite Na-P1

2,24,28,43,77,86,95

Zeolite P

24,36,37,48,61,64

Zeolite P1

87

Zeolite K-G, ZK19 and Linde A

24

Phillipsite

MCM41

286

2,28,77,37

Merlinoite and nosean

77

K-Chabazite

28,287

Hydroxy-cancrinite, perlialite and Kalsilite

28

Zeolite F Linde

28,37

Na-Chabazite

60,287

Nepheline hydrate

29,37

Herschelite and tobermorite

28

Zeolite A

24,28,36,60,64,86,95,270,288

Faujasite

28,36,48,64

Gmelinite

29

Analcime

28,29,37,77

Sodalite and cancrinite

53

Hydroxy-sodalite

28,37,43,48,60,86,95

Zeolite X

48,60,73,86,270,288

Zeolite Y

48,88

Zeolite J and M

287

Zeolite R

60

Geopolymers

51,53,54,109,289-291

Chapter 1: Literature Review of Fly Ash

28

U n i i v e r r s i i t t y o f f

P r r e t t o r r i i a e t t d – L a n d m a n ,

,

A A

(

( 2 0 0 3

)

)

Aspects of solid-state chemistry of fly ash and ultramarine pigments

The amorphous aluminosilicate nature of fly ash makes fly ash a possible starting point for many industrial reactions, such as the synthesis of ultramarine blue

(Chapter 3).

292

Repeated harvesting of foodstuff depletes the trace elements in soil. Although the use of fly ash as soil amendment has been studied, the full-scale application of this technology has not been implemented. In future, farmers might use fly ash, rather than lime, to enrich their soil. The trace elements in fly ash might be used to replace the trace elements in the soil, and to increase the mineral content of the foodstuff.

Fly ash can be considered a valuable resource and needs to be studied, in order to facilitate the application of fly ash to new and innovative areas of economic interest.

This review aimed to act as a stepping-stone for the prospective researcher into the rewarding field of fly ash.

1.6. Conclusion

Several non-cement applications of fly ash were reported briefly, for example as filler in plastics. The characteristics of fly ash were also discussed, with the goal of challenging the scientific community to study and evaluate further potential uses of fly ash.

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37

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