EXP 129

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EXP 129 RICE HUSK ASH MARKET STUDY

ETSU U/00/00061/REP DTI/Pub URN 03/668

Contractor Bronzeoak Ltd

Limited Distribution UK companies only This publication contains information which is commercially valuable to actual or potential renewable energy technology exporters. Permission to lend, give or copy this publication to any person or organisation, in part or in its entirety, is strictly limited to bona-fide UK exporters.

The work described in this report was carried out under contract as part of the DTI New and Renewable Energy Programme. The views and judgements expressed in this report are those of the contractor and do not necessarily reflect those of the DTI.

First published 2003 Crown copyright 2003

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RICE HUSK ASH MARKET STUDY

EXECUTIVE SUMMARY Objectives To determine the current markets for rice husk ash (RHA) through a publication review. To evaluate the current and potential value of each market. To determine the type and quality of RHA produced from different boilers and relate this to market specification. To analyse the economics of producing and selling the different types of RHA in conjunction with bioenergy projects.

Introduction Globally, approximately 600 million tonnes of rice paddy is produced each year. On average 20% of the rice paddy is husk, giving an annual total production of 120 million tonnes. In the majority of rice producing countries much of the husk produced from the processing of rice is either burnt or dumped as a waste. The treatment of rice husk as a resource for energy production is a departure from the perception that husks present disposal problems. The concept of generating energy from rice husk has great potential, particularly in those countries that are primarily dependant on imported oil for their energy needs. Rice husks are one of the largest readily available but most under-utilised biomass resources, being an ideal fuel for electricity generation. Rice husk is unusually high in ash compared to other biomass fuels close to 20%. The ash is 92 to 95% silica, highly porous and lightweight, with a very high external surface area. Its absorbent and insulating properties are useful to many industrial applications. RHA is a general term describing all types of ash produced from burning rice husks. In practice, the type of ash varies considerably according to the burning technique. The silica in the ash undergoes structural transformations depending on the conditions (time, temperature etc) of combustion. At 550C 800C amorphous ash is formed and at temperatures greater than this, crystalline ash is formed. These types of silica have different properties and it is important to produce ash of the correct specification for the particular end use. If a long term sustainable market and price for rice husk ash (RHA) can be established, then the viability of rice husk power or co-generation plants are substantially improved. Many more plants in the 2 - 5 MW range can become commercially viable around the world and this biomass resource can be utilised to a much greater extent than at present. Potential and current uses of RHA An extensive literature search has highlighted many uses of RHA. Two main uses have been identified, as an insulator in the steel industry and as a pozzolan in the cement industry.

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Limited Distribution UK Companies only Steel industry: RHA is used by the steel industry in the production of high quality flat steel. Flat steel is a plate product or a hot rolled strip product, typically used for automotive body panels and domestic 'white goods' products. RHA is an excellent insulator, having low thermal conductivity, high melting point, low bulk density and high porosity. It is this insulating property that makes it an excellent tundish powder. These are powders that are used to insulate the tundish, prevent rapid cooling of the steel and ensure uniform solidification in the continuous casting process.

Cement industry: Substantial research has been carried out on the use of amorphous silica in the manufacture of concrete. There are two areas for which RHA is used, in the manufacture of low cost building blocks and in the production of high quality cement. Ordinary Portland Cement (OPC) is expensive and unaffordable to a large portion of the world's population. Since OPC is typically the most expensive constituent of concrete, the replacement of a proportion of it with RHA offers improved concrete affordability, particularly for low-cost housing in developing countries.

The addition of RHA to cement has been found to enhance cement properties: The addition of RHA speeds up setting time, although the water requirement is greater than for OPC. At 35% replacement, RHA cement has improved compressive strength due to its higher percentage of silica. RHA cement has improved resistance to acid attack compared to OPC, thought to be due to the silica present in the RHA which combines with the calcium hydroxide and reduces the amount susceptible to acid attack. More recent studies have shown RHA has uses in the manufacture of concrete for the marine environment. Replacing 10% Portland cement with RHA can improve resistance to chloride penetration. Several studies have combined fly ash and RHA in various proportions. In general, concrete made with Portland cement containing both RHA and fly ash has a higher compressive strength than concrete made with Portland cement containing either RHA or fly ash on their own. RHA can also replace silica fume in high strength concrete. Silica fume or micro silica is the most commonly used mineral admixture in high strength concrete. The major characterisitics of RHA are its high water demand and coarseness compared with condensed silica fume. To solve these problems RHA needs to be ground finely into particles of 8-10 m and a superplasticizer added to reduce water requirement. There are two patents for a ground RHA cement additive that closely matches the performance of silica fume. Other less wide spread uses have also been identified: Due to its insulating properties, RHA has been used in the manufacture of refractory bricks. There are reports of RHA being used in the manufacture of lightweight insulating boards in developing countries. Several studies have been carried out to purify RHA for use in silicon chip manufacture. The techniques are still being developed, but appear promising.

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Limited Distribution UK Companies only It is known that farmers in Asia will use RHA to prevent insect attack in stored food stuffs, and several scientific studies have been carried out to test the efficacy of this. Greenwich University are researching small-scale paddy milling in Bangladesh and Vietnam, and the possibility of using RHA for water purification. A company in the USA have produced a proto type plant for manufacturing activated carbon from RHA, and the major market for this is in water purification. There are several reports detailing the use of RHA in vulcanising rubber, although in small scale experiments. There are reports of RHA being used as a soil ameliorant to help break up clay soils and improve soil structure. Husks burnt slowly over a period of six months have been found to be effective as an oil absorbent and are marketed in California.

Potential and current markets for RHA Low value or small markets have been identified: The use of RHA as an oil absorbent is very small and localised and much work would need to be done to expand the market from currently just one US State, California. The use of RHA in the manufacture of refractory bricks is too small a market to be considered as an outlet for large quantities of ash, although it may be suitable for a limited number of energy plants. Other uses with limited commercial potential, due to localised low value use, are the control of insect pest in stored food stuffs and as a soil ameliorant. Markets with potential in the future: There are potential markets for RHA in the silicon chip industry, which is expanding. However, the technique of refining RHA to the desired quality has not yet been established on a large scale, and it could be many years before such an application is market ready. The production of lightweight construction materials and insulation from RHA has potential, but current use is not widespread and there is limited knowledge of the methods used. The production of activated carbon using RHA has great potential. The share RHA could play in this market is not yet clear, and more research on the methodology and cost of producing activated carbon from RHA is needed. The use in industrial chemical processes such as in the rubber vulcanising process are a long way from being market ready. Commercially viable markets: Currently the largest and most commercially viable markets appear to be in the concrete and steel industry. Steel industry: The market within the steel industry is well established. However there are constraints to the expansion of this market due to health issues associated with using RHA. Crystalline ash, the form preferred by the steel industry, is carcinogenic and the use of RHA is banned in some European countries. This trend is likely to increase. There is more scope for development in Asian and Eastern markets, but the future size of the market is not certain.

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Limited Distribution UK Companies only Some companies are pelletising RHA, and state that this overcomes the health issues. There is controversy over whether this is the case, but some steel manufacturers have converted to pellets.

Cement industry: The cement markets are not as well developed as steel, but there is great potential for the use of RHA in this area. It is currently not being used to any extent, except in the USA. Two main issues appear to be limiting its use: lack of awareness of the potential for RHA and the quality of the product itself. The cement industry requires amorphous ash, so there are none of the health issues associated with crystalline ash. The cement industry has to produce a consistent, high quality and standard product. This in turn requires RHA from a controlled combustion environment, to ensure a consistent standard ash. Producing RHA of the correct quality may cost more than producing normal ash due to boiler modifications etc. In addition to the use of the ash, it may be possible to generate Certified Emission Reductions (carbon credits) when substituting for Portland cement. Portland cement requires enormous heating in its manufacture and avoiding the energy (derived from fossil fuels) and thus carbon emitted from its manufacture could generate an additional income stream for the producers of RHA. Technical overview There is a wide range in the physical and chemical properties of RHA. The chemical and physical properties of the ash may be influenced by the soil chemistry, paddy variety and fertiliser use. The change from amorphous to crystalline ash occurs at approximately 800C, although the process is often incomplete until 900C is achieved. All the combustion processes devised to burn rice husks remain below 1440C, which is the RHA melting temperature. The most commonly used boilers are based on fixed grate technologies, which tend to produce ash with high carbon content, high LOI content and high proportions of crystalline to amorphous ash. This type of ash is more suited to the steel industry. Suspension fired boilers generally produce more amorphous ash than stoker fired boilers despite the fact that they may operate at higher temperatures. This is because the operating time at high temperatures for suspension fired boilers is comparatively short. Commonly, in the production of highly amorphous ash, low temperatures and fairly long burn-times are used. Fly ash is a fine material and is of higher marketable value since it requires less grinding than the generally coarser bottom ash.

Conclusions Small markets exist for RHA in the manufacture of refractory bricks and as an oil absorbent. Potential markets in the future include silicon chip manufacture, in the manufacture of activated carbon, and in the production of lightweight construction materials and insulation. Currently the largest and most commercially viable markets appear to be in the concrete and steel industry.

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Limited Distribution UK Companies only The market within the steel industry is well established, but there are constraints to the expansion of this market due to health issues associated with using crystalline ash. The cement markets are not as well developed as steel, but there is great potential for the use of amorphous RHA. Two main issues appear to be limiting its use: lack of awareness of the potential for RHA and the quality of the product itself. Boiler modifications may be required to produce ash of the quality required.

Recommendations for the future The best choice would seem to be to produce RHA for the steel industry as this requires no boiler modifications and attracts a high price. However, our market study suggests that, whereas growth in the market for RHA to the steel market is limited, growth in the market for RHA in the cement industry is growing and is potentially very large. A new entrant to the market place may prefer to target the somewhat less high returns but better longer term prospects of the amorphous silica market.

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Limited Distribution UK Companies only

1. 2.

INTRODUCTION TO THE STUDY 1.1 Objectives of study: GLOBAL RICE PRODUCTION AND USE 2.1 Global rice Production 2.2 Factors influencing the use of rice husk 3.1 Steel industry 3.2 Cement and concrete 3.2.1 Introduction 3.2.2 Low cost building blocks 3.2.3 Enhanced properties of RHA cement 3.2.3 RHA as a replacement for silica fume in high strength concrete 3.3 Refractory bricks 3.4 Lightweight construction materials 3.5 Silicon chips 3.6 Control of insect pests in stored food stuffs 3.7 Water purification 3.8 Vulcanising rubber 3.9 Adsorbent for a gold-thiourea complex 3.10 Ceramics 3.11 Soil ameliorant 3.12 Oil absorbent 3.13 Other uses

1 2 3 3 5 9 10 10 11 11 13 14 14 14 15 15 15 15 15 16 16 16 20 20 20 20 20 22 22 23 24 25 25 26 26 26 26 26 27 27 28 28 28 29 29

4.

MARKET REVIEW 4.1 Introduction 4.2 Low value or small markets 4.3 Potential markets in the future 4.4 Current markets 4.4 Steel 4.4.1 Global overview of steel production 4.4.2 Factors affecting the demand for RHA in the steel industry Europe Asia USA Australia 4.4.3 Prices and future trends 4.5 Cement and concrete industry 4.5.1 Introduction 4.5.2 RHA as substitute for silica fume USA UK Australia 4.5.2 Future trends and prices 4.5.3 RHA in building block manufacture

5.

TECHNICAL REVIEW 5.1 Introduction

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Limited Distribution UK Companies only 5.2 Overview of husk to ash process 5.2.1 Rice husk as a fuel 5.2.2 Incineration 5.2.3 Boilers with integral combustion Stoker fired Suspension fired Fluidised bed combustors 5.2.4 Gasification 5.3 Overview of ash production 5.4 Methods of ash analysis 5.5.1 Temperature 5.5.2 Geographical region 5.6 Review of influence of combustion method on properties of RHA 5.6.1 Fixed grate boilers 5.6.2 Fluidized bed 5.6.3 Circulating Fluidised Bed (CFB) 5.6.4 Grate versus conventional 5.6.5 Gasification 5.6.6 Additional Technology 5.6.7 Special market requirements 5.7 Summary of technical analysis 6. HEALTH ISSUES 6.1 Diseases 6.1.1 Silicosis 6.1.2 Cancer 6.1.3 Other diseases 6.2 Exposure limits 6.3 Measures to control exposure 6.4 Health issues in relation to use of RHA 7. COST BENEFIT ANALYSIS 7.1 7.2 7.3 7.4 7.5 8. 8.1 8.2 8.3 9. Introduction RHA Disposal Negative Benefit RHA with Significant Quantity of Crystalline Silica RHA with High Amorphous Ash Content Concluding Remarks Introduction Role of RHA in reducing GHG emissions Calculating the value of CERs from Portland cement substitution 29 29 30 30 31 31 31 32 32 33 33 34 34 35 36 36 36 36 37 37 37 41 41 41 41 41 42 42 42 43 43 43 44 45 45 46 46 46 46 48 49 54

POTENTIAL TO EARN CARBON CREDITS

CONCLUSIONS

REFERENCES ACKNOWLEDGEMENTS APPENDIX A

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Limited Distribution UK Companies only

1.

INTRODUCTION TO THE STUDY

Rice covers 1% of the earths surface and is a primary source of food for billions of people. Globally, approximately 600 million tonnes of rice paddy is produced each year. On average 20% of the rice paddy is husk, giving an annual total production of 120 million tonnes. In the majority of rice producing countries much of the husk produced from the processing of rice is either burnt or dumped as waste. Rice husks are one of the largest readily available but most under-utilised biomass resources, being an ideal fuel for electricity generation. The calorific value varies with rice variety, moisture and bran content but a typical value for husks with 8-10% moisture content and essentially zero bran is 15 MJ/kg. The treatment of rice husk as a resource for energy production is a departure from the perception that husks present disposal problems. The concept of generating energy from rice husk has great potential, particularly in those countries that are primarily dependent on imported oil for their energy needs. For these countries, the use of locally available biomass, including rice husks is of crucial importance. Rice husk is unusually high in ash compared to other biomass fuels close to 20%. The ash is 92 to 95% silica (SiO2), highly porous and lightweight, with a very high external surface area. Its absorbent and insulating properties are useful to many industrial applications, and the ash has been the subject of many research studies. If a long term sustainable market and price for rice husk ash (RHA) can be established, then the viability of rice husk power or co-generation plants are substantially improved. A 3 MW power plant would require 31,000 tonnes of rice husk per year, if operating at a 90% capacity factor. This would result in 5580 tonnes of ash per year. Revenue from selling the ash for beneficial use would decrease the pay-back period for the capital needed to build the project. Many more plants in the 2 5 MW range can become commercially viable around the world and this biomass resource can be utilized to a much greater extent than at present. Rice husk ash has many applications due to its various properties. It is an excellent insulator, so has applications in industrial processes such as steel foundries, and in the manufacture of insulation for houses and refractory bricks. It is an active pozzolan and has several applications in the cement and concrete industry. It is also highly absorbent, and is used to absorb oil on hard surfaces and potentially to filter arsenic from water. More recently, studies have been carried out to purify it and use it in place of silica in a range of industrial uses, including silicon chip manufacture. RHA is a general term describing all types of ash produced from burning rice husks. In practice, the type of ash varies considerably according to the burning technique. Two forms predominate in combustion and gasification. The silica in the ash undergoes structural transformations depending on the temperature regime it undergoes during combustion. At 550C 800C amorphous silica is formed and at greater temperatures, crystalline silica is formed. These types of silica have different properties and it is important to produce ash of the correct specification for the particular end use. There are health issues associated with the use of crystalline

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Limited Distribution UK Companies only ash, inhalation of which can lead to a number of diseases, the most common being silicosis. This affects the potential markets for this type of ash. 1.1 Objectives of study:

An understanding of the market for RHA and the parameters under which it operates will maximise revenue of husk to energy plants by exploiting the market opportunities available for the RHA. World wide, rice husk fuelled power plants have a high replicability potential if the project economics satisfy the required criteria. This market assessment contributes to the project viability and will work as a catalyst in promoting this type of power plant. The objectives of the study are: To determine the current markets for rice ash through a publication review. To evaluate the current and potential value of each market. To determine the type and quality of rice husk ash produced from different boilers and relate this to end-user specification. To analyse the economics of producing and selling the different types of ash in conjunction with bioenergy projects.

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Limited Distribution UK Companies only

2.
2.1

GLOBAL RICE PRODUCTION AND USE

Global rice Production

Rice is grown on every continent except Antarctica and covers 1% of the earths surface. It is a primary source of food for billions of people, and ranks second to wheat in terms of area and production [1]. During growth, rice plants absorb silica from the soil and accumulate it into their structures. It is this silica, concentrated by burning at high temperatures removing other elements, which make the ash so valuable. The annual production of paddy rice (Oryza sativa) globally was 579,500,000 tonnes in 2002 [1]. Of this, 95% was produced by 20 countries, as shown in Table 1. Rice, Paddy Production in 2002 (t) 177,589,000 China 123,000,000 India 48,654,048 Indonesia 39,000,000 Bangladesh 31,319,000 Viet Nam 27,000,000 Thailand 21,200,000 Myanmar 12,684,800 Philippines 11,264,000 Japan 10,489,400 Brazil 9,616,750 USA 7,429,000 Korea 5,776,000 Pakistan 5,700,000 Egypt 4,750,000 Nepal 4,099,016 Cambodia 3,367,000 Nigeria 2,794,000 Sri Lanka 2,353,440 Colombia 2,300,000 Laos 29,091,358 Rest of the World Total (World) 579,476,722 Percentage of Potential Ash Total Paddy Husk Produced Production (18% of Production (20% of total) (t) husk) (t) 30.7% 35,517,800 6,393,204 21.2% 24,600,000 4,428,000 8.4% 9,730,810 1,751,546 6.7% 7,800,000 1,404,000 5.4% 6,263,800 1,127,484 4.7% 5,400,000 972,000 3.7% 4,240,000 763,200 2.2% 2,536,960 456,653 1.9% 2,252,800 405,504 1.8% 2,097,880 377,618 1.7% 1,923,350 346,203 1.3% 1,485,800 267,444 1.0% 1,155,200 207,936 1% 1,140,000 205,200 0.8% 950,000 171,000 0.7% 819,803 147,565 0.6% 673,400 121,212 0.5% 558,800 100,584 0.4% 470,688 84,724 0.4% 460,000 82,800 5.0% 5,818,272 1,047,289 100% 115,895,344 20,861,162

Table 1 Rice paddy, and potential husk and ash production in the 20 highest producing countries,2002 [1]. Production of rice is dominated by Asia, where rice is the only food crop that can be grown during the rainy season in the waterlogged tropical areas. Most paddy is produced by China (31%) followed by India (21%). Assuming a husk to paddy ratio of 20% [2], and a ash to husk ratio of 18% [3], the total global ash production could be as high as 21,000,000 tonnes per year.

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Limited Distribution UK Companies only Globally, rice production is increasing, with an increase of 10% from 1992 2002 (Figure 1). Of the top 20 countries only China and Japan produced less rice in 2002 than in 1992. In China, which produces the most rice in the world, production fell by 10 000 000 tonnes, or approximately 6% [1].
200,000,000 180,000,000 160,000,000 140,000,000 Tonnes of Rice 120,000,000 100,000,000 80,000,000 60,000,000 40,000,000 20,000,000 0
hi C U SA na

Figure 1 Chart showing the 20 highest rice paddy producing countries in 2002.
200,000,000 180,000,000 160,000,000 140,000,000 Tonnes of Rice 120,000,000 100,000,000 80,000,000 60,000,000 40,000,000 20,000,000 0
C hi na

1992 2002

Figure 2 A comparison of rice paddy production in the 20 highest producing countries, 1992 and 2002. Yields are affected by several factors, including the agronomy of the crop. This is influenced by the physical and cultural environments and scale under which the rice is grown (Plate 1). International co-ordination and co-operation in technological advances of rice production is providing

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Limited Distribution UK Companies only alternatives to the limitations of cultural practices, by the use of chemical fertilisers, insecticides, pesticides and introduction of new varieties. Rice production is often set back by the weather, monsoons and droughts, but the effects of this are increasingly being limited by irrigation and water control systems [3]. The chemical properties of ash arising from rice husks are thought to vary from region. The differences have been attributed to the conditions under which the paddy is grown, such as climate, soil, and use of fertilisers (discussed in Section 5.5.2). 2.2 Factors influencing the use of rice husk

Although the potential global estimate of RHA production is 21,000,000 tonnes (Table 1), the actual scope for utilisation is considerably less. The majority of mills from which the husks are sourced are small and dispersed within developing countries. For example in Indonesia, 93 % all mills produce less than 10,000 t/year [4, 5]. This makes collection of the resource logistically problematical, and currently husks are dumped and burnt in open piles (Plates 3 and 4). The ash produced is of poor quality and is often used domestically in small quantities for cleaning glassware and cooking utensils (Plate 10 and Figure 3). Thus in rural catchment areas the collection of rice husks and security of fuel supply tends to limit the practical size of biomass power plants. It is estimated that the optimum size of power plants in such areas is between 2-5 MW, producing up to 10,000 tonnes of ash per year [5]. Larger rice mills such as the Patum rice mill in Thailand produce 320,000 t/year, and already utilise husk for cogeneration (Plate 2) [6]. In developed countries, where the mills are typically larger, disposal of the husks is a big problem. Burning in open piles is not acceptable on environmental grounds, and so the majority of husk is currently going into landfill (Figure 3). The cost of this (discussed in Section 7) erodes the profit of the milling company. This has led to many research programmes into potential end uses of both husk and ash, primarily in the USA.

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Limited Distribution UK Companies only Paddy fields

Rice mills with cogeneration or similar facilities ASH FROM BOILER Domestic Market International Market Developing countries

Rice mills without cogeneration or similar facilities HUSKS

Developed countries

6 eg steel industry building block manufacture research uses landfill eg steel industry Burnt in open piles Local uses Landfill Ash collected for local use eg cleaning glassware control of pests in stored food eg fuel building Figure 3 Flow chart showing movements of rice husk and ash under two scenarios mills with cogeneration or similar facilities, and mills without.

Plate 1

Planting rice in Indonesia

Plate 2

Rice arriving at Patum Rice Mill, Thailand

Plate 3

Rice husks piles being burnt in Nicaragua

Plate 4

Close-up of burning rice husk

3.
3.1

PUBLICATION REVIEW OF USES FOR RICE HUSK ASH

Steel industry

RHA is used by the steel industry in the production of high quality flat steel. Flat steel is a plate product or a hot rolled strip product, typically used for automotive body panels and domestic 'white goods' products [7]. This type of steel is generally produced by continuous casting, which has replaced the older ingot method. In the ingot method molten steel was poured into a large mould where it would be allowed to cool and solidify to form an ingot. The ingot would then be rolled in primary mills, in the first stage of its transformation into a usable steel product. In developed countries this process has largely been superseded by the continuous casting process (concaster), although the ingot method is retained for certain applications where it is the most suitable way of producing the steel required. Elsewhere this is not always the case, with many of the steel industries of Eastern Europe and Asia still relying heavily on the old ingot method [7,8]. In continuous casting, a ladle of steel, containing more than 200 tonnes of molten metal at 1650C, empties into a tundish, a receptacle that holds the steel and controls its flow in the continuous process. From the tundish the steel passes in a controlled manner to a water cooled mould where the outer shell of the steel becomes solidified. The steel is drawn down into a series of rolls and water sprays, which ensure that it is both rolled into shape and fully solidified at the same time. At the end of the machine, it is straightened and cut to the required length. Fully formed slabs emerge from the end of this continuous process [7, 8, 9]. It is in continuous casting that RHA plays a role. RHA is an excellent insulator, having low thermal conductivity, high melting point, low bulk density and high porosity. It is this insulating property that makes it an excellent tundish powder. These are powders that are used to insulate the tundish, prevent rapid cooling of the steel and ensure uniform solidification [10]. Traditionally ash is sold in bags which are thrown on to the top of the surface of the tundish of molten steel (Plate 6). Approximately 0.5 to 0.7 kg of RHA is used per tonne of steel produced [11]. There are health issues associated with the use of RHA in the steel industry. Traditionally crystalline ash is preferred to amorphous. This poses problems as the ash has a tendency to explode over the operator when it is being thrown on top of the tundish, exposing them to crystalline silica and possible silicosis (refer to Section 7). A new innovation is the production of pellets from RHA which can be much better controlled, and are better from an operational and safety point of view [12, 13]. RCL Ricegrowers Ltd with Biocon in Australia have devised a method for making pellets, although no details are publicly available [12]. The National Research Development Centre (NRDC) in India have also devised a method for making pellets, which they claim will spread over the top of the molten steel more easily. Details of the technique are sparse, the husk is first pulverised in a mill prior to combustion and then certain chemicals added, the pellets formed and then dried at 350C [13]. The resulting pellets have the following characteristics:

SiO2 Bulk density Size Strength Porosity Table 2

90% 0.5 0.6g/cc 110mm diameter 20 50kg/cm2 60 70%

Characteristics of silica nodules produced by the NRDC [13].

However, research by CORUS (formerly British Steel) at the Teeside Technology Centre, has cast doubts on the safety even of pellets [10]. They tested amorphous ash and found that there were few health problems, as there was no crystalline silica, and the ash proved to be equally as good an insulator as the traditionally used crystalline ash. The problems occurred when emptying the tundish at the end of the process. It was found that the heating of the steel for 4 hours at 1500C had transformed the silica from its amorphous form into cristobalite and tridymite, crystalline forms of silica with serious health risks associated (discussed in Section 7). It is likely that the same chemical transformation will occur with pellets, and so CORUS do not see them as the ideal solution [10]. There are also issues of steel quality relating to the use of RHA. Although RHA is an excellent insulator, it will oxidise with elements in steel such as aluminium to form alumina (Al2O3). This is a non-metallic compound that remains in the steel and is a nuisance in future use. Despite this it is still used in the production of certain steel where its insulating properties are necessary. Approximately ten years ago some tundish powders were produced incorporating a proportion of RHA, but these are not currently being used [10]. 3.2 Cement and concrete

Substantial research has been carried out on the use of amorphous silica in the manufacture of concrete. There are two areas for which RHA is used, in the manufacture of low cost building blocks and in the production of high quality cement. 3.2.1 Introduction

Concrete is produced by mixing Portland cement with fine aggregate (sand), coarse aggregate (gravel or crushed stone) and water [14] (Figure 4).

Figure 4

The composition of concrete [15]

Approximately 11% of ready mix concrete is Portland cement (Figure 4). It is the binding agent that holds sand and other aggregates together in a hard, stone-like mass. Cement is made by heating limestone and other ingredients to 1450C in a kiln to produce clinker, this involves the dissociation

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of calcium carbonate under heat, resulting in lime (calcium hydroxide) and CO2. The lime then combines with other materials to form clinker, while the CO2 is released to the environment. The pulverised/ground clinker mixed with gypsum is called Portland cement [14]. Small amounts of admixtures are often added. Admixtures are either naturally occurring compounds or chemicals produced in an industrial process, which improve the properties of the cement [14]. Most admixtures are pozzolans. A pozzolan is a powdered material, which when added to the cement in a concrete mix reacts with the lime, released by the hydration of the cement, to create compounds which improve the strength or other properties of the concrete [16, 17, 18]. Pozzolans improve strength because they are smaller than the cement particles, and can pack in between the cement particles and provide a finer pore structure. RHA is an active pozzolan. RHA has two roles in concrete manufacture, as a substitute for Portland cement, reducing the cost of concrete in the production of low cost building blocks, and as an admixture in the production of high strength concrete. The type of RHA suitable for pozzolanic activity is amorphous rather than crystalline.

3.2.2

Low cost building blocks

Ordinary Portland cement (OPC) is expensive and unaffordable to a large portion of the world's population. Since OPC is typically the most expensive constituent of concrete, the replacement of a proportion of it with RHA offers improved concrete affordability, particularly for low-cost housing in developing countries [19]. The potential for good but inexpensive housing in developing countries is especially great. Studies have been carried out all over the world, such as in Guyana, Kenya and Indonesia on the use of low cost building blocks [20, 21, 22]. Portland cement is not affordable in Kenya and a study showed that replacing 50% of Portland cement with RHA was effective, and the resultant concrete cost 25% less [21]. Using a concrete mix containing 10% cement, 50% aggregate and 40% RHA plus water, an Indonesian company reported that it produced test blocks with an average compressive strength of 12N/mm2 [22]. This compares to normal concrete blocks, without RHA, which have an average compressive strength of 4.5 to 7N/mm2 or high strength concrete blocks which have a compressive strength of 10N/mm2. Higher strength concrete with RHA allows lighter weight products to be produced, such as hollow blocks with enhanced thermal insulation properties, which provide lighter walls for steel framed buildings (Plate 7). It also leads to reduced quantities of cement and aggregate. 3.2.3 Enhanced properties of RHA cement

Portland cement produces an excess of lime. Adding a pozzolan, such as RHA, which combines with lime in the presence of water, results in a stable and more amorphous hydrate (calcium silicate). This is stronger, less permeable and more resistant to chemical attack [23]. A wide variety of environmental circumstances such as reactive aggregate, high sulphate soils, freeze-thaw conditions, and exposure to salt water, de-icing chemicals, and acids are deleterious to concrete. Laboratory research and field experience has shown that careful use of pozzolans is useful

11

in countering all of these problems. The pozzolan is not just a "filler, but a strength and performance enhancing additive. Pulverised fly ash and ground granulated blast furnace slag are the most common pozzolan materials for concrete. Many studies have been carried out to determine the efficacy of RHA as a pozzolan. They have concentrated on the quantity of ash in the mix and the improved characteristics resulting from its use. A comprehensive study undertaken by the Asian Institute of Technology in Bangkok, is summarised below, together with other results. Comparison of Setting Times

Table 3 compares the setting characteristics of OPC and RHA cement paste [24]. It can be seen that the addition of RHA speeds up setting time, although the water requirement is greater than for OPC. Type of Mortar OPC RHA Table 3 Water Requirement 29 litres 36 1itres Initial Setting Time 105 minutes 113 minutes Final Setting Time 225 minutes 180 minutes

Influence of RHA on setting times of cement at a replacement rate of 35% [24].

Compressive Strengths

Figure 5 compares the compressive strengths of OPC and RHA mortars. At 35 % replacement, the RHA cement had improved early strength and, due to its higher percentage of silica, the RHA cement also had a higher compressive strength at later dates. Other studies have also shown that at 28 days RHA cement had significantly greater rates of compressive strength compared with OPC [25]. Highest compressive strength has been obtained when 35% of Portland cement is replaced with RHA. If 50% is replaced then strength can be considerably reduced [24].

60

50 Compressive strength (MPa)

OPC RHA

40

30

20

10

0 3 7 Maturity (days) 28

Figure 5 Compressive strength of RHA cement and OPC [24].

12

Resistance against Acid Attack

RHA cement was exposed to a mixture of 10% Hydrochloric Acid and 10% Sulphuric Acid and was found to have more resistance than OPC. It is the silica present in the RHA which combines with the calcium hydroxide and reduces the amount susceptible to acid attack as well as reducing permeability . Resistance against chlorine

More recent studies have shown RHA has uses in the manufacture of concrete for the marine environment [26]. Replacing 10% Portland cement with RHA can improve resistance to chloride penetration. Capillary suction and accelerated chloride diffusity are also improved by addition of RHA, (Table 4). Water binder ratio 0.6 0.5 0.4 Accelerated chloride diffusity (m2/s10-12) Control RHA 2.4 1.7 1.3 1.0 0.3 0.1 Electrical resistivity (ohm m) Control RHA 31 44 53 63 107 172 Effective chloride diffusity (m2/s10-12) Control RHA 63 2.5 3.6 2.4 1.5 1.4

Table 4 Effect of RHA on the resistance of concrete against chloride penetration after one year of exposure to seawater. Mixing RHA and fly ash from coal fired power plants

Several studies have tried combinations of fly ash and RHA. In general, concrete made with Portland cement containing both RHA and fly ash has a higher compressive strength than concrete made with Portland cement containing either RHA or fly ash on their own [27, 28]. 3.2.3 RHA as a replacement for silica fume in high strength concrete

Silica fume or micro silica is the most commonly used mineral admixture in high strength concrete [19]. Though difficult (and expensive) to handle, transport, and mix, it has become the chosen favourite for very high-strength concretes (such as for high rise buildings). The American Society for Testing and Materials (ASTM) place RHA in the same class as silica fume that of a highly reactive pozzolan. The previously cited results demonstrate that RHA strengthens concrete and RHA could potentially replace silica fume. Silica fume is a waste product of the silicon metal and ferrosilicon industry. The electrometallurgical processes involve the reduction of high purity quartz in electric arc furnaces at temperatures of over 2000C. The silica fume is formed when SiO gas, given off as quartz reduces, mixes with oxygen in the upper parts of the furnace. Here the SiO is oxidised to SiO2, condensing into the pure spherical particles of silica fume, forming the major part of the smoke or fume from the furnace. The silica fume is a super-fine powder of almost pure amorphous silica [29]. The average particle size is 0.15m in diameter, so every microsphere is 100 times finer than a cement grain [30].

13

The major characterisitics of RHA are its high water demand and coarseness compared with condensed silica fume. To solve these problems RHA needs to be ground finely (for at least 1hour 15 minutes, depending on the grinding process) into particles of 8-10m and a superplasticizer added to reduce water requirement [29]. There are two patents for a ground RHA cement additive that closely matche the performance of silica fume [31, 32], filed by P.K.Mehta at UC Berkley. In 1995 the Pacific Gas and Electric Company restored the Bowman South Arch Dam using two test blocks of RHA concrete using this additive. Three years later there was no evidence of scaling or cracking, yet the surrounding plain Shotcrete was severely damaged [33]. The patents are currently owned by RHA Technology (RHA Tech), recently acquired by Alchemix Corporation of Carefree, Arizona. So far only one power plant in the USA has been found that is capable of producing the right quality of fly ash as a silica fume substitute Agrilectric Powers suspension-fired 13 MW Louisiana plant [34]. The main quality issue is the carbon content, which for the RHA produced by Agrilectric, is just 4 6%. 3.3 Refractory bricks

Due to its insulating properties, RHA has been used in the manufacture of refractory bricks [11]. Refractory bricks are used in furnaces which are exposed to extreme temperatures, such as in blast furnaces used for producing molten iron and in the production of cement clinker. The market is small, and other synthetic alternatives are preferred. However a UK company, GORICON,is interested in using it [35]. Commercial details of prices and quantities are not available. 3.4 Lightweight construction materials

There is anecdotal evidence of RHA being used in the manufacture of lightweight insulating boards in developing countries [11]. Research at the University of Arkansas has also focused the manufacture of insulation from RHA (Plate 8). The material produced is very low density and so lightweight it floats [36]. 3.5 Silicon chips

The first step in semi-conductor manufacture is the production of a wafer, a thin round slice of semi-conductor material, which is usually silicon. Purified polycrystalline silicon (traditionally created from sand) is heated to a molten liquid and a small piece of silicon (seed) placed in the molten liquid. As the seed is pulled from the melt the liquid cools to form a single crystal ingot. This is then ground and sliced to form wafers which are the starting material for manufacturing integrated circuits [37, 38]. Biocon in Australia have carried out work on purifying amorphous RHA but can only get to about 99.9% purity at a great cost, and so Biocon consider that there are no real market opportunities with silicon chips [12]. However The Indian Space Research Organisation has successfully developed technology for producing high purity precipitated silica from RHA and this has a potential use in the computer industry [38]. A consortium of American and Brazilian scientists have also developed ways to extract and purify silicon with the aim of using it in semiconductor manufacture [39]. A company in Michigan is purifying RHA into silica suitable for several industries, including silicon chip manufacture [40].

14

3.6

Control of insect pests in stored food stuffs

It is known that farmers in Asia will use RHA to prevent insect attack in stored food stuffs. Several scientific studies have been carried out to test the efficacy of this. The ash used is that from open fires, and so is predominantly crystalline. Indonesian soy beans are sometimes infested by Graham bean beetles (Callosobruchus analis). RHA has been shown to prevent this by mixing 0.5% ash to soy bean. RHA was shown to be better than wood ash and lime, and the report concludes that RHA is highly effective in controlling C. analis beetles [41]. It is also thought that RHA can control beetles such as adzuki bean weevil (C. chinensis) which attacks stored mung beans. RHA was also shown to keep stored potatoes free of the Potato tuber moth (Phthorimaea operculelle) for up to 5 months of storage [42]. It is thought that the insects are irritated by the high levels of silicon and the needle like particles [41]. 3.7 Water purification

The use of RHA as a water purifier is generally known, although only one documented study could be found [43]. Greenwich University are researching small scale paddy milling in Bangladesh and Vietnam, an objective is to find end-uses for the ash, and the possibility of using it for water purification. Tests so far have indicated that RHA is inefficient in removing arsenic from water [44]. AgriTech in USA have produced a proto type plant for manufacturing activated carbon from RHA, and the major market for this is in water purification. 3.8 Vulcanising rubber

There are several reports detailing the use of RHA in vulcanising rubber. In the laboratory RHA has been shown to offer advantages over silica as a vulcanising agent for ethylene-propylene-diene terpolymer (EPDM), and is recommended as diluent filler for EPDM rubber [45]. No analysis of the ash is given so it is not known if it is amorphous or crystalline. 3.9 Adsorbent for a gold-thiourea complex

Gold is often found in nature as a compound with other elements. One way it is extracted is to leach it by pumping suitable fluids through the gold bearing strata. RHA produced by heating rice husks at 300C has been shown to adsorb more gold-thiourea than the conventionally used activated carbon [46]. Ash produced by heating husks to 400 and 500C was found not to absorb gold thiourea complex. 3.10 Ceramics

There is very little information on the use of RHA in ceramic glazes, other than that it must be pure and high quality [47].

15

3.11

Soil ameliorant

There are reports of RHA being used as a soil ameliorant to help break up clay soils and improve soil structure [11]. Its porous nature also assists with water distribution in the soil. It is not sold widely on the commercial market for this use, and is a low value market. RHA has no fertilising potential as it does not provide the essential nutrients necessary for plant growth. Research in USA has also been carried out on using it as a potting substrate for bedding plants. RHA was found to increase the pH of the soil, and so was recommended for use with plants which require alkaline soil, or in situations where acid irrigation water is present [48]. Wadham Biomass Facility, California sells its ash to environmental remediation companies as an ingredient in a patented environmental process for treating metals-tainted soil and similar waste streams [49]. 3.12 Oil absorbent

Husks burnt slowly over a period of six months have been found to be effective as an oil absorbent and are marketed in California under the trade name Greasweep (Plate 9). This is a relatively small operation, but there is potential to increase this market. It is thought it is amorphous ash that is being used [50]. Other research studies have examined the absorption of vacuum pump oil [51] and the reduction of fatty acids in frying oils [52]. 3.13 Other uses

There are other uses for RHA which are still in the research stages [11]: in the manufacture of roof tiles as a free running agent for fire extinguishing powder an abrasive filler for tooth paste a component of fire proof material and insulation as a beer clarifier extender filler for paint production of sodium silicate films [53, 54] Throughout Asia, RHA is used domestically to clean glassware (Plate 10).

16

Plate 5

Rice husk ash at Riceland mill, Thailand.

Plate 6

Bags of ash at Riceland mill, Thailand, for shipping to Germany for use in the steel industry.

17

Plate 7

Hakkablocks building blocks in Indonesia.

Plate 8

A scientist at the University of Arkansas, holds a block of insulating material made from RHA.

18

Plate 9

Greasweep, an oil absorbent made from RHA

Plate 10

Women collecting RHA in Indonesia for domestic use.

19

4.
4.1

MARKET REVIEW
Introduction

An opportunity matrix of uses and potential for markets is shown in Table 5. It shows that many of the potential uses for RHA are not yet market ready or are too small to be significant. Ideally, an existing high value market is required. No single market fits this criterion, and some compromise has to be made. 4.2 Small or low value markets

The use of RHA as an oil absorbent is very small and localised and much work needs to be done to expand the market from currently just one US state, California. The current market prices are $8.56 for a 44kg bag, equivalent to US$940 per tonne. The use of RHA in the manufacture of refractory bricks is too small a market to be considered as an outlet for large quantities of ash, although it may be suitable for the output of a limited number of energy plants. Other uses with limited commercial potential, due to localised low value use, are the control of insect pest in stored food stuffs and as a soil ameliorant. The use of RHA in the manufacture of household ceramics is also considered to be localised and low value. 4.3 Potential markets in the future

There are potential markets for RHA in the silicon chip industry, which is expanding. However, the technique of refining RHA to the desired quality has not yet been established on a large scale, and it could be many years before such an application is market ready. Potentially the required volumes are large, but although silicon chips command high prices, this is due to the high manufacturing costs of the chips rather than the low-value cost of the raw materials. The production of lightweight construction materials and insulation from RHA has potential, but current use is not widespread and there is limited knowledge of the methods used. Further research, such as that being carried out at the University of Arkansas, may develop this commercially, but not in the short term [36]. The production of activated carbon using RHA has great potential, with the global demand for activated carbon increasing due to more stringent legislation in water purity, and an increasing focus on water recycling. Current global demand is 800,000 tonnes per year, and prices range from US$564 US$602 per tonne. The share RHA could play in this market is not yet clear, and more research on the methodology and cost of producing activated carbon from RHA is needed [55]. The use in industrial chemical processes such as an adsorbent in gold extraction and in the rubber vulcanising process are a long way from being market ready and will be disregarded from this study. It may be that with further research they are found to be ineffective, as is the case of using RHA as a filter for arsenic removal in water. 4.4 Current markets

The steel and cement industries are identified as having the most potential for a high value, large market and are discussed in detail in Sections 4.4 and 4.5.

20

Application

Current state of development Market already in existence Market in existence, and ongoing research Market in existence, and ongoing research Market in existence, and ongoing research Market already in existence Research Research and anecdotal Research Research Research Anecdotal Anecdotal use Market in existence, and ongoing research

Current demand Medium Low to medium Low Low Low Low Low Low Low Low Low

Potential demand Decreasing High High Low to medium Decreasing High Low High High Low Low Medium

Geographical use World wide Worldwide Worldwide Worldwide Worldwide Worldwide Asia Worldwide Worldwide Asia Asia Currently USA

Flat Steel Production Concrete manufacture Silica fume replacement Lightweight construction materials Refractory Bricks Manufacture of silicon chips Insect control 21 Activated carbon in water purification Vulcanising process Extraction of gold, and other chemical uses Household ceramic products (tiles, glazes) Soil ameliorant Oil absorbent Table 5

Purchase price per tonne Medium Low High Low Medium Low Low High Low Low Medium

Suitability as a Market Not expanding. Expanding and CER potential Expanding and CER potential Currently localised, potential in future Small, not expanding. Not yet market ready, limited potential. Low demand, local use Potentially large market Not yet market ready Not yet market ready Little evidence Low value local use Potential for marketing as a new product

Opportunity matrix of uses and potential markets for RHA

4.4 4.4.1

Steel Global overview of steel production

In 2001, approximately 850 million metric tonnes of steel were produced worldwide. Of this, 730 million metric tonnes were continuously cast steel, the process for which RHA could be used. Globally, steel production has increased from 1970, but there are fluctuations, with the period 20002005 showing a drop of 0.1% on the previous five year period (1995-2000). It is hard to predict future growth of the steel industry, but it can be assummed that over the long term production will remain fairly constant. The production of continuous cast steel is likely to increase as developing countries improve their industrial processes [9].
3 2.5 2 1.5 1 0.5 0

-1 97 5

-1 98 0

-1 98 5

-1 99 0

-1 99 5

-2 00 0 19 95

-0.5 -1

19 70

19 75

19 80

19 85

Figure 6

Average growth rates (% per annum) in world steel production.

Asia and the EU dominate steel production, producing 64% of the worlds continuous cast steel (Figure 6).

Rest of world 24% Asia 43% USA 12% European Union 21%

Figure 7

Global production of contiuous cast steel, by area, 2001 [9].

22

19 90

20 00 -2 00 5

China is the world's biggest producer of continous cast steel, as shown in Table 6. Continuously cast steel production (million metric tonnes) 130 100.1 87.3 43.2 43 30 25.6 24.5 18.3 17.3 17.1 15.9 15 14.9 13.2 12.5 10.7 8.7 7 6.9

Rank 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 Table 6 4.4.2

Country China Japan USA South Korea Germany Russia Italy Brazil France India Taiwan Spain Turkey Canada UK Mexico Belgium South Africa Australia Iran

Continuously cast steel production, ranked by country [9].

Factors affecting the demand for RHA in the steel industry

In 1998 a confidential report estimated that global demand for RHA in the steel industry was 151,000 tonnes a year. Use in 1998 was dominated by Europe, which accounted for 33% of the market, with Korea and the USA also having significant shares (Figure 7). The report concluded that globally RHA demand in the steel industry would increase at an average rate of 6 to 7% per year, expanding from to 268,000 metric tons per year in 2007 [11]. This was attributed to the continually increasing worldwide production both of steel in general and of higher quality flat steel products in particular, as well as growing industry awareness of the benefits of RHA. However a book written at the same time cautioned against the use of ash and stated that a controversy concerning possible harmful health effects of crystalline silica in the ash has somewhat eroded prices for the ash and has raised doubts concerning future ash markets and prices [3]. It appears that this controversy has still not been resolved, with reluctance amongst steel manufacturers to discuss the use of RHA.

23

Others 5% North America 23% Western Europe 33%

Japan 22%

South Korea 17%

Figure 8 Europe

Global share of RHA in the steel industry, 1998 [11].

The 1998 confidential report stated that 62.5% of steel produced in Europe used RHA, and that globally the steel industry in Europe accounted for 33% of RHA use, with Germany being the biggest importer in Western Europe (Figure 8 and Table 7)[11]. Country Germany Italy France United Kingdom Spain Belgium Netherlands Sweden Austria Luxembourg Finland Table 7 Tonnes 14,100 8000 6200 5800 4300 3400 2100 1600 1600 1500 1200 % Global total 9% 5% 4% 4% 3% 2% 1% 1% 1% 1% 1%

RHA use in the steel industry in Western Europe, 1998 [11]

Since 1998 the health issues surrounding ash have become more significant, with Sweden banning the use of RHA. A survey of the major steel producing companies in Europe met with a limited response. The European steel industry is dominated by just a few main companies, due to a recent spate of mergers. For example, Arcelor, a merger of Aceralia, Arbed and Usinor, the worlds largest steel manufacturing group, produces 50 million metric tonnes of steel a year, nearly 6% of global production. No comment was available from them regarding the use of RHA.

24

CORUS (formerly British Steel and Hoogovans of the Netherlands) were available for comment. Although there is no specific ban on the use of RHA from the Health and Safety Executive in the UK, there are strict rules for use of crystalline silica-based products [56]. CORUS does not use RHA on a large scale. With manufacturing operations in the UK, Netherlands, Germany, France, Norway and the USA they are responsible for the production of 2% of global steel production. Eastern Europe may be different with several of the larger steel manufactures setting up plants in the former East Germany, Poland and the Czech republic. However the health issues may still be a problem. It is hard to predict the future of the market for RHA in Eastern Europe, but is appears that the market in Western Europe is shrinking. Asia

Opportunities may be greater in countries that are producing their own RHA, as there will be lower transport costs. Little is known of the significance of the health issues relating to RHA use in Asian countries. It is known that there are several proposals for husk to energy plants, for which sales of ash to the steel industry are expected to bring in significant revenue, although it is unlikely that this will be sold to the European steel manufacturers. It is likely that Korea is an end market for some of this ash, as 75% of all steel in Korea uses RHA in processing, although domestic RHA dominates the market. This ready market for domestic ash could be favourable to husk to energy projects in Korea, which produced 1.3% of the worlds total paddy in 2002, and potentially could produce 250,000 tonnes of ash per year (Table 1). The Thai steel industry does not use RHA as it does not use the continuous casting process required for producing high quality flat steel. It uses rice husks, which provide enough insulation for the lower quality steels requiring shorter casting times. There is anecdotal evidence that in the rare cases when RHA is used, there are health and safety problems with ash becoming airbourne after being tipped on the tundish. There is potential in the future for a market for the ash as the steel industry develops. Thailand is a major rice producer (number six in the world in 2002, Table 1) and has a great potential for husk to energy projects and resulting RHA production, but it is likely that the ash will be exported rather than used domestically in the steel industry. There are several proposed husk to energy projects in Thailand, for example, Jpowers 9.95 MW Roi-et RHA fired plant, due to begin operation in 2003 and ATBiopower is developing several husk to energy projects in Thailand, totalling 90MW, with the RHA being sold to the steel and concrete markets. Agrilectric has husk to energy projects under development in Brazil and Thailand, and it is proposed that the RHA will be marketed again within the steel industry [34]. Other plants within Asia include Ban Heng Bee rice mill in Alor Setar in Malaysia, which are planning to pursue ash sales from its energy plant. It estimates that it can make US$179,000 per year from ash sales, most probably within the steel industry [57]. USA

The USA is one of the largest growers of rice in the developed world, and the 1998 confidential report highlighted the USA steel industry as being a considerable user of RHA, responsible for 23% of the global market share, some 35,000 tonnes a year (Figure 8) [11]. This ash was produced domestically, predominantly by Uncle Bens. Uncle Bens also export to Europe, and in 1998 were responsible for 20% of RHA imports to Europe [11]. The market for RHA in the steel industry in

25

the USA appears to be saturated. Little is known of the significance of health issues. There are US government safety guidelines concerning working with silica that would apply to RHA [58, 59]. Australia

Australia is one of the smaller of the worlds rice producers, producing 957,000 tonnes of paddy in 2002 [1]. It ranks 19 in the production of continuous cast steel (Table 6), so is not a significant producer or user of RHA. Despite this, Rice Growers Ltd and Biocon in Australia are planning a cogeneration plant at Deniliquin and Biocon plan to manufacture pellets from the crystalline silica [12]. They expect to export 1000 tonnes in pellet form packed into 7.5kg bags, selling directly to steel manufacturers, either BHP Steel at Port Kembala, NSW, or to Canada, and have plans to expand the operation.

4.4.3

Prices and future trends

Prices for RHA being sold to the steel industry are commercially sensitive and thus hard to determine. N.P.Singhania in India is selling RHA at US$150/tonne, delivery at Calcutta port, India [60]. Other estimates of RHA on the world market are approximately $200 per ton of ash, [61] although it has been said that Thai RHA is worth US$300-400/tonne [11]. The impact of the emergence of pellets onto the market is hard to predict. Alsical, a small RHA importing company based in East Germany, see that the future for RHA lies in overcoming the health issues. They are developing a pelleting technique which they hope will be accepted in the European steel industry. The largest RHA dealer world wide is Refratechnik, based in Germany. A manufacturer of refractory bricks, Refratechnik uses small quantities of RHA itself, but also sells RHA to the steel industry. Refratechniks import RHA from Thailand, and in 1998 was responsible for 33% of global sales, some 50,000 tonnes. Of this, 60% was sold into the European steel industry [11]. Currently Refratechnik controls the market and it is not thought that it has any plans for the production of pellets. If pellets can be shown to be a safe method of both application and disposal of RHA after heating in the tundish, then the markets in Europe may expand. However, discussions with CORUS imply that as the use of RHA in the steel industry involves heating to extreme temperatures, crystalline silica will always form and be a health hazard, regardless of the form in which the RHA was initially. 4.5 4.5.1 Cement and concrete industry Introduction

In light of economic conditions and the plentiful evidence, both from research and in the field, it seems inevitable that regular and high-volume usage of admixtures will become standard practice in the concrete industry. Although the concrete industry market for RHA is still being developed, it is considered as being potentially a much larger end user than the steel industry. Two markets can be distinguished; as a substitute for silica fume and in the production of low cost building blocks. 4.5.2 RHA as substitute for silica fume

As discussed in Section 3.3.2, RHA can substitute for silica fume in the manufacture of high strength concrete. In 2000, 17.75 billion tonnes of cement were produced worldwide [62]. In the

26

UK silica fume is used at a rate of 0.34% of the volume of cement [63]. Extrapolating this figure worldwide results in a potential global market of up to 590,500 tonnes. The potential for this is currently being restricted by several factors. The cement industry has to produce a consistent, high quality and standard product. This in turn requires RHA from a controlled combustion environment, to ensure a consistent standard ash. Ash of a consistent quality is not readily available and is therefore not used by the cement industry. There are many other cheaper and more abundant pozzolans available. A waste product from coal fired power stations is pulverised fly ash (PFA). It is abundant and cheap and is therefore often used as an admixture in high strength concrete. Ground granulated blast furnace slag produced from iron smelters is also highly pozzolanic and available. However, for high strength and quality, silica fume is preferred, for which RHA is a potential substitute. There is little awareness in the cement industry of the enhanced properties of RHA cement, although this being remedied to some extent in the USA. USA

Pittsburg Mineral & Environmental Tech. Inc. (PMET), part of Alchemix Corporation, Carefree, Arizona, buys RHA that can be used as a substitute for silica fume in the production of specialist concrete [64]. It promots the use of RHA in concrete so well that there is currently a shortage. PMET specify the following for use a substitute for silica fume. Crystalline silica Carbon content Mean particle size Table 8 not to exceed 1% not to exceed 6% 7-9m, 95% passing a 45-micron sieve

Specification of RHA as a substitute for silica fume.

Ash is not usually this fine, irrespective of the combustion technique. PMET grinds the ash to achieve the fineness required and does not anticipate receiving ash that would be too coarse for its grinding process. The only plant supplier to guarantee ash of the correct quality is Agrilectric [34]. Purchase prices of RHA, which meet the technical specifications in Table 8, are from $100 to $120/tonne delivered to a US gulf coast port. This price is before grinding to meet final size requirement. UK

The cement industry in the UK produced 12 million tonnes in 2001 [64], making it a significant producer in global terms. The silica fume market was analysed to estimate the potential market for RHA in the UK. Cement manufacturers (Heidelberg Cement, Lafarge), concrete/aggregate suppliers (Hanson building materials, Tarmac, RMC) and silica fume suppliers (Elkem, INVENSIL and Fesil Microsilica) were contacted to determine the size of the silica fume market and potential for substitution with RHA. Although specific quantities and costs for silica fume were not available (due to their commercially sensitive nature), the market is estimated at between 3000 - 5000 tonnes per year. Currently no RHA is being used in the UK concrete industry. Several companies had been offered the ash but 27

were not using it due to the availability of PFA, granulated blast furnace slag and silica fume. According to one source, the demand for silica fume is higher than supply and there could be an opening for RHA. One of the main concerns with RHA is supply and consistency of quality within the product. Australia

According to CSR Ready Mix, a major construction materials supplier in Australia and North America, there is very limited use of RHA in Australia commercially and it is not used as substitute for silica fume. Many of the rice growing areas in the eastern part of Australia are distant from the big markets of Sydney and Melbourne. Up to now it has been difficult for RHA to compete with other supplementary cementitious materials such as fly ash which is commonly used in concrete in Sydney and Melbourne (approximately 95% of the pre-mixed concrete volume). CSR Ready Mix is the biggest user of silica fume in Australia using about 9000 tonnes per annum. There are two suppliers in Australia: Simcoa in Western Australia and Tasmanian Silicon in Tasmania. The price depends on how much is being used. Typically cement costs in excess of AUS$150 per tonne for large users and silica fume is approximately AUS$450. 4.5.2 Future trends and prices

There is great potential for RHA use in the cement industry, but it is currently not being used to any extent, except in the USA. Two main issues appear to be limiting its use: Lack of awareness of the potential for RHA. Quality.

PMET in USA appear to have overcome both these problems. The patented process [31,32], filed by Dr Mehta, and owned by Alchemix should overcome the quality issue. PMET have also shown that, if awareness is raised, then there will be a demand for RHA, and as demand increases, so should prices However producing RHA of the correct quality may cost more than producing normal ash due to boiler modifications etc, this is discussed in detail in the Cost Benefit Analysis discussed in Section 7. 4.5.3 RHA in building block manufacture

In developing countries RHA is used extensively in the production of low cost building blocks, in its raw form as an additive to cement. In India alone approximately 30,000 tonnes of RHA cement is manufactured annually [18]. SDH in Java manufacture lightweight blocks made from RHA, Hakkablock (Plate 7), and market them for use in high-rise construction where weight of construction materials is important. Prices were not available.

28

5.
5.1

TECHNICAL REVIEW
Introduction

Commercially, it is important to determine and control the type and quality of rice husk ash produced. These can vary depending upon the different combustion techniques used. For example, stoker fired boilers tend to produce higher quantities of crystalline ash, whereas similar boilers with suspension firing produce more amorphous ash. The additional revenue stream provided by the sale of RHA may be the key to an energy projects viability. If this is the case the appropriate technology should be chosen to produce ash of the required type and quality for the target RHA market. For example, the colour of the ash is important for some cement markets where the ash influences the colour of the final cementitious product, as well as being a major indicator of the samples residual carbon. For example, from Thailand, blackish and whitish ash can command $150 and $400 a tonne respectively [11]. RHA can be produced from rice husks by a number of thermal processes which are described below. 5.2 5.2.1 Overview of husk to ash process Rice husk as a fuel

The husk surrounding the kernel of rice accounts for approximately 20% by weight of the harvested grain (paddy) [65]. The exterior of rice husks are composed of dentate rectangular elements, which themselves are composed mostly of silica coated with a thick cuticle and surface hairs. The mid region and inner epidermis contains little silica. In small single stage mills in developing countries, where bran (the layer within the husk) is not fully separated from the husk, the husk plus bran stream can rise to 25% of the paddy. For larger mills, where the husk and bran are fully separated (the type more likely to be providing the husk for electrical generation), a husk to paddy ratio of 20% is appropriate [65]. Most heating values for rice husk fall in the range 12.5 to 14MJ/kg, lower heating value (LHV). If some bran remains with the husk, a somewhat higher calorific value results. Rice husks have low moisture content, generally in the range of 8% to 10% [3, 65]. The following are typical chemical analyses of rice husks: Property Bulk density (kg/m3) Length of husks (mm) Hardness (Mohs Scale) Ash Carbon (%) Hydrogen (%) Oxygen (%) Nitrogen (%) Sulphur (%) Moisture (%) Table 9 Source 67 67 67 3 3 3 3 3 3 3 Source 34

96-160 2.5-5 5.5 6.5 22.24 35.77 5.06 36.59 0.32 0.082 8.05

128

13.2 29.0 36.66 4.37 31.68 0.23 0.04 8.76

68 34 34 34 34 34 34

Typical husk analysis from various literature sources

29

The high ash content of rice husks and the characteristics of the ash impose restrictions on the design of the combustion systems. For example, the ash removal system must be able to remove the ash without affecting the combustion characteristics of the furnace (especially if the ash produced is mostly bottom ash). The temperatures must be controlled such that the ash melting temperature of approximately 1440C is not exceeded and care must be taken that entrained ash does not erode components of the boiler tubes and heat exchangers [3, 65]. This influences the design of the combustion system, a review of which is presented below. 5.2.2 Incineration

Incineration is the term usually used for deliberate combustion of husk without the extraction of energy and encompasses: open burning (such as deliberately setting fire to piles of dumped husk), enclosed burning (typically a chamber made from fire resistant bricks with openings to allow air to enter and flue gases to leave). Boilers with integral combustion

5.2.3

For energy recovery from the combustion of fuels, the most common type of combustion system incorporates heat extraction from the combustion chamber using steel tubes through which water circulates. In so doing the water removes heat from the combustion chamber while at the same time increasing in temperature. This type of boiler is called a water wall boiler. An alternative type uses an uncooled combustion chamber (sometimes called a firebox) connected to a large drum of water through which tubes are placed to carry the hot exhaust gases from the combustion chamber to the boiler chimney. This type is called a fire tube boiler. Such boilers tend to be less expensive for applications where a boiler size of less than 20tonne/hr and a pressure below 20 bar is appropriate. A variant of the fire tube boiler configuration is one in which the combustion chamber remains uncooled but the hot gases go to a separate water tube heat exchanger. Sometimes the heat exchanger is called a heat recovery steam generator (HRSG). This configuration avoids a potential problem that can occur with high ash fuels which can cause ash build-up in the tubes of fired tube units. For power production using rice husks, water tube boilers are the most common choice. The combustion chamber is normally of rectangular cross section. The walls of the chamber are formed either by tubes welded to each other or with the interstitial space filled with refractory. The tubes may extend to the base of the chamber or finish at a higher level with uncooled fire-brick walls filling the lower area. The chamber is closed at the base. The type of closure depends on the type of boiler but there is always a means of extracting ash from the base. This ash is called bottom ash to distinguish it from fly ash which leaves with the hot flue gases and is removed later in the process. Generally, the chamber tapers at the top before connection to a gas passage where the exiting hot gases pass over additional water or steam filled tubes before release to atmosphere. Sometimes steam or water filled tubes are suspended from the chamber roof into the central combustion zone of the chamber.

30

Combustion boilers with water cooled tubes for rice husk application may be further sub-divided into three main categories: stoker fired, suspension fired and fluidised-bed. Stoker fired

Stoker fired boilers employ a grate at the bottom of the combustion chamber. Rice husks are fed above the grate on which they form a pile where combustion mainly occurs. Secondary combustion of released volatile gases occurs above the pile. Typically temperatures vary over a wide range but are highest in the pile. As a result the fusion temperature for ash can be reached. Most ash drops through the grate. The smaller volume residual fly ash is carried away by the flue gases. Suspension fired

Suspension firing is an adaptation of the nozzle burners used to burn liquid fuels such as oil. This arrangement avoids the need for a grate at the base of the combustion chamber. This has several potential advantages including: the elimination of an expensive and high maintenance piece of equipment, improved combustion using finer particles, easier control of excess air to the combustion chamber, improved combustion efficiency.

The solid fuel has to be prepared so that it is sufficiently fine to be blown into the combustion chamber such that combustion occurs within the short period of time available whilst the fuel is in suspension. Otherwise, the fuel will fall to the base of the chamber which would then need to have a grate similar to a stoker-fired unit. For rice husks, this means that the husks have to be ground to a fine powder before combustion. Fluidised bed combustors

The term fluidised bed combustor (FBC) encompasses a range of combustion/boiler combinations where combustion of the fuel takes place within a bed of inert material that is kept fluid by an upward draught of air. The combustion chamber is similar to conventional boilers, such as stoker fired designs, except that the floor of the boiler is covered with numerous air nozzles and some ash removal outlets. Primary combustion air enters the boiler through the nozzles and in so doing causes the mix of fuel and inert material to mix continuously in a manner similar to a fluid. The fuel is often fed from apertures located some distance above the bed. Depending on the ash content of the fuel, additional inert material may also be introduced to ensure that sufficient bed inventory exists for stable fluidisation. The mixing caused by fluidisation produces a relatively uniform combustion temperature and avoids the extremes in temperature that occur in other types of combustion. FBCs are conveniently subdivided into bubbling and circulating types. Bubbling FBCs have a relatively low fluidising air velocity. This creates a bed which remains within the lower part of the combustion chamber (ie there is no deliberate entrainment of fuel and inert bed material in the flue gas). Circulating FBCs employ a higher air velocity which causes a portion of the fluidised bed material, the lighter particles, to be transported upward with the flue gas. These particles are caught in a cyclone, or similar mechanical separation device, and returned 31

to the main bed, hence the term circulating. Circulating FBCs tend to be more efficient that bubbling beds but the added complexity has resulted in their application only for larger boiler sizes - typically for outputs greater than 150MWth. Relatively few FBCs have been used for rice husk applications. Where used, bubbling bed types seem to have been employed. 5.2.4 Gasification

Gasification is a type of combustion in which the fuel is heated to release volatiles and convert carbon to carbon monoxide. The gaseous products in the volatile form a producer gas which can then be used in a manner similar to gaseous fuels. The heat to produce gasification is normally derived from the fuel itself. The producer gas contains varying amounts of hydrogen, carbon monoxide and methane depending on the fuel and the gasifier design. An important potential advantage of gasification is that the producer gas (after cleaning) can be used as fuel for reciprocating internal combustion engines (ICE) or for gas turbines. This avoids the Rankine steam cycle as the means to convert thermal energy to electrical energy and avoids need for cooling water. Theoretically, a gasifier coupled with an ICE or gas turbine can lead to a significantly higher energy conversion efficiency. This might be approximately 33% at relatively small unit sizes (down to about 1500kWth). At the same size, a steam boiler system might achieve only 15% conversion efficiency or less. 5.3 Overview of ash production

The different types of combustion have one common characteristic. They all result in the oxidation of most of the combustible portion of the husk while leaving the inert portion. The inert portion is generally called ash or, after gasification, char. The distinction is somewhat blurred. Originally the term char referred to the uncombusted residue that had not been taken to a sufficiently high enough temperature to change its state, whereas the term ash implied that a higher temperature and change of state had occurred. However, when applied to RHA, the term ash appears to be reserved for all processes apart from gasification irrespective of whether a change of state has occurred. In chemical analyses of husks the term ash refers to the chemical constituents of the residual from complete combustion without consideration of the morphology of the components. The term ash, in this study refers to the residual of the particular combustion or gasification process which produced the ash. The fine particulate matter which is carried away from the combustion zone by the flue gas produces fly ash. With stoker and suspension fired boilers this ash is close to 100% amorphous since the crystalline portion of the ash does not seem to carry in the flue gas. Bottom ash is denser than fly ash, and for rice husks tends to be more crystalline than the fly ash. Where fluidised beds and gasifiers are concerned the distinction is not so readily made, since the combustion occurs at lower temperatures and thus a higher proportion of amorphous ash would be expected in the bottom ash compared with bottom ash from stoker and suspension boilers. The proportion of bottom ash to fly ash depends upon the boiler type and operating conditions. For example, McBurney Corporation offer a suspension fired boiler with pregrinding of the husks. This produces approximately 10% bottom ash and 90% fly ash [34]. Suspension fired boilers by other manufacturers, such as Fortum, are expected to produce similar proportions of ash. Combustion

32

units with uncooled chambers, such as challenger units by Advanced Recycling Equipment Inc appear to produce nearer to 50% bottom ash and 50% fly ash. At least one manufacturer, Torftech UK Ltd has a compact bed reactor (Torbed reactor) which produces almost 100% fly ash [68]. For stoker fired boilers 20-30% of the ash is expected to be bottom ash, the remainder fly. An example of typical fly ash and bottom ash is shown in Plates 12 (a) and (b). 5.4 Methods of ash analysis

Typically, the ash will contain some unburnt components as well as inert components of the husks. The unburnt component is predominantly carbon. It is typically measured by reheating a sample of the ash in an oven. The difference in mass of the sample before and after heating is referred to as the Loss on Ignition (LOI). The LOI value is normally the same as the carbon content of the ash. The carbon content of RHA varies according to the combustion process. RHA analyses from a literature search and from analyses performed on RHA material for this study indicate carbon (or LOI) values ranging from 1% to 35%. Typically, commercial RHA combustion appears to result in RHA with 5-7% maximum carbon. The high silica content in the husk may be responsible, in part, for the residual carbon in RHA by cocooning the carbon such as to prevent air circulating around it or by bonding to the carbon at the molecular level to form silicon carbide. The silica in the rice husks is at the molecular level, and is associated with water. It occurs in several forms (polymorphs) within the husks. In nature, the polymorphs of silica (SiO2) are: quartz, cristobalite, tridymite, coesite, stishovite, lechatelerite (silica glass), and opal; the latter two being amorphous [3]. For RHA as a potentially marketable product we need only distinguish between amorphous silica and crystalline silica. From the technical literature, two forms appear to predominate in combustion and gasification. These are lechatelerite (silica glass), an amorphous form, and cristobalite, a crystalline form. SiO2 can also occur in a very fine, submicron form. This form is of the highest commercial value although it is the most difficult to extract. The major and trace elements are conventionally expressed as their respective percentage oxides and may not actually be present in this oxide form. SiO2 is generally determined as total SiO2, since the proportion of crystalline to amorphous silica requires further costly analysis, usually by XRay Diffraction (XRD). Determining the quantity of these polymorphs is fundamental to investigating a market for the ash. The colour of the ash generally reflects the completeness of the combustion process as well as the structural composition of the ash. Generally, darker ashes exhibit higher carbon content (with the exception of those that may be darker due to soil chemistry/region (see below). Lighter ashes have achieved higher carbon burnout, whilst those showing a pinkish tinge have higher crystalline (tridymite or cristobalite) content. 5.5 5.5.1 Factors influencing ash properties Temperature

XRD patterns of ash combusted at a range of temperatures from 500-1000C have shown a change from amorphous to crystalline silica at 800C, and the peak increased abruptly at 900C [13]. The change from amorphous to crystalline silica at 800C was also found in other studies [69]. In Vietnam, a series of experiments using a laboratory oven under conditions designed to simulate the

33

conditions of combustion from a rural facility were carried out [70]. SEM analysis of the ash found that the globular amorphous silica increased in size from 5-10m to 10-50m with rising combustion temperatures from 500-600C. The transition to completely crystalline silica was complete by 900C. This can be described by Equation 1 below [20]:
amorphous Qtz 400 600 deg C 153 deg C Qtz

( 1 + 2 )
117 163 deg C

Tri

1470 deg C

(1 + 2) Tri

Crist 228 800 deg C Crist

Equation 1 Note:

Transition from amorphous to crystalline silica

quartz converts to quartz at 573C quartz converts to tridymite at 870C tridymite converts to crystobalite at 1470C

These changes affect the structure of the ash. As such, the grindability and therefore reactivity of the ash is affected since, after grinding, a greater surface area is available for chemical reactions if the ash is to be used as a pozzolan. For the steel industry, more crystalline ash is preferred as this increases its refractory properties. 5.5.2 Geographical region

It has been reported that chemical variations in husk composition (and consequently ash composition) are influenced by such things as the soil chemistry, paddy variety and climate. However, only one report of a change in the physical and chemical properties of ash influenced by region was found [66]. A variation in colour and trace metal was found in ash from husks burnt in different regions, with ash produced from husks from Northern India resulting in a much darker ash than husks from the US [66]. The colour variation was not related to differences in the carbon remaining in the ash, although it is not known the precise regional features that affected the ash. It could be due to the agronomy of the paddy as studies have shown that differences in mineral composition of ash can be attributed to fertilizers applied during rice cultivation, with phosphate having a negative affect on the quality of the ash in terms of its ability to act as a pozzolan [20]. It has also been said that the high K2O found in some ashes could be a consequence of K-rich fertilizers used during the paddy cultivation [71]. 5.6 Review of influence of combustion method on properties of RHA

The main factors in the various combustion and gasification processes that determine the type of ash produced are time, temperature and turbulence. These effect all chemical changes that occur in the combustion process including the way the ash morphology is altered. A broad explanation of combustion techniques was given in Section 5.2. Specific chemical and physical properties of ash, taken from literature accounts, are described below. Appendix A compiles the chemical analyses of rice husk ash from the literature review, going back several decades. It also includes the analyses of two samples of RHA (one bottom ash and one fly ash sample) obtained specifically for this study. In most of the analyses there were no details of combustion or analytical techniques, making it impossible to associate the chemistry of ash directly with a specific combustion technique. This lack of information may be due in part to many of the 34

analyses having been conducted under laboratory conditions, and also due to the commercial sensitivity of giving exacting technological specifications alongside chemical analyses of ash. A summary of all the ash analyses is at the end of this chapter. A study in 1972 compared a range of data for ash composition (Records 5-13 in Appendix 1) [67]. The wide range of values was as a result of the variation of purity of the samples and the accuracy of the analytical procedures used. However, since there is no information on different combustion techniques employed in the husk combustion, or analytical techniques used, it is difficult to tell whether any of the reported ranges in chemistries seen could be attributed to particular combustion techniques. The patent filed by P.K.Mehta, for producing RHA of a quality ideally suited to the cement market, [31,32], describes burning the husk continuously at a low temperature to preserve the amorphous nature of the silica [71]. The method utilizes the fly ash after its separation from the flue gases by a multi cyclone separator. Ash analyses 27-29 in Appendix A are taken from two of P.K. Mehtas Patents [31, 32]. Commonly, in the production of highly amorphous ash, low temperatures and fairly long burntimes are used, as for Mehtas patent. Other work in India has also concentrated on this technique, and has shown how a two-stage process of combustion could control the chemical and physical properties of the resultant ash, increasing its pozzolanic activity by taking the husk through a carbonising process without flaming. This type of burning was shown to produce a fine white ash which did not carbonize [72]. By comparison, a normal combustion process (taking the furnace from room temperature up to the fixed burning temperature, where it was held until combustion was completed) produced a black coloured ash [72]. This same study compared the RHA in terms of electrical conductivity and compressive strength tests with concrete. The electrical conductivity is an effective measure of the amorphousness of the ash and showed that the slow-burn process produced significantly more amorphous ash. Similar results were found in a study in Guyana to ascertain the relationship between operation conditions and ash chemistry produced in terms of ash colour, carbon content and silica activity index (a measure of its pozzalanicity) [20]. Comparing 5-hour with 7-hour burn times showed higher LOI in the shorter burn-time experiments (~6%) compared with ~3% LOI for longer burn times. In addition, higher percentages of silica were produced over longer combustion periods although no details were given concerning the percentage of amorphous and crystalline ash. 5.6.1 Fixed grate boilers

None of the reports in the literature made specific reference to conventional grate (fixed- or moving-grate) technology, and although reference to normal or conventional boilers may well be a reference to a grated boiler we cannot assume this in terms of the reported ash properties. However, a sample of ash (Patum) from a fixed grate boiler in Thailand was analysed, the results of which are given in analysis 31 in Appendix 1. A significant difference between this and other ash samples is the large grain size, with 50% of the sample larger than 0.425mmsq/hole sieve. Compared with the circulating fluidised bed RHA (see Fortum ash analysis below) the Patum RHA showed a higher LOI (4.1% versus 2.2%), a higher total carbon content (3% versus 0.5%) and higher crystalline silica content as one would expect comparing the two technologies. The coarseness of the ash samples has market significance, because for the majority of marketable purposes (steel, cement, absorbent etc) a fine material is preferred, and the grinding of husks before combustion or RHA after combustion adds a significant cost to the process.

35

5.6.2

Fluidized bed

Since FBCs have a more uniform and lower combustion temperature than stoker boilers, it is possible that such boilers produce less crystalline ash. Burning husk in a fluidised bed burner has been found to give mainly amorphous ash with a high specific surface area [73]. Best results have been obtained by controlling the temperature of the burner via fuel feed rate, with the air supply set at an optimum velocity of 15m/s and the temperature set at an optimum 750C. Comparing the properties of this ash for pozzolanic reactivity with Portland cement, with ash obtained from conventional combustion techniques, (although no description of conventional combustion techniques was given) gave excellent results in terms of its compressive strength [73]. An analysis from a study involving a series of experiments using a fluidised bed, at differing velocities, bed temperatures, husk feedrate and excess air levels is presented in analysis 4 in Appendix A [74]. There was no information giving of the proportion of amorphous to crystalline ash although the silica recovery was high (97.6%) and the carbon content ranged from 1-4%. 5.6.3 Circulating Fluidised Bed (CFB)

The only RHA sample available that can be unequivocally assigned to combustion by a circulating fluidised bed is Fortum, a sample obtained specifically for this study. The sample is a very fine material, with approximately 50% by volume passing through a 0.150mm sq/hole sieve. It is a pale grey ash (see Plate 12b) compared with the coarser bottom ash from Patum (Plate 12a). It has a low carbon content of 0.5% as is often, although not always, the case with pale coloured ash. Generally one would expect more amorphous ash from CFB combustion since the time spent at higher temperatures tends to be short, and due to the suspended nature of the fuel the temperature is evenly distributed and does not result in extremely high temperature hot-spots. However, the analysis of the Fortum ash reveals a fairly high crystalline silica content of 33% crystobalite and 20% (transitional amorphous to crystalline) quartz. In terms of trace elements the Fortum and Patum samples exhibit similar concentrations. 5.6.4 Grate versus conventional

The National Research Institute in Chatham, UK is conducting a two year long investigation into improving the boiler efficiency of rice furnaces in Bangladesh, with a view to producing RHA of a consistent quality to sell to the cement industry. The NRI have conducted a series of experiments both on the RHA itself and also on blocks made with varying proportions of RHA, substituting for cement, to examine changes in its strength properties. The NRI obtained several samples, mainly from two types of boiler (grate and conventional), however no additional information about the exact type and operating conditions were taken. The results so far show a clear correlation between the types of ash produced, in terms of crystalline vs. amorphous silica content, and the boiler type. The average percentage of crystalline silica in the ash was 75.1% and 17.45% for grated and conventional furnaces respectively.

5.6.5

Gasification

36

Literature sources reviewed to date focus more on the relatively high unburnt carbon content of char/ash from gasifiers without providing data on the relative amounts of amorphous to crystalline ash. The unburnt carbon can exceed 40%. This would preclude use of the ash for other than low cost uses and may explain why no extensive beneficial use of gasifier ash has been found. Joseph [25], investigated the combustion processes necessary to burn husks under controlled conditions such that the ash remains mainly amorphous and that the C content is reduced to below 15%, in order that it can be used as an additive in lime, bricks or cement. The findings from this fairly early research concluded that combustion through gasification, rather than through a vortex furnace produced the better quality ash, and the quality of the ash was further improved by varying the gasification conditions. Significantly, and so far unreported from other publications, they found that variations in collection methods and ash cooling significantly affected the properties and characteristics of the ash. Once collected from the gasification system carbon burnout occurred over the proceeding four days in the concrete ash pit, the carbon content of the ash after four days had dropped to 7-10% from 26% immediately after collection. 5.6.6 Additional Technology

Torftech, a Canadian based company, supplies Torbed reactor based rice hull combustion systems. The technology provides ash with a high percentage of amorphous silica for use in the concrete and cement industries. They are able to produce low carbon, high surface area low crystalline ash by maintaining the temperature of their expanded bed reactors below 850C (at 830C with an estimated residence time of approximately 5 minutes, no crystallization occurs) [68]. The technology has been a joint venture between Torftech and the University of Western Ontario. Ash analysis 14 (Appendix A) shows the chemical analysis of the ash produced using their reactor technology. 5.6.7 Special market requirements

Little data is available regarding ash quality for the currently small and potential markets (sections 4.2 and 4.3). For the established market of the steel industry and the emerging market in the cement industry more data is available, and this is discussed in the cost benefit analysis (section 7). 5.7 Summary of technical analysis Indistinct and vague details are often given for boiler descriptions and RHA analyses. In such cases the value of RHA analyses in a commercial sense is minimal. There is a wide range in concentrations of physical and chemical properties of RHA as shown in Table 10 above. The change from amorphous to crystalline ash occurs at approximately 800C, although the process is often incomplete until 900C is achieved. Generally, lighter coloured ash has achieved a more complete carbon burnout. Al1 combustion processes devised to burn rice husks remain below 1440C, which is the RHA melting temperature. The chemical and physical properties of the ash may be influenced by the soil chemistry, paddy variety and fertiliser use. Suspension fired boilers generally produce more amorphous ash than stoker fired boilers despite the fact that they may operate at higher temperatures. This is because the operating time at high temperatures for suspension fired boilers is comparatively short.

37

Commonly, in the production of highly amorphous ash, low temperatures and fairly long burn-times are used. Fly ash is a fine material and is of higher marketable value since it requires less grinding than the generally coarser bottom ash. Fixed grate technologies tend to produce ash with higher carbon content, higher LOI and higher proportions of crystalline to amorphous ash.

A summary of the above studies (resulted in full in appendix 1) is shown below. Determinant PH SiO3 SiO2 (Total) SiO2 Amorphous SiO2 Crystalline Al2O3 Fe2O3 CaO MgO P2O5 Na2O K2O TiO2 Cl L.O.I. Carbon Table 10 % (unless otherwise stated) 8.1 - 11 0.1 1.23 62.5 97.6 0.16 97.6 <1.0 88.4 0.01 1.01 <0.01 2.78 0.1 1.31 <0.01 1.96 <0.01 2.69 <0.01- 1.58 0.1 2.54 <0.01 0.03 0.01 0.04 1.56 5.5 2.71 6.42

Summarising the major and trace elements from analyses given in Appendix A

38

Plate 10

De-ashing at Patum Rice Mill Thailand

Plate 11

Rice husk boiler at Riceland Mill, Thailand.

39

(a)

(b)

Plate 12 Photograph of typical samples of (a) bottom ash from a fixed grate boiler and (b) fly ash from a circulating fluidised bed boiler. Both samples are from rice mills in Thailand.

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6.

HEALTH ISSUES

All forms of crystalline silica represent a very serious health hazard [58]. The forms that develop at higher temperatures ie cristobalite and tridymite are particularly harmful. Exposure to crystalline silica via inhalation can lead to a number of diseases, the most common being silicosis. Amorphous ash does not contain the more harmful forms of silica, but can be a respiratory hazard, particularly if finely ground. No information specific to RHA is available, and the following applies to crystalline silica from any source. 6.1 6.1.1 Diseases Silicosis

Silicosis is the result of the bodys response to the presence of silica dust in the lungs. The respirable fraction of the dust can penetrate to the alveoli (airsacs) where the exchange of oxygen and carbon dioxide occur. When workers inhale crystalline silica, they land on the alveoli, and white blood cells (macrophages) try and remove them. The particles of silica cause the white blood cells to break open, resulting in fibrotic nodules and scarring on the lungs. Exposure may result in shortness of breath on exercising, possible fever and occasionally bluish skin at the ear lobes or lips. Progression of silicosis leads to fatigue, shortness of breath, loss of appetite and respiratory failure which may cause death [59]. There are three classes of silicosis: Chronic silicosis

Usually occurs after ten or more years of exposure to silica at relatively low concentrations. Accelerated silicosis

Results from exposure to high concentrations of crystalline silica and develops five to ten years after initial exposure. Acute silicosis

Occurs where exposure concentrations are the highest and can cause symptoms to develop within weeks to four or five years after initial exposure. 6.1.2 Cancer

Crystalline silica is classified as carcinogenic to humans, and the International Agency for Research on Cancer (IARC) concluded that there was sufficient evidence in humans for the carcinogenity of crystalline silica [75,76]. 6.1.3 Other diseases

Silicosis has been shown to increase susceptibility to scleroderma, lupus, arthritis, tuberculosis and kidney disorders [77]. 41

6.2

Exposure limits

The UK Health and Safety Executive (HSE) has assigned a maximum exposure limit of 0.3mg/m3 for crystalline silica, expressed as an eight hour time weighted average [14]. The USA Permissible Exposure Limit (PEL) is 10mg/m3 divided by the % SiO2 + 2 [15]. This level is considered as being too high and there are additional recommended, but not statutory levels, of 0.1mg/m3 for crystalline silica, 0.05mg/m3 for cristobalite and 0.05mg/m3 for tridymite [58]. 6.3 Measures to control exposure

The UK HSE do not have regulations relating specifically to RHA, and state that the rules for silica should be followed. The UK HSE advise that samples should be taken if dust levels are expected, and that they should be regarded as significant of they are above 0.1mg/m3 [56]. In this case dust control levels should be implemented. Capturing and controlling dust at source is always easier than attempting to control exposure by ventilating the whole area. Suggestions for controlling dust levels include [59, 77]: 6.4 Dust control programme. Medical surveillance/disease reporting. Training and information to workers. Equipment maintenance programme. Isolated personal hygiene facilities, eating facilities and a clothing change area. Record keeping. Regulated areas/warning signs. Health issues in relation to use of RHA

Within the power plant, exposure could occur when de-ashing the boiler, collecting, packaging and transporting the ash. End uses involving crystalline ash such as in the steel industry and in silicon chip production should be considered carefully. Methods to limit exposure within the steel industry are already being developed. The other major market for RHA, concrete, only uses amorphous ash so carcinogenic heath issues should be minimal.

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7.
7.1

COST BENEFIT ANALYSIS

Introduction

In earlier sections of this report, information has been provided on the characteristics of, and potential uses for RHA. In summary, depending on the combustion method chosen, RHA can vary from having a negative value, where costs have to be incurred to dispose of it, to having various positive values depending on its quality and the market for it beneficial use. The main characteristics that determine the potential value of RHA are: residual carbon content, significant quantity of crystalline phases of silica dioxide present mainly amorphous silica with little or no crystalline phases

Given the premise that a viable rice husk fuelled power plant is to be built, the cost benefit resulting from increased expenditure to produce a RHA with higher value than would otherwise result is assessed in this section. In order to examine the cost benefit analysis for RHA, we have chosen a generic rice husk fuelled power plant sized to produce 3MWe (net) has been chosen. Unless stated otherwise, the analyses use the following assumptions: ash content of fuel is 18% annual operating time of plant 7,500 hours all prices are in US$

In order to put into perspective the additional revenues attributable to RHA use, it is useful to keep in mind that, if electricity has a value of 6 US cent/kWh and all the plant output is sold at this price, the annual revenue from electrical sales is $1,350,000. 7.2 RHA Disposal Negative Benefit

The predominant reason why RHA would only be suitable for disposal is when its residual carbon content exceeds 7%. Based on the power generation technologies examined within the scope of this work, those that seem to result most often in a higher residual carbon content are gasifiers. A plant producing 3MWe using gasifier technology will have multiple units because the application of gasification to rice husks has not been proven in units larger than about 750kWe. The rice husk consumption will be approximately 3.75 tonne/hr and the RHA leaving the gasifiers will be 0.675 tonne/hr. Over the course of a year of operation, the total RHA produced will be 5063 tonnes. Typical disposal cost for RHA for transport and disposal at disposal site range from approximately $5/tonne for local disposal in developing countries where land costs are low, to $50/tonne and higher for disposal to engineered landfills in developed countries. When disposal costs are as low as $5/tonne, the negative cost of producing RHA which has no beneficial use would be $25,315/year or less than 2% of the revenue from electricity. However, when they are $50/tonne, the negative cost attributable to disposal could be $253,150/year, almost 20% of the revenue from electricity.

43

One solution that has been considered for removing carbon from RHA is to use a fluidised bubbling bed incinerator that would burn off the residual carbon in the RHA. A bubbling bed incinerator is estimated to have a capital cost of $315,000. Assuming that operating costs are no more than the costs to operate the basic power plant and allowing for maintenance costs of about 3% of capital cost, the annual maintenance cost would be $9450. The application of this type of unit could reduce the RHA carbon content to below 7%. This would eliminate a disposal cost of $25,315 (developing country) to $253,150 (developed country). Allowing for the maintenance costs, the potential benefit from installing the fluidised bed boiler could be $15,865/year (developing country) to $243,700/year (developed country). Based on the additional capital cost of $315,000, the number of years to recover this amount could be 20 years (developing country) to 1.3 years (developed country). The above suggests that in developing countries, where sites for RHA disposal are low cost, treating RHA from gasifiers to reduce residual carbon content is unlikely to be attractive. In developed countries, where disposal costs are high, such treatment of ash could be attractive provided there is a beneficial use for RHA with below 7% residual carbon exists. 7.3 RHA with Significant Quantity of Crystalline Silica

Combustion of rice husks, typically in stoker fired boilers, where the ash experiences sustained temperature above 750C leads to a significant quantity of crystalline silica in the resultant ash. The steel market is preferred for this type of ash. A stoker boiler power plant designed to produce 3MWe (net) will typically consume 4.11tonne/hr rice husk. This will result in 0.74 tonne/hr RHA. Over a full year of operation, 5550 tonnes of RHA will be available. The net value to the producer for RHA sold to the steel industry has been reported to fall in the range $100 to $150/tonne. Based on the mid-range value of $125/tonne, the potential revenue from producing RHA acceptable to the steel industry is $694,000/year. This could be more than 55% of the revenue stream from sales of electricity and is, therefore, an important commercial objective. There are no significant additional costs needed to achieve RHA with qualities suitable for acceptance by the steel industry. On the contrary, stoker boiler technology with over grate feeders for the fuel, and no need to pre-grind the husks, is at the low cost end of the range of equipment choices. It is wise to choose need to choose boiler suppliers who can demonstrate their track record in producing consistent quality RHA for the steel industry. This could tend to limit competition and hence introduce a hidden cost in the final price. With a typical boiler cost of about $1,200,000, it is clear that a premium of 10% to ensure RHA quality would be recovered in a few months of sales of RHA. The only other additional costs for rice husk power plant generation will be related to tests on ash samples, a higher level of quality control and probably an additional employee to handle the RHA side of the business. Clearly, with revenue from sales of potentially $694,000/year, these costs will often be no more then 10% of the revenue.

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7.4

RHA with High Amorphous Ash Content

The only technology to have achieved a good long term record in producing a high amorphous RHA uses suspension firing of pre-ground rice husk ash. Although the ground husk material can be expected to experience temperatures above 750C, the time at temperature seems to be insufficient to change the amorphous ash to crystalline form. The cost of the boiler will be similar to a stoker fired unit of the same size. The main difference will be that there is no need for a moving grate, but the fuel will be fed pneumatically using burners suited to fine particulate material. The extra cost for this approach is mainly associated with husk preparation which will require rice husk grinders. Based on a 4.11tonne/hr husk feed, as required for the generic 3MWe (net) plant, installed cost of hammer mill grinders is estimated to be $143,000. In addition to the capital cost, the grinders require considerable maintenance, including replacement screens, hammers and refurbishment of cutting plates. Based on an annual throughput of 32,500 tonne/year, the maintenance is estimated at $27,000/year. In addition, the hammer mills will consume electricity at an annual rate of 772,000kWh. Based on a value of electricity of 6US cent/kWh, the value of the electricity for grinding the husk is $46,300/year. The RHA from a plant producing predominantly amorphous ash has a net value of approximately $70/tonne (allowing $30/tonne for freight to market). On this basis the total yearly revenue from sale of the RHA from the generic plant would be $388,500. After deducting the annual cost for maintaining the hammermills and the value of electricity to run them, the remaining revenue is $315,200. Even allowing for additional work related to managing the sale of the RHA, the payback time for the additional equipment needed to produce amorphous RHA will be less than six months. 7.5 Concluding Remarks

Based on the above, the best choice would seem to be to produce RHA for the steel industry as this has the best returns. However, growth in the market for RHA to the steel market is limited. Growth in the market for RHA in the cement industry is potentially very large. For this reason, a new entrant to the marketplace may prefer to target the somewhat less high returns but better longer term prospects of the cement market.

45

8.
8.1

POTENTIAL TO EARN CARBON CREDITS

Introduction

The Kyoto Protocol is part of the UNs Framework Convention on Climate Change and has set an agenda for reducing global greenhouse gas emissions. If CO2 emissions can be shown and verified to be reduced due to different practices, then Certified Emission Reductions (CERs) can be generated. If RHA is used in concrete manufacture as a cement substitute then there is the potential to earn CERs [78]. Cement manufacturing is a major source of greenhouse gas emissions, accounting for approximately 7% to 8% of CO2 globally. There is an emerging market globally for CERs, with current prices around US$5/tonne of CO2. It is hard to predict the size and future prices within the market, but using RHA as a cement substitute can generate CERs, and one company (Alchemix) has already investigated selling these on the international market [64]. 8.2 Role of RHA in reducing GHG emissions

The cement industry is reducing its CO2 emissions by improving manufacturing processes, concentrating more production in the most efficient plants and using wastes productively as alternative fuels in the cement kiln. Despite this, for every tonne of cement produced, roughly 0.75 tonnes of CO2 (greenhouse gas) is released by the burning fuel, and an additional 0.5 tonnes of CO2 is released in the chemical reaction that changes raw material to clinker (calcination). The potential to earn CERs comes primarily from substituting Portland cement with RHA. There are other environmental benefits of substituting Portland cement with RHA. The need for quarrying of primary raw materials is reduced, and overall reductions in emissions of dust, CO2 and acid gases are attained. 8.3 Calculating the value of CERs from Portland cement substitution

The World Bank Prototype Carbon Fund provides examples of acceptable CERs from substituting Portland Cement [79]. Their guidelines have been adapted to show the potential income from CERs for the generic 3MW rice husk to energy power plant used for the Cost Benefit Analysis (Section7). A 3MW suspension fired boiler plant would typically produce 5550 tonnes annually of RHA. Assuming 50% of RHA produced is sold for cement substitution: Rice Husk Ash produced x (5555 tonne/yr) RHA sold for cement substitution (2775 tonne/yr)

50%

Emission reductions from substitution of Portland cement are calculated as totalling 1.25 tonnes of CO2 per tonne of cement substituted, derived as follows [79]: 0.75 tonnes of CO2 per tonne of cement from energy use 0.50 tonnes of CO2 per tonne of cement from calcinating limestone Thus the total annual emission reduction for cement with RHA substitution in cement is:

46

RHA sold for cement substitution x (2775 tonne/yr)

1.25 tonnes of CO2 per tonne cement

Annual Emissions (3469 tonnes CO2/yr)

Using current estimates of approximately US$5/tonne of CO2, this could provide an additional annual income stream of US$17,345. This is not significant compared to the potential income from sales to the steel market of $694,000 and to the cement market of $315,200 (Section 7.3 and 7.4), but could make a difference in a marginal project.

47

9.

CONCLUSIONS
Small markets exist for RHA in the manufacture of refractory bricks and as an oil absorbent. Potential future markets include silicon chip manufacture, the manufacture of activated carbon, and in production of lightweight construction materials and insulation. Currently the largest and most commercially viable markets appear to be in the concrete and steel industries. The market within the steel industry is well established, but there are constraints to the expansion of this market due to health issues associated with using crystalline ash. The cement markets are not as well developed as steel, but there is great potential for the use of amorphous RHA in this area. Two main issues appear to be limiting its use: lack of awareness of the potential for RHA and the quality of the product itself. Boiler modifications may be required to produce ash of the quality required. The best choice seems to be to produce RHA for the steel industry as this requires no boiler modifications and attracts a high price. However growth in the market for RHA to the steel market is limited. Growth in the market for RHA in the cement industry appears to be growing and is potentially very large. A new entrant to the market place may prefer to target the somewhat less high returns but better longer term prospects of the cement market.

48

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53

ACKNOWLEDGEMENTS
Bronzeoak would like to acknowledge the assistance of Charoen Lertrushtakorn, Patum Rice Mill, Bangkok, Thailand and Prasong Limsirichai, Fortum Engineering, Bangkok, Thailand for providing ash samples for analysis. The Geology Department, University of Leicester carried out the X Ray Diffraction analyses and Minton Treherne and Davies Ltd the other analyses. Dr Nandini Dasgupta and Stephen Graham (Greenwich University) provided data and useful background information.

54

APPENDIX A

A55

Determinant % unless otherwise stated

N.P.Singhania Analysed by Siam City Cement Plc, http://ricehuskash.ebifchina.com Saraburi Province, Thailand. Source, [11].

F. Preto Energy Research Laboratories, energy Mines and Ron Bailey Jr. Producers Rice Mill Resources, Canada Energy Systems Inc. +1 (501)767-2100 gasifier Sand fluidised bed, depth range 0.3-0.6m. Temp 650-900oC, fluidising velocity 0.4-2.2m/s, excess air levels 30-95%. Combustion efficiency>97% bottom ash (except where indicated to be fly ash, see below) 0.25 97.55 97.6 (in the fly ash) 0.00 0.19 0.59 0.00 0.44 0.11 -

Reference [67]. Year of analysis 1870

Boiler details Bottom/fly ash? pH SiO3 SiO2 (Total) SiO2 Amorphous SiO2 Crystalline Al2O3 Fe2O3 FeO2 CaO MgO P2O5 Na2O K2O TiO2 CI L.O.I Fixed Carbon Total Carbon Carbon Size Specific gravity Colour Bulk density Additional analysis Notes 8.1 88.65 0.16 88.4 4.90 (FeO3) 0.30 0.89 0.96 0.10 0.10 0 1.56 500 mesh 5 grey Sold to steel industry 0.18 89.29 0.54 2.45 1.09 0.18 0.03 2.43 0.01 3.67 99.65% passed through #325 sieve 2.082 grey 0.39gm/1 MnO 0.13 Blaine Fineness 7684cm2/gm

90-98 -

0.42 93.21 0.45 0.51 0.07 2.69 0.3 1.53 0.15 -

A56

1-4 (fly ash) Ash melting temperature 1400oC Boiler can be operated to Range of operating conditions in experimental circumstances. achieve SiO2 amorphous Only one result of chemical composition recorded as below. content

Determinant % unless otherwise stated Boiler details

Reference Reference Refernce Refernce [67]. Year of analysis Refernce Refernce [67]. [67]. Year [67]. Year of [67]. Year 1928 [67]. Year Year of analysis of analysis analysis 1916 of analysis of analysis 1952 1871 1925 1933 -

Refernce Refernce [67]. [67]. Year Year of analysis of analysis 1970 1966

B Foutnier International Centre for Sustainable Development of Cement & Concrete (CANMET), Canada Torbed Reactor. Gas and combustion kept at a steady 830C and ash kept below this temp. Assumed fly ash since TORBED reactor will produce all fly ash. 0.1 (XRD) 90.7 At most, minor cristobalite 0.4 0.4 0.4 0.5 0.4 0.1 2.2 0.03 4.7 8.3 m (mean) 2.05 -

Bottom/fly ash? pH SiO3 SiO2 (Total) SiO2 Amorphous SiO2 Crystalline Al2O3 Fe2O3 FeO2 CaO MgO P2O5 Na2O K2O TiO2 CI L.O.I Fixed Carbon Total Carbon Carbon Size Specific gravity Colour Bulk density Additional analysis Notes 87.71 0.54 1.01 1.96 0.57 1.58 -

Assumed to be bottom ash 96.97 0.57 0.12 0.57 0.58 -

97.3 0.38 0.43 1.44 1.13 94.50 Trace 0.25 0.23 0.53 0.78 1.10 Trace -

95.49 0.94 0.86 0.28 0.36 1.88 -

0.40 96.62 0.32 0.76 0.0 1.59 0.42 -

96.20 0.24 0.24 0.46 0.79 -

0.1 91.16 0.21 0.65 0.99 4.75 -

A57

Determinant % unless otherwise stated Boiler details Bottom/fly ash? pH SiO3 SiO2 (Total) SiO2 Amorphous SiO2 Crystalline Al2O3 Fe2O3 FeO2 CaO MgO P2O5 Na2O K2O TiO2 CI L.O.I Fixed Carbon Total Carbon Carbon Size Specific gravity Colour Bulk density Additional analysis Notes

Reference [80]

Asian Institue of Technology, Bangkok, Thailand Cyclonic suspension combustion technology. Steam flow 21,000lbs/hr at Travelling grate stoker with pneumatic spreaders made Simple incinerator in Japan. 60psig and 250F. 0.14 >90 <1 <0.01 0.032 0.60 0.37 0.92 0.14 2.3 <0.01 4 to 6 black/grey 288kg/m3 NnO 0.12 Husks are pre-ground at the adjacent mill. Unburned carbon 2-7 moisture 3% maximum Boiler code JTS B-8201. Designed for 50 bar, superheater outlet steam at 405oC, gas -air heater outlet at 210oC and 27oC at steam-air heater outlet. 90% minimum 0.03 90.40 1.01 2.78 1.31 0.28 0.78 2.40 3.54 2.17 3.16 Blaine Fineness 16,976 cm2/g

Charles Weiss Agrielectric

Denthep Theppratuangthip

Assumed to be bottom ash bottom and fly ash used 96.01 0.96 0.08 0.3 0.28 0.88 0.06 0.96 -

A58

Determinant % unless otherwise stated

Asian Institute Reference [25] of Technology, Thailand

Department of Mineral Department of Mineral Science, Turkeyen, Science, Turkeyen, Guyana [20] Guyana [20]

Department of Mineral Department of Mineral Science, Science, Turkeyen, Turkeyen, Guyana [20] Guyana [20] 7 hour burn 94.26 0.91 0.17 0.52 0.04 0.72 3.27 white other elements 3.38 5 hour burn 94.12 0.69 0.17 0.7 0.0 0.84 3.1 light grey other elements 3.44

Boiler details Bottom/fly ash? pH SiO3 SiO2 (Total) SiO2 Amorphous SiO2 Crystalline Al2O3 Fe2O3 FeO2 CaO MgO P2O5 Na2O K2O TiO2 CI L.O.I Fixed Carbon Total Carbon Carbon Size Specific gravity Colour Bulk density Additional analysis

bottom ash 0.18 92.28 0.18 0.03 3.67 2.082 Moisture 0.67 Blaine Fitneness 7684 (cm2/g)

gasifier bottom ash 'practically' amorphous -

5 hour burn 88.04 0.1 0.26 0.69 0.3 2.5 6.42 light grey other elements 8.11

7 hour burn 94.55 1.22 0.17 0.52 0.05 0.62 2.71 off-white other elements 2.87

A59

Notes

Burnt at approx 900oC followed by retention for approx 1-11/2 hours at 500-600oC.

Determinant % unless otherwise stated Boiler details

Department of Mineral Science, Turkeyen, Guyana

Government Industrial Research Institute, Kyushu, Japan

P.K. Mehta [31]

P.K. Mehta [31]

P.K. Mehta [20]

Bui and Stroeven

Fluidised bed. Temp of combustion controlled by feed rate not air velocity (which is fixed at 15cm/s) 5 hour burn 91.04 fly ash 91.69 100 0.14 0.06 0.58 0.26 0.52 0.09 2.54 0.01 -

Bottom/fly ash? pH SiO3 SiO2 (Total) SiO2 Amorphous SiO2 Crystalline Al2O3 Fe2O3 FeO2 CaO MgO P2O5 Na2O K2O TiO2 CI L.O.I Fixed Carbon Total Carbon Carbon Size Specific gravity Colour Bulk density Additional analysis Notes

91.3 (XRD) 100 <0.1 <0.1 0.5 0.5 2.1 -

93.00 (XRD) 99 (XRD) 1 <0.1 <0.1 0.3 0.4 0.50 -

62.5 (XRD) 90 (XRD) 10 <0.1 <0.1 0.2 0.3 0.1 -

Eperimental laboratory oven 96.7 0.08 0.03 0.30 0.16 0.73

0.77 0.17 1.00 0.04 0.84 -

A60

4.18 4.9 5.5 35 5.8 off white other elements 6.14 These results taken from ash left Analysis from US Analysis from US Analysis from US Data is average from preheating smouldering on a heated plate for a few Patent 4,105,459.1978 Patent 4,105,459.1978 Patent 4,105,459.1978 at 150C then 600C for 10 minutes then heated to 600C for 15 hours and 900C for 15 hours. mins.

Contact Name: Charoen Lertrushtakorn Company Details: Patum Rice Mill and Granary Public 88 MOO 2 Tivanont Pathumthani Bangkok Thailand Ash type (bottom/fly?): Bottom Ash Details of Boiler type: Fixed Grate Yoshimine Boiler, moisture between 14-20%, outlet steam 18bars, 360C. They have 2 boiler sizes, 35 and 20 tonnes. Additional Details: Analysed on behalf of Bronzeoak Ltd. Ash Analyses normalised to 100% Determinant pH SiO3 SiO2 (Total) SiO2 Amorphous SiO2 Crystalline Al2O3 Fe2O3 FeO2 CaO MgO P2O5 Na2O K2O TiO2 Cl L.O.I. Fixed Carbon Total Carbon % (unless otherwise stated) 10.5 95.36 32 61 cristobalite 4 quartz 0.18 0.16 0.70 0.36 0.46 0.41 1.95 0.01 0.03 4.1 3.0 Analytical technique (if known) 1:2 water extract ICPMS ICPMS XRD XRD ICPMS ICPMS ICPMS ICPMS ICPMS ICPMS ICPMS ICPMS ICPMS ICPMS ICPMS

SIZE MM SQ/HOLE
+2.36 +2.00 +1.18 +0.60 +0.425 +0.30 +0.212 +0.150 +0.063 Passing 0.063 0.1 0.1 2.0 24.6 24.5 15.1 11.3 7.7 9.5 5.1

specific gravity colour

BULK DENSITY
Loose poured Vibrated compacted Additional Analyses Moisture SO3 MnO2 156 211 239

0.5 0.33 0.08

- = no analysis ICPMS Inductively Coupled Plasma Mass Spectrometer

A61

Contact Name: Prasong Limsirichai Company Details: S.T. Fortum Engineering Co., Ltd. 5th Floor SP Building 388 Phaholyothin Rd Bangkok 10400 Thailand +662 273 0037 ext. 104 Prasong.limsirichai@fortum.com Ash type (bottom/fly?): Fly Ash Details of Boiler type: Circulating Fluidized Bed Boiler, 35t/hr of Chinese make. 399bar.g at 450C. FD fan 4.1375m3/s, ID 14.77m3/s. Cyclonic ash removal system. Additional Details: Analysed on behalf of Bronzeoak Ltd. Ash analysis normalised to 100%

Determinant pH SiO3 SiO2 (Total) SiO2 Amorphous SiO2 Crystalline Al2O3 Fe2O3 FeO2 CaO MgO P2O5 Na2O K2O TiO2 Cl L.O.I. Fixed Carbon Total Carbon Size (mm sq/hole) +2.36 +2.00 +1.18 +0.60 +0.425 +0.30 +0.212 +0.150 +0.063 Passing 0.063 specific gravity colour

% (unless otherwise stated) 11 94.29 46 33 cristobalite 20 quartz 0.61 0.24 0.67 0.35 0.79 0.27 2.25 0.03 0.04 2.2 0.5

Analytical technique (if known) 1:2 water extract ICPMS ICPMS XRD XRD ICPMS ICPMS ICPMS ICPMS ICPMS ICPMS ICPMS ICPMS ICPMS

Nil Traces 0.1 0.2 1.9 6.6 14.2 28.7 43.8 4.5 -

BULK DENSITY (KG/M3)

loose poured vibrated compacted Additional Analyses moisture SO3 MnO2 404 473 483

0.2% 0.37 0.13

Loss at 105C

- = no analysis

A62