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International Journal of Food Science and Technology 2008, 43, 958988

Original article Corn and rice waste: a comparative and critical presentation of methods and current and potential uses of treated waste
Ioannis S. Arvanitoyannis1* & Persefoni Tserkezou2
1 Department of Animal Production and Aquatic Environment, School of Agricultural Sciences, University of Thessaly, Fytokou Street, 38446 Nea Ionia, Magnesias, Volos, Hellas (Greece) 2 Department of Crop Production and Agricultural Environment, School of Agricultural Sciences, University of Thessaly, Fytokou Street, 38446 Nea Ionia, Magnesias, Volos, Hellas (Greece) (Received 1 July 2006; Accepted in revised form 12 January 2007)

Summary

Although corn and rice waste can be hardly classied among the most hazardous waste, their treatment is very important in view of the great volume of waste materials involved. In this review article, an update is provided for most of the waste treatment techniques (composting, pyrolysis, gasication, combustion) used to alter the physical, chemical or biological character of the waste, to reduce its volume and or toxicity and to make the waste safer for disposal. Furthermore, all current and potential uses of treated corn and rice waste such as fertilisers, biomass and biogas biofuel are summarised. Four comprehensive tables and six gures provide a thorough presentation of both waste treatment methods (characteristics, advantages and disadvantages) and uses of treated corn and rice waste.
Biogas, biomass, combustion, composting, gasication, pyrolysis, rice waste, uses of treated corn waste, waste treatment techniques.

Keywords

Introduction

Cereal crops are mostly grasses cultivated for their edible seeds (actually a fruit called a caryopsis). Cereal grains are grown in greater quantities worldwide than any other type of crop and provide more food energy to the human race than any other crop (http:// en.wikipedia.org/wiki/Grains). Cereals have been part of the human diet since prehistoric times (http:// www.nutrition.org.uk/upload/Cereals%20pdf.pdf). In some developing nations, cereal grains constitute practically the entire diet of common folk. In developed nations, cereal consumption is more moderate but still substantial. The word cereal has its origin in the Roman goddess of grain, Ceres (http://en.wikipedia.org/wiki/Grains). Wheat and rice are the most important crops worldwide as they account for over 50% of the worlds cereal production. In the UK, wheat is the cereal, most commonly used for the manufacture of food products, although many other types of cereals (e.g. maize and barley) are used. Each cereal has unique properties which make it suitable for a variety of food products (http://www.nutrition.
*Correspondent: Fax: +302421093157; e-mail: parmenion@uth.gr

org.uk/upload/Cereals%20pdf.pdf). The starchy carbohydrates which are provided by cereals are essential in human nutrition. Rice is a staple diet for half of the worlds population, the remaining half cultivate the other cereals depending on climate and soil (http:// www.geocities.com/napavalley/6454/cereals.html). Today cereals provide a very signicant proportion of both human and animal diets despite the fact that most grains are to a greater or lesser extent decient in a number of essential nutrients. A primary problem is the low level of essential amino acids such as lysine, methionine and threonine in the major cereal storage proteins (http://www.agrsci.dk/afdelinger/forskningsafdelinger/gbi/grupper/molekylaer_genetik_og_bioteknologi/ cereals). The seven principal cereals grown in the world are wheat, rice, maize, barley, sorghum, oats, rice and rye. Globally, maize is the rst-largest cereal crop, the second being wheat and the third being rice (http:// en.wikipedia.org/wiki/Wheat). Maize (or corn, Zea mays) is a cereal grain that was domesticated in Mesoamerica. It is called corn in the United States, Canada and Australia, but in other countries that term may refer to other cereal grains (http://en.wikipedia.org/wiki/Maize). Hybrid maize is favoured by farmers over conventional varieties for its

doi:10.1111/j.1365-2621.2007.01545.x
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high grain yield. It may be processed to make many dierent ingredients (e.g. high fructose corn syrup which can be used as an alternative to sucrose derived from sugar cane and sugar beet) and food products. Its germ is rich in oil and can be rened to produce corn oil (http://www.nutrition.org.uk/upload/Cereals%20pdf.pdf). Finally, maize is one of the rst crops for which genetically modied varieties make up a signicant proportion of the total harvest. Rice is a dietary staple of more than half of the worlds human population (most of Asia and Latin America), making it the most consumed cereal grain. Rice cultivation is well suited to countries and regions with low labour costs and high rainfall, as it is very labour-intensive to cultivate and requires plenty of water for irrigation. However, it can be grown practically anywhere, even on steep hillsides. Rice is the worlds third largest crop, behind maize (corn) and wheat (http://en.wikipedia.org/wiki/Rice). Brown rice has its outer husk removed, and white rice is milled and polished further to remove the bran and germ. There are many dierent types of rice, categorised by size, shape and the region where they are grown. Rice can be ground to make our and is used to make Japanese rice wine (http://www.nutrition.org.uk/upload/Cereals% 20pdf.pdf). The aim of this work was to make a comparative and critical presentation of corn and rice waste treatment methods in an attempt to disclose the most eective and low cost methods. The treatment methodologies of corn and rice wastes are summarised in Tables 1 and 2, respectively, whereas the chemical analysis of corn stalk, corn cob and rice straw is given in Table 3. Moreover, other main issues which are the current and potential uses of treated corn and rice wastes are summarised in comprehensive Table 4.
Waste treatment methods

Waste treatment techniques are used to alter the physical, chemical or biological character of the waste, to reduce its volume and or toxicity, and to make the waste safer for disposal. Waste treatment may be required for radioactive, hazardous and other Department of Energy (DOE) wastes. Mixed wastes (which contain both hazardous and radioactive components) pose special management challenges as they are dicult to treat with existing treatment technologies (http:// web.em.doe.gov/em30/wasttrea.html). The following are examples of waste treatment technologies or practices. Biological treatment usually involves treatment of waste by bacteria, fungi or algae to remove and degrade the hazardous constituents. Boiler is a type of device that can be used to treat hazardous waste. Boilers use controlled ame combustion and recover thermal energy in the form of steam or heated

gases (http://www.epa.gov/epaoswer/osw/treatech.htm). Methods of treatment in which the application of physical forces predominate are known as unit operations. Methods of treatment in which the removal of contaminants is brought about by chemical or biological reactions are known as unit processes (Tchobanoglous et al., 2003). The preferred use for surplus straw is as fuel in a suitable on-farm boiler, providing heat for hot water, buildings and grain drying and other operations, thus cutting energy bills and avoiding ploughing-in costs (http://www.bia.co.uk/les/pdfs/MassBalance_ Agriwastes_08_Treatment.pdf). Carbon adsorption uses activated carbon to adsorb hazardous waste constituents. Gaseous and aqueous waste streams can be treated by carbon adsorption. Chemical oxidation: uses strong oxidising agents (e.g. hypochlorite, peroxides, persulfates, percholorates, permanganates, etc) to break down hazardous waste constituents to render them less toxic or mobile (http://www.epa.gov/epaoswer/osw/treatech. htm). Treatment methods are selected based on the composition, quantity, and form of the waste material. Some waste treatment methods are prescribed by regulations and DOE Orders; other treatment methods are being developed for specic wastes. Waste treatment methods being used today include solidication (e.g. calcining and vitrication) and volume reduction (e.g. incineration, compaction and sizing). There are two principal types of biological sewage treatment: (a) the percolating lter (also referred to as trickling or biological lter, (b) activated sludge treatment. Both types of treatment utilise two vessels, a reactor containing the microorganisms which oxidise the BOD and a secondary sedimentation tank, which resembles the circular radial ow primary sedimentation tank, in which the microorganisms are separated from the nal euent (Harrison, 2001). Solidication processes such as calcining and vitrication can be used to treat non-solid radioactive waste. DOE processing plants take liquid waste or semi-solid sludge and convert it to a solid waste form that can be safely disposed in a geologic repository (http://web.em. doe.gov/em30/wasttrea.html). Solidication is a method for mixing of cement, y ash from the incinerator and waste lter cake from the physico-chemical treatment to form a virtually insoluble mass (http://www.zazemiata.org/bw/radnevo/resume_ovos_en.pdf). Extraction is a process that removes hazardous constituents from either gaseous or liquid waste streams by means of settling, ltration, adsorption, absorption, solvents or other means. Although the extracted hazardous constituents are removed from the waste stream, they usually must be treated further to render them less toxic. Incineration is the high temperature burning (rapid oxidation) of a waste, usually at 8701370 C. It is also known as controlled-ame combustion or calcination

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Table 1 Treatment methodologies of corn wastes; Parameters, Quality control methods and Results
Parameters Changes characteriza-tion in C and N isotope during composting Compost pH measured in a 1:2 slurry of 25 g compost and water Composting Changes in carbon, nitrogen, d13 C and d14 N content during composting Highly recalcitrant composts with prolonged C storage in non-mineral soil fractions. The sensitivity of the natural abundance tracer technique to characterise their fate in soil improves during composting, as a more Methodology Quality control methods Results References Lynch et al. (2006)

Kind of waste

Treatment

International Journal of Food Science and Technology 2008


Chemical activation with zinc chloride (ZnCl2) for producing high surface area carbons with ZnCI2 activation The temperature of 500 C was found to be the optimal condition Pyrolysis Zink chloride activation homogeneous C isotope signature develops, in addition to the relatively large amounts of stable C applied in composts Activated carbons yield varied in the range of 2730.4%. The surface areas of the resulting activated carbons, increased rapidly with impregnation ratio of ZnCI2 The ZnCI2 activation of corn cob was suitable for the activated carbons preparation microporous. Flash pyrolysis Plasma heated laminar entrained ow reactor Thermolysis Yields of volatile pyrolysis products depended on the nal pyrolysis temperature and residence time Shuangning et al. (2005) Tsai et al. (1998) Thermogravi-metric analyzers (TGA) were one of the main techniques used in analyzing the characteristics Materials are rapidly heated to high temperatures in the absence of air (oxygen) of solid fuel volatilisation at low heating rates TGA were one of the main techniques used in analyzing the characteristics of solid fuel volatilisation at low heating rates The heating process consists of fast sample heating (2570 K s)1) to the desired temperature Pyrolysis kinetics The ratio between the conversion and heating time varied from a maximum of about 1050 (low temperatures) to a minimum of about 65 (high temperatures) with the corresponding solid mass fraction at the beginning of the true isothermal stage equal to 0.99 and 0.75. The weight loss curves obtained for corn stalks have the same qualitative behaviour as wheat straw Lanzetta & Di Blasi (1998)

Corn waste

Composting

Current and potential uses of treated waste I. S. Arvanitoyannis and P. Tserkezou

Corn cob waste

Chemical activation

Corn stalk waste

Pyrolysis

2007 The Authors. Journal compilation 2007 Institute of Food Science and Technology Trust Fund

Corn straw waste

Pyrolysis

Table 1 (Continued)
Parameters H2, CH4, CO, CO2 and C2H2 (for analysis), Pyrolysis Gas chromatography Mass spectrometry higher the temperature, the greater the yield of emitted gases and lesser the amount of the liquid and the solid residue Beyond 400 C, only a part of the components decomposed and exhibited a slower weight loss The analytic semi-empirical model provides a simple and useful way of distilling the essence of the observed thermo-chemical response of corn stover to temperature and heating rate Comparison of physical characterisations of the carbon products with those of commercial activated carbons indicates that the activated carbons prepared from agricultural waste corn cob by using a cleaner process is an available route for the biomass utilisation and bioresource recycling. The high-surface-area carbon products obtained were very promising Green & Feng (2006) The experiments showed the CH4, C2H6, C3H8 and C3H6 (for ame ion detector, FID) the reactor, then nitrogen passed through the reactor with a ow of 80 mL min)1. The reactor is heated to 110 C at a heating rate of 10 K min)1 and held the temperature for 1 h in order to remove the water Corn stover, the leaves and stalks that are usually left in the eld after corn harvest, can serve as a representative biomass feedstock Pyrolysis The corn cob was rst placed in Methodology Quality control methods Results References Cao et al. (2004)

Kind of waste

Treatment

Corn cob waste

Pyrolysis

Corn stover waste

Pyrolysis

Analytical system to the determination of yield parameters apart from H2O, CO, CO2 and H2, the products were divided into family groups, e.g. parafns, olens, alcohols, aromatics etc. Under the experimental conditions in the activation temperature ranges of 500800 C with less pollution characteristics of KOH: True density and porosity increase with increase in the activation temperature Gasication of corn cob K2CO3) as chemical agents

2007 The Authors. Journal compilation 2007 Institute of Food Science and Technology Trust Fund Tsai et al. (2001a) KHCO3 was added to the mixture of starch and water before the formation of the gel The inuence of pressure, temperature, residence time and alkali addition on the gasication of corn starch Gasication of corn starch adsorbents for pollution control and for other applications An increase in temperature improved the biomass conversion. Longer residence time showed an improvement in gasication yield DJesus et al. (2006) KOH and K2CO3 were effective activating agents or chemical activation during a period of 10 C min)1. Subsequent gasication at a soaking period of 800 C Gasication Pyrolysis until a maximum was reached. Gas composition changed with residence time and temperature. Potassium addition affected the gasication yield of corn starch. The porosity created in the acidunwashed carbon products is substantially lower than that of acid-washed carbon products because of potassium salts left in the pore structure Tsai et al. (2001a)

Corn cob waste

Gasication

Corn starch waste

Gasication

Corn cob waste

Chemical and

Current and potential uses of treated waste I. S. Arvanitoyannis and P. Tserkezou

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physical activation

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962

Table 1 (Continued)
Parameters Removal of carbon from fossil fuels prior to use in Corn renery industry produces a wide range of products Biomass combustion Gasication combustion energy could be possible in the future. Biological systems can already be tailored to produce fuels such as hydrogen. Policy drivers for increased use of biomass for energy and Green plants developed to produce desired products and including starch-based ethanol fuels for transportation nergy production is likely to be far less costly than attempting to remove CO from dispersed sources Methodology Quality control methods Results References Chum & Overend (2001)

Kind of waste

Treatment

Corn waste

Combustion and gasication

International Journal of Food Science and Technology 2008


Engine power performance, fuel consumption and emissions (CO2, CO, HC and NO) have been studied Temperature range from 110 to 220 C Combustion biobased products are reviewed for their potential contributions for a carbon constrained world No signicant difference in performance between diesel fuel and mixed fuel. The mixed fuel operation produced low fuel consumption at the various loading. Mixed fuel with 11.7% and 6.6% oil-economising rate, had better oil-economising compare to diesel fuel, respectively. Zhang & Wang (2006) Calcium, Cu, K, Mg, Na, P, S and Zn were recovered with the bomb washings The procedure involves sample combustion in a commercial stainless steel oxygen bomb operating at twenty-ve bar Combustion Inductively coupled plasma optical emission spectrometry The mixed fuel showed signicant improvement at CO2 emissions Most of the element recoveries in the samples varied between 91% and 105% and the certied and determined contents exhibited a fair agreement at a 95% NIR spectroscopy Combustion condence level. NIR spectroscopy showed (a) a rapid drop in soluble glucan, (b) increase in lignin and (c) increase in xylan. As product yield in fermentation-based biomass conversion processes is proportional to the structural carbohydrate content of the feedstock, timing of stover collection and the proportion of anatomical fractions collected affect the quality of corn stover as fermentation feedstock Souza et al. (2002) The fertilisation consisted of 168 kg N, and 90 kg each of P2O5 and K2O equivalents To minimise the effect of water in the biomass spectra, each sample was air-dried to less than 10% moisture prior to NIR spectroscopic analysis Pordesimo et al. (2005)

Current and potential uses of treated waste I. S. Arvanitoyannis and P. Tserkezou

Corn cob and corn tar waste

Combustion

Corn waste

Combustion

2007 The Authors. Journal compilation 2007 Institute of Food Science and Technology Trust Fund

Corn stover waste

Combustion

Table 1 (Continued)
Parameters Control of HC, CO, NOx Biodiesel The two types of biodiesel appeared to have equal performance and irrespective of the raw material used for their production, their addition to the marine diesel fuel improved the particulate matter, unburnt hydrocarbons, nitrogen oxide and carbon monoxide emissions. The NOx emissions were reduced The engine was fuelled with pure marine diesel fuel and blends containing two types of biodiesel, at proportions up to 50%. Kalligeros et al. (2003) Methodology Quality control methods Results References

Kind of waste

Treatment

Corn oil

Biodiesel

Corn waste Biodiesel Ethanol production

Ethanol and biodiesel production

Production of 1000 L of ethanol from corn

Under relatively high prices for gasoline the costs for using ethanol and biodiesel are much higher per equivalent litre of gasoline

in all cases when the two biodiesel containing fuels were used. Either the costs for generating ethanol or biodiesel have to be reduced substantially, by e.g. technical change or the price for oil has to increase

Wesseler (2007)

Corn stover waste

Biodiesel and bioethanol harvesting corn stover lignin rich fermentation residues from corn stover are utilised to generate electricity and steam, which are used in the ethanol production system

2007 The Authors. Journal compilation 2007 Institute of Food Science and Technology Trust Fund Soil nitrogen-related burdens (e.g. N2O, NOx, NiO3) would be reduced by When corn stover is harvested, ethanol is produced from both corn stover and corn grain and Biodiesel Bioethanol further before ethanol and biodiesel will become economically competitive Corn stover removal would reduce soil organic carbon accumulation rates, but cultivation of winter cover crops, even with corn stover removal, could increase soil organic carbon accumulation rates because of increased carbon inputs from winter cover crops. Utilisation of corn stover and winter cover crops can improve the Pyrolysis Gas chromatography Mass spectrometry eco-efciency of the cropping systems Differential thermogravimetric analysis showed that thermal decomposition process involves two steps. The heating rate affects both the activation energy of the decomposition reaction, but also the path of the reaction. The maximum rate temperature of the decomposition reaction shifted to a higher temperature, and the order and activation energy of the total decomposition reaction decreased. Cao et al. (2004) Kim & Dale (2005) The gas products were analyzed by gas chromato-graphy (GC) as CO2, CO, H2, CH4, C2H4, C3H6, C3H8, etc. The temperature was 350400 C

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Corn cob waste

Pyrolysis

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964

Table 1 (Continued)
Parameters Diene hydro-peroxide con-centration and a-tocopherol concentration as analytical indicators Corn oil stored at 60 C Antioxidative extract Gas chromatography The stabilisation of stripped corn oil, free from any genuine antioxidant, proves the occurrence of class I antioxidants generated during roasting. Methodology Quality control methods Results References Krings et al. (2000)

Kind of waste

Treatment

Corn oil

Chemical method

Corn waste 7.27.5 for about 40 days and M. phlei Methanogenesis In situ remediation

International Journal of Food Science and Technology 2008


pH was maintained around Mycobacterium smegmatis Anaerobic fermentations Protection of genuine a-tocopherol in corn oil indicates the presence of class II antioxidants which are able to protect or to regenerate a-tocopherol Bioremediation that includes anaerobic fermentations of wastes to produce methane and hydrogen, the genetics of methanogenesis and in situ remediation of contaminated aquifer systems, landll leachates and industrial efuents Land application of fermentation byproducts and their use in animal feeds. Biocatalytic studies of transformations of components of corn Biochemical reactions for the production of de-icers from industrial water streams, biodiesel production from fats and greases, biodegradable plastics from polymerizable sugar derivatives, single cell foods derived from fungal growth on waste streams, and bacterial polysaccharides from Erwinia species Montgomery (2004) In chemical activation, the precursor materials are impregnated with chemical agents such as ZnCl2 and H3PO4 to inhibit the formation of chars and enhance the yield of the resulting activated carbon The higher activation temperature can overcome the drawbacks of a longer period of activation required to attain larger surface area and can offer higher potential to produce activated carbon of greater adsorption capacity from agriculture wastes such as corn cobs Burn-off in gasifying agents and at 800 and 900 C. Steam activation Separation and recovery of components by membrane technologies BET surface areas of activated carbons after about 71 and 59 wt% burn-off of CO2 and steam activations at 900 C were 1705 and 1315 m2 g)1, respectively, indicating high adsorption capacities. Production of high-quality microporous activated carbon from corn cob agrowaste using N2 carbonisation followed by physical activation with CO2 or steam Chang et al. (2000)

Current and potential uses of treated waste I. S. Arvanitoyannis and P. Tserkezou

Bioremedation

2007 The Authors. Journal compilation 2007 Institute of Food Science and Technology Trust Fund

Corn cob agrowaste

Chemical activation

Table 1 (Continued)
Parameters The corn husks were passed through a Hobart chopper, blended with 1.25 M NaOH (20 g per 100 mL) An enzyme preparation derived from Aspergillus niger and Trichoderma reesei Enzymatic saccharication of corn husks The products of the enzymatic reaction were identied as glucose, cellobiose, xylobiose, arabinose and xylose Hang & Woodams (1999) Methodology Quality control methods Results References

Kind of waste

Treatment

Corn husks waste

Enzyme preparation

Corn cobs waste Enzymatic saccharication of corn cobs and Trichoderma reesei.

Enzyme preparation

Pretreated with NaOH, followed by 48 h of reaction at 50 C and pH 5

An enzyme preparation derived from Aspergillus niger

Increasing the concentration of corn husks in the reaction mixture adversely affected the production of total and individual soluble sugars The products of the enzymatic reaction were identied as glucose,

Hang & Woodams (2001)

Corn cob waste Enzyme determination Protein determination NRRL 6361 and Coriolus versicolor NRRL 6102

Biodegradation

The optimum pH for cellulase production was found to be 5.5

Phanerochaete chrysosporium NRRL 6359, P. chrysosporium

cellobiose, xylobiose, arabinose and xylose. Increasing the concentration of corn husks in the reaction mixture adversely affected the production of total and individual soluble sugars Phanerochaete chrysosporium NRRL 6359 was selected as a better producer for release reducing sugars The highest levels of xylanase, glucanase and cellulase were detected in culture P. chrysosporium NRRL 6359 after 48 h

Abd El-Nasser et al. (1997)

2007 The Authors. Journal compilation 2007 Institute of Food Science and Technology Trust Fund Corn stover transported by pipeline at 20% solids concentration (wet basis) or higher could directly enter an ethanol fermentation plant Heat loss in a 1.26 m pipeline carrying 2 M dry tonnes year)1 is about 5 C at a distance of 400 km in typical prairie clay soils Saccharication of corn stover Transport of corn stover in multiple pipelines offers the opportunity to develop a large ethanol fermentation plant, avoiding some of the diseconomies of scale that arise from smaller plants whose capacities are limited by issues of truck congestion. Kumar et al. (2005) The enzymatic hydrolysis was carried out using citrate buffer (50 raM, pH 4.5) at 5253C for different time intervals. Use of Apergillus sp. Enzymatic hydrolysis The hydrolysis products wereanalysed by HPLC Saccharication in the pipeline would reduce the need for investment in the fermentation plant, saving about 0.2 cents L of ethanol. Xylose was found to be the major end product with traces of xylobiose and xylotriose at the beginning of hydrolysis. Corn cob powder showed lower extent of hydrolysis when treated with higher enzyme concentrations for longer periods of time. Gamma radiation After the heat radiation treatment, succession of the residual microorganism in the compost could inuence the bioconversion of the substrate to utilizable nutrients for the mushroom development. Pleurotus ostreatus and P. eous are macrofungi which utilise polysaccharides Gbedemah et al. (1998) Gokhale et al. (1998) Gamma irradiation of corn stover in combination with sodium hydroxide for bioconversion of polysac-charide into protein by Pleurotus sp.

Corn stover waste

Chemical activation

Corn cob waste

Hydrolysis

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Corn stover waste

Radiation

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Table 1 (Continued)
Parameters The usual commercial choices of activation gas are steam, CO2, air or their mixtures CO2 and O2 Temperature control for the reactor consisted of a three-zone temperature control system Physical activation Methodology Quality control methods Results Both the surface area and the nature of porosity were signicantly affected by the conditions of activation, the extent of which depended on the nature of the precursors. The higher the activation temperature, the greater are the surface areas and micropore volumes of the resultant activated carbons. Various precursors were affected differently by the duration of activation. For oak, the longer the duration References Zhang et al. (2004)

Kind of waste

Treatment

International Journal of Food Science and Technology 2008


Chemically activated method with solution of KOH and soap which acted as surfactant The temperature is between 450 and 850 C Chemical method of activation, the greater the adsorption capacity of resultant activated carbons, and vice versa for corn hulls and corn stover. The specic surface area of activated carbon from corn cobs reached 2700 m2 g)1. And the addition of the soap as surfactant may shorten the soaking time. The structure of the activated carbon prepared had narrow distribution of pore size and the micro-pores accounted for 78%. Easy and feasible method Cao et al. (2006)

Current and potential uses of treated waste I. S. Arvanitoyannis and P. Tserkezou

Corn hull and corn stover waste

Physical activation

2007 The Authors. Journal compilation 2007 Institute of Food Science and Technology Trust Fund

Corn cob waste

Chemical activation

Table 2 Treatment methodologies of rice wastes; parameters, quality control methods and results

Kind of waste Parameters The composts reached maturity in 90 days. nomic performance of faba bean using locally available recycled organic materials. The total organic C concentration declined slightly for all mixtures during composting. Compost N increased with increasComposting Benet of compost without chemical fertiliser demonstrated the validity and possibility of sustainable agroMethodology Results References

Treatment

Quality control methods

Rice straw total C and CEC)

Composting

pH 7, the addition of compost (20200 g pot)1) improved selected soil chemical (increased total N,

Abdelhamid et al. (2004)

Rice straw Psychrophilicand mesophilic microorganisms Anaerobic composting

Composting

Total Kjeldahl nitrogen (TKN), total organic carbon (TOC) and organic matter (OM) and humic substance(HS)

ing amounts of oilseed rape cake and poultry manure in the feedstocks. As a result of biodegradation of organic compounds, the temperature increased and reached 4050 C. pH tended to be stable

Zhu (2007)

2007 The Authors. Journal compilation 2007 Institute of Food Science and Technology Trust Fund Aspergillus sp. Composting and appeared to be consistent in all the composts. Organic nitrogen supplementation showed a higher enzyme production compared with inorganic source. Optimum enzyme activity Anto et al. (2006) 1, FeSO4 7H2O 0.02,K2HPO4 1.4 and KH2PO4 0.6, in 250 ml Erlenmeyer asks initially maintained at pH 7. The respiration activity of microorganism was determined on different initial C N (17, 24 and 40) raw materials Composting was observed at 55 C, pH 5. Enzyme activity was enhanced in the presence of calcium whereas presence of EDTA gave reverseeffect. Straw residues from rice cultivation are rich in organic matter content (80%) and oxidizable organic C (34%) and have a high C N ratio (very variable and near the average of 50), which means a feasible carbon source for the microorganisms which able to survive the Fast pyrolysis Gas chromatographyMass spectrometry composting conditions. The total yield of liquid products signicantly increased as the pyrolysis temperature was raised from 400 to 500 C. The high water content in the pyrolysis liquid product may be due to the high moisture Pyrolysis temperature, heating rate and holdingtime on the yields of pyrolysis products and their chemical compositions content in the feeding biomasses and the release of volatile organic products during the preparation of condensed liquid sample. Tsai et al. (2006) Iranzo et al. (2004) (weight loss on ignition at 550 C for 72 h), oxidizable organic carbon (WalkleyBlack method) and total nitrogen (Kjeldahl method) were determined.

Rice akes

Composting

The production media contained 5 g of solid substrateand 10 mL mineral solution containing (mg gds)(NH4)2SO4 4, MgSO47H2O

Rice straw

Composting

The moisture content (oven dried at 105 C for 24 h),total organic matter

Current and potential uses of treated waste I. S. Arvanitoyannis and P. Tserkezou

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Rice straw

Pyrolysis

Oxygen content of the bio-oils was signicantly reduced because of the evolution of catalytic gases such as H2O, CO and CO2

967

968

Table 2 (Continued)

Kind of waste Parameters Weight loss curves for the pyrolysis of rice husk grain in N2 and CO2 Different levels of temperature different heating rates of rice husk. Non-isothermal heating in air Pyrolysis The burning of rice husk produces SiO2 with globular structure and well developed specic area. The pyrolysis in nitrogen medium gives SiO2 mixed with carbon. The optimised productionprocess was developed using as a FeCl2.4H2Ocatalyzer, 1370 Cas process temperature, 1.5 L min)1 argon ow and 40 min residence time. Alternative uses for the rice husk are Vlaev et al. (2003) Rice husk pyrolysis The method was found to predict satisfactorily the pyrolysis data at Methodology Results References

Treatment

Quality control methods

Rice husk

Pyrolysis

Sharma & Rao (1999)

Rice husk

Pyrolysis

atmospheres under non-isothermal conditions The content of SiO2 in the solid residue was determined gravimetrically after treatment with hydrouoric acid and the content of carbon The spectrum of catalyzed samples with FeCl24H2O. Temperature, pyrolysis time, type of catalyst, and process atmosphere Pyrolysis

International Journal of Food Science and Technology 2008


Martinez et al. (2005) Nitrogen was used as the sweeping gas with the ow rates of either 50, 100, 200 and 400mL min)1 and the highest bio-oil yield was obtained when ow rate was 200 mL min)1. Pyrolysis temperature, particle size, sweepinggas ow rate and steam velocity Pyrolysis Gas chromatographyMass spectrometry generated as new products that are manufactured from a remainder material. The pyrolysis oils were conducted with H-NMR, oils and aliphatic subfractions with FT-IR. The chemical Putun et al. (2004) The main element in rice husk ash is silicon (87.7% as SiO2), followed by potassium (5.4% as K2O) and phosphorous (3.7% as P2O5) Normal temperature Combustion characterisation has shown that the oil obtained from rice straw may be potentially valuable as fuel and chemicals feedstocks. The combustion tests using rice husk as fuel were done using different furnace temperatures and uidisation velocities. The effect of these variables on combustion efciency, CO emissions and ash characteristics were studied. The combustion tests were operated in the temperature range of 840880 C and in the Armesto et al. (2002) CO emissions varies from 200 to 800ppm, SO2 ranges from 50 to 100 ppm and NOx ranges from 150 to 220 ppm The temperature measuring and gas sampling ports are installed at different heights. Combustion uidisation velocity range of 11.2 m s. The experiments show that CO emissions varies from 200 to 800 ppm, whereas SO2 ranges from 50 to 100 ppm and NOx ranges from 150 to 220 ppm. If the uidising velocity grows further, the strong combustion intensity zone will move to thetop of the freeboard and increases the losses in unburned combustibles. Fang et al. (2004)

Rice husk

Pyrolysis

Current and potential uses of treated waste I. S. Arvanitoyannis and P. Tserkezou

Rice straw

Pyrolysis

Rice husk and

Combustion

straw

2007 The Authors. Journal compilation 2007 Institute of Food Science and Technology Trust Fund

Rice husk

Combustion

Table 2 (Continued)
Quality control Parameters The available period for mechanised collection of rice straw after the winter period ranges from 0 to 45 days. Thermal conversion The moisture contents are similar to those of rice plants just prior to harvest. Results for the subtreatments show that shielded stubble has signicantly higher concentraMethodology methods Results References Bakker & Jenkins (2003)

Kind of

waste

Treatment

Rice straw

Combustion

K and Cl content of Miscanthus and determined that a substantial decline in K and Cl occurred as a result of over-wintering

Rice husk High temperature Pyrolysis magnesium carbonate and zinc carbonate

Pyrolysis

Using some carbonates like mixture of sodium carbonateand bi-carbonate,

tions of K and Cl than exposed stubble and loose straw, suggesting that the thatching effect of straw does reduce leaching rate. The drastic weight loss pattern observed between 350 and 400 C was due to the destruction of cellulose and hemicellulose in the original biomass. Pyrolysis apparently started at around 350 C where the volatile matter in the biomass began to vaporise. The yield became almost constant after this stage,

Maiti et al. (2006)

Rice husk Using heating rates of 5, 10, 15, 20 C min)1.

Combustion

Both ne carbon silica and pure silica powders can be obtained by carbonisation and combustion of rice husk under non-isothermalconCombustion Carbonisation ditions

2007 The Authors. Journal compilation 2007 Institute of Food Science and Technology Trust Fund which marked the maximum char yield. After heating the rice husk in N2 or air, the impurity content is lower than that in acid-leached sample, indicating that the metals are also probably carried out from the volatiles during thermal decomposition. By comparing the carbon silica molar ratio in the carbonised husk, it was found that the carbon silica molar ratio increased with increasing the heating rate. Temperatures between 420 and 540 C Combustion Gas chromatographyMass spectrometry Experiments show that a temperature below 420 C is not sufcient for pyrolysis as some rice husks or sawdust were found in the charcoal and ash. The data shows that:(a) the energy cascade is about 49% for Zheng et al. (2006) Liou (2004) Mechanical, thermal and chemical (ammonia) treatment Biogasication Anaerobic digestion liquid fuel and about 86% for all products,(b) the thermal energy contained in the charcoal is more than the energy consumed by electric heating. A combination of grinding (10 mm length), heating (110 C), and ammonia treatment (2%) resulted in the highest biogas yield, 0.47 Lggl VS-fed, which is 17.5% higher than the biogas yield of untreated whole straw. Pretreatment temperature has a signicant effect on the digestibility of straw Zhang & Zhang (1999) digestion.

Rice husk

Combustion

Sulphur and nitrogen contained in the liquid fuel aretested to be 0.1% and 0.2% for rice husks

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Rice straw

Biogasication

Ammonia is used as a supplemental nitrogen source for rice straw

969

970

Table 2 (Continued)

Kind of waste Parameters Pleurotus sajor caju Biogas Methodology Results

Treatment

Quality control methods

References Banik & Nandi (2004)

International Journal of Food Science and Technology 2008


Supplementation of rice straw with biogas residual slurry manure has strong impact in improving the yield Temperature below 730 C to produce syngases for power generation and to recover valuable amorphous silPyrolysisGasicationSteam gasication ica materials. potential, protein and mineral nutrient contents of Pleurotus sajor caju mushroom in Indian subcontinent or similar climatic conditions. Gasication of rice husk was accompanied by a substantial production of syngas at 450630 C. It appears that in order to generate 10 kW electric power, approximately 28 kg h of rice husk must be gasied. The rice husk gasication process, in terms of heat requirements, can be self-sustaining. Air gasication The higher heating value of the gas obtained at this uidisation velocity and equivalence ratio (3.09 5.03 MJ Nm)3) compared very well with published data from air-blown biomass gasiers of similar scale of Mansaray et al. (1999) Lin et al. (1999) curred while CO gas was detected at 450 C. High temperature Different levels of temperature Steam gasication operation. The gas yield and carbon conversion were in the range of 1.301.98 Nm3 kg)1 and 5581%, respectively. At the higher temperature of 900 C, the reaction mechanism is not only chemically controlled but also be inuenced by diffusional resistance. Bhat et al. (2001)

Rice straw

Biogas

Disinfection of straw and manure by means of 0.1% KMnO4 plus 2% formalin solution in hot water

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Rice husk

Gasication

The infrared band intensity of CO2 gas was starting to grow at 200300 C, indicating an oxidation reaction oc-

Rice husk

Gasication

Using a gasifying medium such as air, oxygen, steam

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Gasication

CO2 is introduced by replacing N2 gas

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Table 3 Chemical analysis of corn stalk, corn cob and rice straw (adapted from Demirbas & Sahin, 1998; Zhang & Zhang, 1999; Tsai et al., 2001a,b; Singh & Sharma, 2002; Shuangning et al., 2005) Parameter Carbon Hydrogen Oxygen Nitrogen Cellulose Lignin Ash Corn stalk 43.6 5.4 42.3 0.6 50.4 13.7 0.9 0.5 0.2 0.9 0.1 7 1.1 0.1 Corn cob 45.8 5.5 45.3 0.9 50.2 14.5 0.9 0.9 0.5 0.9 0.3 2.7 1.5 0.2 Rice straw 38.8 4.6 43.7 0.46 41.2 12.7 20.5 0.4 0.05 1.1 0.02 3 2.1 0.2

technology mainly applied towards removal of organic compounds from liquid waste streams (http://www.epa.gov/epaoswer/osw/treatech.htm). Solid Waste Reduction By reducing the volume of waste that requires disposal, DOE can use the existing storage and disposal sites for a longer period of time. Solid waste reduction includes treatment methods that reduce the volume of solid waste such as incineration, compaction and sizing (http://web.em.doe.gov/em30/ wasttrea.html).
Composting

and is a technology that destroys organic constituents in waste materials (http://www.epa.gov/epaoswer/osw/ treatech.htm). Incineration of some commercial and industrial wastes which are hazardous and have low throughputs, use incineration as a means of disposal, and energy recovery is often a secondary objective. Sewage sludge incineration generates heat which is often used to dry the input sewage sludge to levels where the combustion is self-sustaining (Williams, 2005). The activated sludge process may have up to four phases: (a) clarication, by occulation of suspended and colloidal matter, (b) oxidation of carbonaceous matter, (c) oxidation of nitrogenous matter and (d) autodigestion of the activated sludge (Harrison, 2001). Neutralisation is a process used to treat corrosive hazardous waste streams. Low pH acidic corrosive waste streams are usually neutralised by containing bases. High pH corrosive waste streams are usually neutralised by adding acids (http://www.epa.gov/epaoswer/osw/treatech.htm). Vitrication is a solidication process that combines semi-liquid waste with glass, resulting in a stable glass form. In this process, highly radioactive liquid and sludge is mixed with glass particles and heated to very high temperatures to produce a molten glass (http:// web.em.doe.gov/em30/wasttrea.html). The physicochemical treatment plant will neutralise inorganic hazardous waste, including cyanides, chromium waste, waste acids, waste alkalis, heavy-metal containing waste. The main methods used will be cyanide oxidation, chromium reduction with subsequent settling, settling of heavy metals, neutralisation of acids and alkalis (http://www.zazemiata.org/bw/radnevo/resume_ovos_en.pdf). Physical removal is a process that removes the hazardous constituents from waste streams by separation techniques such as ion exchange, adsorption, reverse osmosis, chelation, solvent extraction, crystallisation, precipitation, distillation, ltration, evaporation, etc. The removed hazardous constituents may require further treatment to make them less toxic. Smelting is a technology employing high temperature heating in order to recover metals from waste streams (e.g. lead, zinc). Steam stripping is a treatment

Composting is the most popular technology for treatment of organic wastes, as it can be applied to process wastes of widely varying origin, including animal manures and mortalities, sewage sludges and municipal and industrial wastes (Lynch et al., 2006). Over the past few years, the dialogue between compost producers and the agricultural community has increased reective of the interest in determining composts many applications. Generally, compost as a soil amendment is known to provide many benets including improved soil structure, increased waterholding capacity, improved root and plant growth and reduced wind and water erosion (http://www. compost.org/pdf/ccc.rs.testing.compost.PDF). Composting is a decomposition of the organic, biodegradable fraction of waste to produce a stable product such as soil conditioners and growing material for plants. Composting of garden and food waste has been encouraged for home owners as a direct way of recycling. It has been extended to the larger scale for green waste from parks and gardens and also to municipal solid waste and to sewage sludge. The quality of the compost produced from waste, compared with non-waste sources, has been an issue for waste composting, particularly in the area of contamination (Williams, 2005). At the time the composting operations were started, little trial data for agricultural crops existed for biowaste compost, and it was felt necessary to investigate the performance of the material under soil and climate conditions, which are typical for the prospective compost market area (Erhart et al., 2005). The composting process is aerobic and consequently relies on a plentiful supply of oxygen. Regular aeration is required to maintain aerobic conditions. The composting process may be characterised by three stages (Swan et al., 2002). The rst stage is characterised by increasing temperatures and involves a high rate of microbiological activity. Simple carbohydrates and proteins are readily biologically degraded by mesophilic microorganisms, followed by thermotolerant and thermophilic microorganisms as the temperature rises above 45 C (Swan et al., 2002). The second stabilisation stage involves biodegradation of the waste by thermophilic

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Table 4 Treatment methods, physicochemical characteristics, substrate to be applied and nal product uses Substrate to be applied Wheat straw, corn cobs, barley husks Treatment methods Adsorption

Physicochemical characteristics Use of chemical (NaOH and NH4OH) and physical treatments (steam and milling) to help break down the complex lignin complex in order to improve the performance of the substrates. Experiments were carried out statically at room temperature, 20 2 C The temperature of the mixture rose to >40 C within 1 week of the onset of composting of CSC, and thermophilic phase (>40 C) temperatures were sustained for the rst 7 months of the 9 months composting period. Impregnation ratio of 20200 wt% Heating rate of 10 K min)1 Pyrolysis temperature of 6731073 K Soaking time of 0.54.0 h

Final products uses Soil conditioner or fertiliser

Reference Robinson et al. (2002)

Corn cob, barley husk and wheat straw Corn

Adsorption Composting

Soil fertiliser. Composting has long been used for management of manure on farm

Robinson et al. (2002) Lynch et al. (2006)

Corn cob

Chemical activation and pyrolysis

Corn stalk and fresh wheat straw Corn straw and wheat straw

Pyrolysis Pyrolysis

Corn cob

Pyrolysis

Pyrolysis temperature Residence time At low temperatures (400 K), only equilibrium moisture content and presumably extractives are released, even for very long residence times of the solid. The temperature was at 350400 C.

Raw materials for preparing activated carbons or adsorbents to apply in the removal of some organic and inorganic compounds from liquid and gas phases Bio-oil Gas and volatile

Tsai et al. (1998)

Shuangning et al. (2005) Lanzetta & Di Blasi (1998)

Corn stover Corn cob

Pyrolysis Gasication

Corn starch

Gasication

Corn cob

Chemical and physical activation

High levels of temperature Temperature ranges of 500800C with less pollution characteristics of potassium hydroxide: potassium carbonate (KOH:K2CO3) as chemical agents and subsequent gasication at the soaking time of 1 h. The inuence of process variables like temperature pressure, residence time and catalyst on supercritical water gasication of model compounds has been investigated. Chemical activation with potassium salts Physical activation with CO2

Xylan from corn cob is an additive in papermaking, textile printing and the pharmaceutical industry. Low-grade fuels Biomass feedstock Raw material for the preparation of activated carbon

Cao et al. (2004)

Green & Feng (2006) Tsai et al. (2001a)

Feedstock

DJesus et al. (2006)

Renewable source for energy production

Tsai et al. (2001a)

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Table 4 (Continued) Substrate to be applied Corn Corn cob and corn tar Corn Treatment methods Combustion and gasication Combustion Combustion

Physicochemical characteristics Carbon, hydrogen and mixed alcohols Temperature range from 110 to 220 C Combustion was carried out in a high pressure stainless steel oxygen bomb with a capacity of 340 mL. To minimise the effect of water in the biomass spectra, each sample was air-dried to less than 10% moisture prior to NIR spectroscopic analysis. The engine was fuelled with pure marine diesel fuel and blends containing two types of biodiesel, at proportions up to 50%. Under relatively high prices for gasoline the costs for using ethanol and biodiesel are much higher per equivalent litre of gasoline. When corn stover is harvested, ethanol is produced from both corn stover and corn grain. Pyrolytic temperatures below 600 C at the heating rate of 30 K rain. Use of different antioxidants Ascorbyl palmitate (0.02% w w) BHA Tert-butyl-4-hydroxyanisole (0.02% w w) Different amounts of solvent extracts, to 25 g of stripped corn oil or plant oils. Varying pH (4.57.5) Temperature between 35 and 55 C Physical activation involves the carbonisation of a carbonaceous precursor followed by the gasication of the resulting char in the presence of suitable oxidising gasifying agents such as CO2 and steam at high temperatures. Chemical preparation with ZnCl2. pH 5.0 Temperature 50 C Pretreated with NaOH Followed by 48 h of reaction Temperature 50 C pH 5.0 Xylanase, glucanase, cellulase, Phanerochaete chrysosporium NRRL 6359, P. chrysosporium NRRL 6361 and Coriolus versicolor NRRL 6102

Final products uses Renewable fuels Burning oil of biomass (BOB) Renewable fuels

Reference Chum & Overend (2001) Zhang & Wang (2006) Souza et al. (2002)

Corn stover

Combustion

Fuel or industrial feedstock

Pordesimo et al. (2005)

Corn oil

Biodiesel

Alternative fuels

Kalligeros et al. (2003)

Corn

Ethanol and biodiesel production

Alternative liquid fuels and ethanol production

Wesseler (2007)

Corn stover

Biodiesel and bioethanol Pyrolysis Chemical method

Biofuels

Kim & Dale (2005)

Corn cob Corn oil and wheat germs

Liquid products of biomass Edible products as corn oil

Cao et al. (2004) Krings et al. (2000)

Corn Corn cob agrowaste

Bioremedation Chemical activation

Methane and hydrogen Biofuels Renewable source for energy production

Montgomery (2004) Chang et al. (2000)

Corn husks Corn cobs

Enzyme preparation Enzyme preparation

Enzymatic production of soluble sugars Enzymatic production of reducing sugars

Hang & Woodams (1999) Hang & Woodams (2001)

Corn cob and wheat straw

Biodegradation

Production of enzymes

Abd El-Nasser et al. (1997)

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Table 4 (Continued) Substrate to be applied Corn stover Treatment methods Chemical activation

Physicochemical characteristics Heat loss in a 1.26 m pipeline carrying 2M dry tonnes per year is about 5 C Gamma irradiation of corn stover in combination with sodium hydroxide for bioconversion of polysaccharide. Temperatures around 800 C

Final products uses Production of ethanol and sugars Fertiliser for the production of Pleurotus spp.

Reference Kumar et al. (2005)

Corn stover

Radiation

Gbedemah et al. (1998)

Corn hull and orn stover Corn cob

Physical activation

Activated carbon

Zhang et al. (2004)

Chemical activation

Rice straw

Composting

Rice straw

Composting

Rice akes

Composting

Rice straw

Composting

Rice straw Rice husk Rice husk Rice straw

Pyrolysis Pyrolysis Pyrolysis Pyrolysis

Many chemicals can be used as activators such as ZnCl2, H3PO4, KOH, K2CO3, water vapour, CO2. EC, pH were measured in the aqueous extracts of rice straw, oilseed rape cake, poultry manure and compost in a solid: distilled water of 1:20 (w v dry weight basis). Temperature, aeration, moisture and nutrients should be appropriately controlled. It is considered C N ratio at 2530 as the initial optimum ratio for composting. (NH4)2SO4 4 mg gds)1 MgSO4 7H2O 1 mg gds FeSO4 7H2O 0.02 mg gds K2HPO4 1.4 mg gds KH2PO4 0.6 mg gds. pH 7 The C N ratios were the lowest (1724) A temperature of 62 C during 48 h removed pathogenic microorganisms from rice straw Moisture 13.61% wt. Pyrolysis temperature of 400800 C Temperature 250550 C Temperature 13001500 C Moisture 7.16%wt

Renewable fuels

Cao et al. (2006)

Composting of rice straw with oilseed rape cake and poultry manure effects faba bean (Vicia faba L.) growth and soil properties.

Abdelhamid et al. (2004)

The mixture of swine manure with rice straw is used as fertiliser

Zhu (2007)

Edible products

Anto et al. (2006)

Paper production, construction materials, incorporation in soil, compost, energy source, animal feed, etc.

Iranzo et al. (2004)

Fuel gases, liquids and solids Source of thermal energy. Fuel gases Raw material for paper industry, or as animal feed sources. Bio-oils Fuels

Tsai et al. (2006) Sharma & Rao (1999) Martinez et al. (2005) Putun et al. (2004)

Rice husk and straw

Combustion

Rice husk

Combustion

The inuence of different variables such as temperature, uidisation velocity on the combustion efciency and CO emissions was investigated. Moisture 16.92%wt Temperature is 340 C

Armesto et al. (2002)

Renewable fuels

Fang et al. (2004)

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Table 4 (Continued) Substrate to be applied Rice straw Rice husk Treatment methods Combustion Pyrolysis

Physicochemical characteristics Temperature 575 C The optimum temperature is 400 C

Final products uses Fuel Fodder for livestock and industrial fuel for boilers Renewable source of thermal energy Liquid fuel Fertiliser for the production of Pleurotus sajor caju Renewable source of energy Fuel gas

Reference Bakker & Jenkins (2003) Maiti et al. (2006)

Rice husk Rice husk Rice straw Rice husk Rice husk

Combustion Combustion Biogas Gasication Gasication

Temperature ranging between 300 and 700 C pH about 7 Temperature range of 450-550 C 2% formalin 0.1% KMnO4 High moisture content (10.0% wt) Low heating value (HHV 3450 kcal kg)1) Temperature range of 200 1372 C

Liou (2004) Zheng et al. (2006) Banik & Nandi (2004) Lin et al. (1999) Mansaray et al. (1999)

microorganisms and is an exothermic process so that temperature in the compost pile can reach up to 70 C. The high temperature stage involves the thermal destruction of weed seeds and pathogenic microorganisms. The compost also includes a third maturation stage and is characterised by lower temperatures (Williams, 2005). The nal stages of composting would be processes such as sieving and grading to remove non-composted materials and contaminants. Composting is commonly used to improve the properties of manures for organic farming. Available N in raw manure is immobilised during optimal composting allowing more stable slow release of N forms for crops (Vuorinen & Saharinen, 1997). High quality compost is increasingly available and it oers farmers considerable benet when used on land in a way that other materials, whether conventional fertilisers or wastes such as sludges, do not. Users of compost should ensure that material complies with an accredited standard, most commonly UK BSI PAS1002. Good quality compost is a valuable and safe resource, not a waste product. As a general principle, all material such as compost that has signicant fertiliser value should be applied only up to the level of crop requirements. However, the way in which compost can be used is dierent when compared with mineral fertilisers. To identify the use-thresholds it is important to understand the nature of compost (http://www.remade.org.uk/ organics/organics_documents/compostbenetsscottishcrops. pdf). During composting, putrescible material is progressively broken down by microorganisms in a series of distinct stages. In the mesophilic stage, microorganisms begin to actively break down the organic material, the temperature of the composting material rising to around 50 C in about 2 days. During the second or thermophilic stage, temperatures begin to rise so that only the most temperature resistant microorganisms survive. In the third stage, the material continues to cool and

microorganisms begin to complete for the remaining organic material, in turn leading to breakdown of cellulose and lignin in the waste. During the nal levels of microbial activity continue to fall as the remaining organic material is broken down and the microorganisms die as their food sources deplete (Harrison, 2001). Turning compost is important as it ensures proper mixing, wetting, aeration and decomposition. The compost heap is allowed to settle for 1 month, and then turned using pitch forks. Material on the top of the heap and along the edges is laid on the ground rst, followed by the materials in the middle of the heap. Materials at the bottom are then placed at the top of the heap (http://www.formatkenya.org/ormbook/Chapters/chapter9. htm). Because much C from plant residues such as straw materials is only slowly available to micro-organisms, leading to low growth eciency, a limited amount of N may be required during decomposition, and recycling of N may then be adequate to meet the N requirements. Micro-organisms, especially fungi, have a considerable capacity to adapt to N decient conditions. A large amount of N initially could consequently result in immobilisation. This greater N immobilisation may depend on (a) synthesis of microbial biomass with a lower C N ratio; (b) higher N losses; or (c) reduced N mineralisation or re-mineralisation, which may have been related to reduced microbial activity (Dresbll & Thorup-Kristensen, 2005). Composting of urban waste has emerged as a valuable alternative because of the high proportion of organic matter in urban waste. The bio-degradable fraction is estimated at about 25% (fresh weight) in France, along with an additional 25% made up of paper and cardboard. Composts have long been used in agriculture and urban waste composts may be applied in arable elds as organic amendment to maintain soil organic matter (SOM) as well as supply nutrients to crops (Gabrielle et al., 2005). Organic wastes make up a large

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part up to 40%- of the municipal solid waste stream. Therefore, organic wastes should be recycled from an ecological as well as from an economical point of view. In the late 1980s, composting of separately collected organic household wastes was introduced in Vienna and subsequently a municipal composting plant was set up. As a result of extensive quality control measures, all compost lots produced were suitable for agriculture and 22% even for organic farming. With wheat, a wide range of yield responses to compost fertilisation has been recorded. Non-signicant wheat yield increases followed the application of 6.9 t ha)1 biowaste compost on a parabrown soil in Germany (Erhart et al., 2005). Control of a composting process and the properties of the end product can be achieved by at least two dierent strategies. One strategy is to adjust process parameters, such as moisture level, temperature or oxygen content. Another is to alter the starting conditions by changing the composition or type of material used so that C N ratio or bre composition is changed (Dresbll & Thorup-Kristensen, 2005). Compost is likely also to contain a wide range of minor plant nutrients and benecial microbes not normally present in mineral fertilisers. Together these are likely to have an additive positive eect on general soil health. Composts derived from segregated wastes are generally acceptably low in heavy metals and compost complying with an appropriate standard will have data to conrm this (http://www.remade.org.uk/organics/organics_documents/ compostbenetsscottishcrops.pdf). Composted solids are usually dark brown to black, but the colour may vary if bulking agents such as recycled compost or wood chips have been used in the composting process. The odour of well-composted solids is inoensive and resembles that of commercial garden-type soil conditioners (Tchobanoglous et al., 2003). The remaining nutrient rich material should be added later in the process when the turnover of the wheat straw would already be proceeding. Decomposition of the newly added material would then result in less N immobilisation compared with compost produced by a single addition at the beginning of the process (Dresbll & Thorup-Kristensen, 2005). Decomposition of plant tissue depends on various factors including temperature, moisture content, oxygen content and residue quality. In general, both resource quality and physiochemical parameters aect the composition and activity of the decomposer communities conducting the mineralisation immobilisation processes of decomposition. Thus, when producing plant based compost to be used as growing medium in horticultural productions choice of plant material is a key factor, as root proliferation and development depend heavily on the physical structure and stability of the medium. The physical properties are mainly dependent on the starting material and are dicult to

alter during strongly aected by production (Caton et al., 1999). Nitrogen was often recognised as a limiting factor for microbial growth and activity during the decomposition of plant residues, especially in materials with a high C N ratio such as wheat straw. However, experiments on the eect of additional N supply on the decomposition of plant residues showed dierent results, ranging from positive to negative eects on the decomposition rate (Dresbll & Thorup-Kristensen, 2005). Organic compost from waste may be used for various purposes, among which are soil recovery, commercial production, pastures, lawns and reforestry and agriculture. However, the quality of compost determines the plant growth and development of plants. The eect of compost made from urban waste on corn plant (Zea mays L.) growth was investigated. Two types of compost were used: the selected compost, produced from organic waste selectively collected; and the non-selected compost. Chemical analyses of the compost and growth properties of the plant like chlorophyll content; height and stem diameter; aerial and radicular dry biomasses were used to evaluate compost quality (Lima et al., 2004). However, a technical diculty was the lack of a reliable and inexpensive methodology to examine the fate of compost in soil and to quantify compost eects on SOM. Organic amendments often supply much greater C inputs to soil than are derived from crop residues. Relatively few studies applied the d13C technique to improve our understanding of the transformation, utilisation and stabilisation of amendment carbon in soil. However, the high degree of microbial processing occurring during composting of organic amendments reduced the inherent variability of their 13C signature, an aspect of composting which had not been examined (Lynch et al., 2006). Composting temperature is inuenced by moisture content, degree of aeration, size and size of the pile, and climatic conditions, particularly air temperature and rainfall. The nished compost is friable humus with moisture content less than 40%. Although too low in nutrients to be considered a fertiliser, compost is an excellent soil conditioner. For example, when mixed with soil, the added humus content increases the capacity for retention of water (Hammer & Hammer, 2004).
Pyrolysis

Pyrolysis (PY) is the rst and most basic thermochemical step to convert biomass into gaseous or liquid fuels. However, despite the fact that PY underlies humankinds oldest technology (the use of re) PY is still not a predictive science (Green & Feng, 2006). PY is the decomposition of a complex organic substance to one of a simpler structure by means of heat in the

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absence of oxygen or any other reagents, except possibly steam. Some polymers will depolymerise in the presence of excessive temperatures either to polymers of lower molecular weight, or back to the monomers from which they were derived (http://composite.about.com). Pyrolysis typically occurs under pressure and at operating temperatures above 430 C. In practice, it is not possible to achieve a completely oxygen-free atmosphere. Because some oxygen is present in any PY system, a small amount of oxidation occurs. If volatile or semi-volatile materials are present in the waste, thermal desorption will also occur (http:// www.cpeo.org/techtree/ttdescript/pyrols.htm). PY is thermal degradation of waste in the absence of air to produce char, PY oil and syngas, e.g. the conversion of wood to charcoal (http://www.juniper.co.uk/services/ Our_services/P&GFactsheet.html). The manner, in which PY works, oers some advantages over conventional incineration. Firstly, because no air is fed into the combustor, far less waste gases are produced and therefore the gas cleaning system can be smaller and hence less costly. Secondly, the waste itself must be preprepared to make it homogeneous and to remove bulky materials. Finally, in theory the solid, liquid and gaseous streams can be further processed into useful products and hence there should be less material to discard to landll (Harrison, 2001). Organic materials are transformed into gases, small quantities of liquid and a solid residue containing carbon and ash. The o-gases may also be treated in a secondary thermal oxidation unit. Particulate removal equipment is also required. Several types of PY units are available, including the rotary kiln, rotary hearth furnace or uidised bed furnace (http://www.cpeo.org/ techtree/ttdescript/pyrols.htm). Flash PY gives high oil yields, but because of the technical eorts required to process pyrolytic oils this energy generating system does not seem to be very promising at the present stage of development. However, PY as a rst stage in a two-stage gasication plant for straw and other agricultural feedstocks posing technical diculties in gasication does deserve consideration (http://www.tab.fzk.de/en/ projekt/zusammenfassung/AB49.htm). Pyrolysis is usually consindered to be anhydrous and occuring whenever solid organic material is suciently heated, e.g. when frying, roasting, baking, toasting. The process also occurs when burning compact solid fuel, like wood. In fact, the ames of a wood re are as a result of combustion of gases released by PY, not combustion of the wood itself. Thus, the PY of common materials like wood, plastic and clothing is extremely important for re safety and re ghting (http://en. wikipedia.org/wiki/Pyrolysis). Pyrolysis is an interesting degradative technique because it can be easily coupled to gas chromatography (GC), mass spectrometry (MS) or GC MS thus allowing

the online degradation of polymers and the analysis of their fragments by hyphenated techniques such as PY GC, PY GC MS or PY MS (Rodriguez et al., 1997). The PY products identied were mostly related to carbohydrates (furans), proteins (nitriles and pyrrols), chitin (pyridines and pyrazols), lipids (alkanes and derivatives of benzene) and lignin (phenols). The relative yield of all individual PY products was similar in the samples from the maize (C4) and control wheat (C3) soil. In detail the 23-year maize cropping added 2-methylfuran, pyridine and xylene but, on the contrary, decreased the content of furan-3-carboxaldehyde and phenol (http://dbs.clib-jena.mpg.de/dbs-publ/pubi/bgc/BGC0130. pdf). Some of the main objectives were to characterise and study the preparation of biomass to meet the necessary specications to be used for bio-oil production in the rotating cone PY technology. This included selection of a number of relevant biomass materials based on primary criteria such as their high availability in the EU and low production costs (http://www.biomatnet.org/secure/Fair/F538.htm). Bio-oil from fast PY is in many ways dierent from other liquid fuels (such as rape seed oil or bio ethanol derived) from biomass like. It also diers signicantly from diesel fuel in both physical properties and chemical composition. Bio-oil contains water and solids; it is acidic and has a low caloric value (http://www. dynamotive.com/biooil/technology.html). Fast PY process that converts forest and agricultural residue (including bark) into liquid Bio-oil and char. Biooil is a clean burning, greenhouse gas neutral fuel that will initially be used to replace fossil fuels to generate power and heat in stationary gas turbines, diesel engines and boilers and to replace natural gas in the forest industry and to replace another product in the coal industry. The char is a high heating value solid fuel that can be used in kilns, boilers and the briquette industry. Three products are produced: Bio-oil (6075% wt), char (1525% wt) and non-condensable gases (1020% wt) (http://www.biomatnet.org/secure/Fair/F538.htm). Fast PY refers to the rapid heating of biomass (including forest residue such as bark, sawdust and shavings; and agricultural waste such as wheat straw and bagasse) in the absence of oxygen. It used a bubbling uidised bed reactor (FBR), which is considered to be a simpler and more robust process than other PY technologies under development (http:// www.dynamotive.com/biooil/technology.html). Thermogravimetric analyzers (TGA) were one of the main techniques used in analyzing the characteristics of solid fuel volatilisation at lowheating rates. The maximum heating rate of TGA could reach as high as 100 LC min-1. For years, PY and combustion reactions of pulverised biomass were investigated in various applications using TGA (Shuangning et al., 2005).

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Understanding PY kinetics is important for the eective design and operation of the thermochemical conversion units given that solid devolatilisation is always a fundamental step. The TGA technique has been applied in several cases for such a purpose. Thermogravimetric curves for wheat, barley, oats and rye straw have been measured in both inert and oxidising atmospheres. In terms of global kinetics, (for all types of straw), two distinct reaction zones are detailed, the thermal degradation rates of the rst zone is higher than the second (Lanzetta & Di Blasi, 1998). The pyrolyser consists basically of a rotating, vertically orientated, electrically heated disk. Solid wood boards with a cross sectional area of 10 47 mm and a length of approximately 350 mm are pressed against the disk by a piston. The pressure ranges between 30 and 50 bar, and the heated disk temperature is approximately 700 C (http:// www.pyne2005.inter-base.net/docs/PyNews%2017.pdf). The core of the PY pilot plant is the rotating cone reactor which is a compact high intensity reactor in which biomass of ambient temperature is mixed with hot sand. Upon mixing with the hot sand at 550 C the biomass decomposes providing 70 weight per cent condensable vapours, 15 weight per cent non-condensable gases and 15 weight per cent char. During the Biomass Technology Group (BTG) and KARA projects a fully automated PY plant with a capacity of 260 kg h)1 was successfully designed and constructed. This was operated over a number of trial periods, during which the following conditions were established as those that gave the highest oil yield and produced the best quality bio-oil: (a) reactor temperature of 470 C, (b) vapour residence time<one second and (c) biomass particles<4 mm (http://www.biomatnet.org/secure/Fair/ F538.htm). Based on the dierences in isotopic enrichment of chemical structures after vegetation change the PY products could be divided into three groups: (a) PY products with a nearly complete C4 signal, e.g. phenol, derived from lignin degradation products, (b) PY products with an intermediate isotopic enrichment of 68 per thousand, most likely to be a composite of remaining fragments derived from both maize and native wheat and (c) PY products showing only low enrichments in 13C of 13 per thousand. Most of their precursors were found to be proteinaceaous materials. This indicated that proteins or peptides were indeed preserved during decomposition and humication processes occurring in the soil. Our study highlights the potential of PyGC MS-C-IRMS to further novel insights into the dynamics of soil organic constituents (Gleixner et al., 1999). Insight at the chemical structure of complex biomacromolecules can be obtained via pyrolytic studies and this technique has been applied to a large range of natural compounds. Among the various methods used

for isolating lignin-containing materials from biomass, the one aording the so-called ligno-cellulosic substrate. This material was obtained from wheat straw by successive acid and base treatments (Gauthier et al., 2003). PY in the presence of tetramethylammonium hydroxide (TMAH) has been used to analyse phenolic acids, natural resins, resinites, humic acids, asphaltenes, kerogens, lignins and organic matter in nearshore marine sediments. PY of lignin in the presence of TMAH induces cleavage of propylaryl ether bonds and methylation of hydroxyl (OH) groups located on both alkyl side chains and aromatic rings. The technique avoids decarboxylation of polar moieties and yields phenolic derivatives, which are not observed during conventional analytical PY (Vane et al., 2001). Combined Py GC MS of complex macromolecular materials can provide detailed structural information but suers limitations for the identication of compounds comprising polar functional groups like carboxylic and OH groups. This technique is improved by introducing thermochemolysis with telramethylammonium hydroxide, TMAH thermochemolysis corresponds to a thermally-assisted chemolytic degradation rather than degradation simply induced by thermal bond cleavage. In addition, in situ methylation occurs so that a number of polar products become volatile enough for gas chromatographic analysis (Gauthier et al., 2003). Analytical PY is one of the many tools utilised for the study of natural organic polymers. Analytical PY methodology covers two distinct subjects, the instrumentation used for PY and the analytical methods that are applied for the analysis of the PY products. A variety of pyrolytic techniques and of analytical instruments commonly coupled with PY devices are given (http://www.elsevier.com/wps/nd/bookdescription.cws_ home/600279/description#description). The term PY is sometimes used to encompass also thermolysis in the presence of water, such as steam cracking of oil, or more generally hydrous PY. An example of the latter is thermal depolymerisation of organic waste into ligh crude oil (http://en.wikipedia.org/wiki/Pyrolysis). The applications of analytical PY included topics such as polymer detection used for example in forensic science, structure elucidation of specic polymers, and identication of small molecules present in polymers (anti-oxidants, plasticisers, etc.). In addition, the degradation during heating is a subject of major interest in many practical applications regarding the physical properties of polymers (http://www.elsevier.com/wps/ nd/bookdescription.cws_home/600279/description# description). Analytical methods based on PY-GC coupled to MS present great potential because of the small amount of sample necessary for analysis and the type of information provided (Camarero et al., 2001). Analytical PY was shown to be very eective in the characterisation of lignins, where most of the pyrolytic

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fragments are not secondary rearrangement products, but diagnostic compounds in which the structure of the main building blocks of the macromolecule is preserved. In this way, a semiquantitative assessment of the monomer composition for the dierent lignin types can be made: in fact, PY combined with GC and MS proved to be a valuable tool for the analysis of pulp samples (Galletti et al., 1997). Pyrolysis was carried out at 600 C for 5 s. PyGC interface was set at 200 C. The GC column was a SPB5 and was operated from 50 to 290 C at 5 C min)1, holding the initial temperature for 10 min. The injector was set at 250 C in the split mode. Mass spectra were recorded under electron ionisation at 70 eV, spectral range from 40 to 450 m:z, 1 scan per s. To optimise Py GC:MS quantitation of lignin and polysaccharide PY products correction factors for the use of 1,3,5-tri-tertbutylbenzene as internal standard were obtained for dierent phenolic standards (Martinez et al., 2001). PY and gasication are thermal processes that use high temperatures to break down any waste containing carbon (http://www.foe.co.uk/resource/triengs/ gasications_pyrolysis.pdf). Pyrolysis yields of carbon products prepared from agricultural waste corn cob by chemical physical activation are presented in Fig. 1 and element analysis of rice husk heat treated under pyrolytic conditions at dierent temperature is given in Figs 2 and 3. A system boundary in the various cropping and alternative production systems is presented in Fig. 4. Material and energy balances of the rice husk gasication process and ow sheet of rice husk uidised bed fast PY and uidised bed fast PY catalytic treatment processes are given in Figs 5 and 6, respectively.
Gasication

80 70 60 50 40 30 20 10 0 150 350 450 550 Temperature 650 750

Figure 2 Elemental analysis of rice husk heat treated ( for C, for H and m for N) under pyrolytic conditions at dierent temperatures (adapted from Maiti et al., 2006).

Elements
Elements

70 60 50 40 30 20 10 0 150 350 450 550 Temperature 650 750

Figure 3 Elemental analysis of rice husk heat treated ( for O-dry ash free and for dry ash) under pyrolytic conditions at dierent temperatures (adapted from Maiti et al., 2006).

The gasication process breaks down the hydrocarbons left into a syngas using a controlled amount of oxygen. Gasication and PY typically rely on carbon-based waste such as paper, petroleum based wastes like
40 35 30 25 20 15 10 5 0 500 600 700 750 Activation temperature 800

Figure 1 Pyrolysis yields of carbon products prepared from agricultural waste corn cob ( for KOH activating agent, ; for K2CO3 activating agent) by chemical physical activation (adapted from Tsai et al., 2001a,b).

plastics, and organic materials such as food scraps. Gasication involves a small amount of oxygen whereas PY uses none (http://www.foe.co.uk/resource/triengs/ gasications_pyrolysis.pdf). Gasication can be used in conjunction with gas engines (and potentially gas turbines) to obtain higher conversion eciency than conventional fossil-fuel energy generation (http://www.juniper.co.uk/services/ Our_services/P&GFactsheet.html). Gasication involves subjecting solid biomass to hot steam and air to produce a gaseous biofuel. This gas, often known as synthesis gas may be burnt directly for heating and or electricity production, or may be further converted to act as a substitute for almost any fossil fuel. The advantage of gas, over biomass, is that it is a better fuel, having a higher caloric value, and being more easily stored and transported (http://www.ecocentre. org.uk/biomass.html). The gasication process was originally developed in the 1800s to produce town gas for lighting and cooking. Natural gas and electricity soon replaced town gas for these applications, but the gasication process were utilised for the production of synthetic chemicals and fuels since the 1920s. Gasication relies on chemical processes at elevated temperatures >700 C, contrary to biological processes such as anaerobic fermentation (digestion) which releases biogas (http://en.wilipedia. org/wiki/Gasication).

Pyrolysis yields

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Liquid fuel Ethanol Corn grain Wet milling Corn oil Corn gluten meal Corn gluten feed Edible oil

Corn culture

Liquid fuel Corn stover Corn stover process Ethanol electricity Export to power grid

Figure 4 System boundaries in the various cropping and alternative production systems (adapted from Seungdo et al., 2005a, b).

The gasication of herbaceous biomass is still at an early stage of research and development. Intensied development eorts on gasication technologies for herbaceous biomass feedstocks are desirable as the potential supply of this group of fuels is comparatively large (http://www.tab.fzk.de/en/projekt/zusammenfassung/AB49.htm). A wide range of biomass fuels such as wood, charcoal, wood waste (branches, roots, bark, saw dust) as well agricultural residues- maize cobs, coconut shells, cereal straws, rice husks, were used as fuel for biomass gasication. Theoretically, almost all kinds of biomass with moisture content of 530% can be gasied; however, not every biomass fuel lead to the successful gasication. Most of the development work was carried out with common fuels such as coal, charcoal and wood (http://mitglied.lycos.de/cturare/ fue.htm). The gasication technologies developed by competing suppliers of gasication power plants, are based either on xed bed gasication or uidised bed gasication. In both cases, a limited number of commercial running plants is present. In xed bed gasication reactors, the fuel is fed into the top of a vertical reactor. The fuel is transported downwards by gravity while undergoing the gasication reactions (http://www.ecn.nl/docs/library/ report/2000/c00080.pdf). Compared with other biomass energy conversion technologies, supercritical water gasication (SWG) is the most ecient one for biomass with a high moisture content (40%). In spite of the high pressure and high temperature required for biomass conversion with supercritical water the process is technically feasible, because tubular or slim vessel type reactors can be used (DJesus et al., 2006). The fuel size aects substantially the pressure drop across the gasier and power that must be supplied to draw the air and gas through gasier. Large pressure drops will lead to reduction of the gas load in downdraft gasier thus resulting in low temperature and tar production. Excessively large sizes

Rice husk 28 kg h1

Carbon 10.95 kg h1

Water 2.8 kg h1

Ash 4.67 kg h1 Carbon 3.11 kg h1

Air

Downdraft gasifier

Tar (108 g h1)

Tar/water absorbent

Syngas (54 000 L h1) Carbon (7.84 kg h1) Water (14.77 kg h1)

Internal combustion engine

Electric power 10 KW

Figure 5 Material and energy balances of the rice husk gasication process (adapted form Lin et al., 1999).

of particles give rise to reduced reactivity of fuel, causing start-up problem and poor gas quality. In general, wood gasiers work well on wood blocks and wood chips

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Rice husk

Grinder

Sieve

Drier GAS

Fluidized bed reactor

Feeder

Char collector

Cyclone

Cyclone

Char

Condenser

Catalytic Reactor

Catalyst

Regeneration Liquid collector

Condenser

Coked catalyst Liquid collector

Figure 6 Flow sheet of rice husk uidised bed fast pyrolysis and uidised bed fast pyrolysis catalytic treatment processes (adapted from Islam et al., 2004a, b).

Pyrolysis oil

ranging from 80 40 40 mm to 10 5 5 mm. For charcoal gasier, charcoal with size ranging from 10 10 10 mm to 30 30 30 mm is quite suitable (http://mitglied.lycos.de/cturare/fue.htm#size). The electric eciency of a gasication plant is directly related to the cold gas eciency of the gasier. This parameter is mainly determined by the carbon conversion, the heat loss of the reactor and the fuel gas temperature leaving the reactor. Fixed bed reactors generally show a lower carbon conversion but also have a lower exit temperature of the gas. The heat loss should be lower as the specic surface (m2 m3) is lower (http:// www.ecn.nl/docs/library/report/2000/c00080.pdf). The inuence of process variables like temperature pressure, residence time, and catalyst on SWG of model compounds was investigated. The best hydrogen yield for the SWG of sawdust and dierent starches was reached at high temperatures. The same important eect

of the temperature has been reported in other publications (DJesus et al., 2006). One of the major advantages of BIVKIN-technology over xed bed technology involves the superior fuel exibility. BIVKIN-technology was demonstrated to be suitable to handle a broad range of feedstocks with varying moisture content and physical shape. Fixed bed gasiers do require properly sized wood chips, briquettes or pellets with a dened moisture content. In case of pellets, high quality standards were set regarding the mechanical strength of pellets at high temperatures. This mechanical strength would probably not be realised for all kinds of feedstock. Not only expensive pretreatment steps can be omitted in the case of uidised bed compared with xed bed processes, but long-term contracts with fuel suppliers may not be necessary anymore as the fuel input is exible (http://www.ecn.nl/ docs/library/report/2000/c00080.pdf).

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The moisture content of the most biomass fuel depends on the type of fuel, its origin and treatment before it is used for gasication. Moisture content of the fuel is usually referred to inherent moisture plus surface moisture. The moisture content below 15% by weight is desirable for trouble free and economical operation of the gasier (http://mitglied.lycos.de/cturare/fue.htm# moisture). The form in which fuel is fed to gasier has an economical impact on gasication. Densifying biomass has been practiced in the US for the past 40 years. Cupers and Pelletisers densify all kinds of biomass and municipal waste into energy cubes. These cubes were available in cylindrical or cubic form and had a high density of 6001000 kg m-3. The specic volumetric content of cubes was much higher than the raw material they were made from (http://mitglied.lycos.de/cturare/ fue.htm#form). Corn has a high energy content and high organic matter yield (per hectare). Corn silage is chemically stable because it does not degrade and maintains its properties over long period of time. Corn silage is available all year through thereby preventing shortages in the continuous production of hydrogen from biomass. As a result of all these advantages, corn silage is a feedstock suitable for an industrial SWG process. To optimise the process of SWG of biomass, the inuence of the process variables on the gasication of real biomass feedstock like corn were studied. A down-ow reactor (1000 mm long and 8 mm inner diameter) with preheater (250 mm long and 8 mm inner diameter) was used for investigating the inuence of temperature on corn silage the gasication with the aim of improving gasication yield and reducing the problems of solid formation (DJesus et al., 2006). Energy content of fuel is determined in most cases in an adiabatic, constant volume bomb calorimeter. Using this method higher heating values were obtained because the condensation heat from water formed in the combustion of fuel was included. Heating values are also reported on moisture and ash basis. Fuel of higher energy content is always better for gasication. Most biomass fuels (wood, straw) have heating values in the range of 1016 MJ kg-1, whereas liquid fuel (diesel, gasoline) display higher heating value (http:// mitglied.lycos.de/cturare/fue.htm#energy).
Combustion

The combustion of biomass is considered a three step process; devolatilisation to char and volatiles, and combustion of volatiles and char. A number of parameters are required as inputs to existing computational uid dynamics (CFD) particle combustion models, such as devolatilisation yields and rates, composition of volatiles, amount of char formed and char burning rates (Jones et al., 2000).

Although combustion involves complicated chemical reactions and uid dynamical processes, including the development of instabilities, the team had a high degree of experimental control over combustion and could study it in detail by using a two-dimensional chamber that prevented convection (http://www.esam.northwestern.edu/~matkowsky/ngering.html). The combustion gases typically pass though a boiler system to recover energy. The most exible means of recovering energy from the hot gases is to produce steam for direct use or for electricity generation. To generate electricity, superheated steam is passed from the boiler system to a turbine generator (Harrison, 2001). During combustion, all fuel is converted to a hot gas (ue gas), which can be used to generate steam in a boiler and subsequently generate electricity in a steam turbine generator. The electric eciency is mainly the result of the eciency of the steam turbine. Fuel gasication resulted in production of a combustible fuel gas (http:// www.ecn.nl/docs/library/report/2000/c00080.pdf). The use of an elevated pressure of oxygen inside a closed metal container in the form of oxygen bomb combustion is an alternative procedure for complete oxidation of biological samples. Combustion with oxygen in sealed bomb was used to convert solid and liquid combustible samples into soluble forms for chemical analysis. In this system, the organic matter was oxidised to carbon dioxide and water by the combustion reaction, and the volatile components, formed by burning, are trapped in an absorption solution (Souza et al., 2002). The o-gases containing volatile organic compounds (VOCs) from covered treatment facilities will have to be treated before they can be discharge to the atmosphere. Options for the o-gas treatment include: (a) vapourphase adsorption on granular activated carbon or other VOC selective resins, (b) thermal incineration, (c) catalytic incineration, (d) combustion in a are, (e) bioltration and (f) combustion in a boiler or process heater (Tchobanoglous et al., 2003). Nitrogen freed by combustion at high temperature in pure oxygen was measured with thermal conductivity detection and converted to equivalent protein by appropriate numerical factor. Any instrument or device designed to determine nitrogen by combustion may be used provided it is equipped as follows: (a) furnace to maintain minimum operating temperature of 950 C for PY of sample in pure (99.9%) oxygen, (b) system to isolate liberated nitrogen gas from other combustion products for subsequent determination with thermal conductivity detector, (c) detection system to interpret detector response as % nitrogen (weight weight). Other features tentatively included are calibration on standard material, blank determination and barometric pressure compensation (http://www.foragetesting.org/lab_procedure/ sectionB/3/part3.3htm).

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The world has for sometime witnessed growing concern over the environmental impact and or exhaust of conventional fossil fuel energy sources. The concern has highlighted the need for diversication and prompted research world-wide into potential alternative sources of fuel energy for internal combustion engine. Environmental well-being requires a modied mix of energy sources to emit less carbon dioxide, starting with a move to wards alternative fuels (Zhang & Wang, 2006). Such propagation of combustion waves is called ltration combustion. The latter is of great importance because it occurs not only in natural processes such as smoldering and underground res, but also in coal gasication, the self-propagating high-temperature synthesis of materials, regeneration of coked catalysts, calcination and agglomeration of ores, oil extraction and waste incineration (http://www.esam.northwestern.edu/~matkowsky/ngering.html). Problems faced in the combustion procedure were discussed and tentative solutions were evaluated. The reliability of the oxygen bomb IC procedures was established by testing the recoveries of a large group of organic compounds containing various heteroatoms. Combustion was carried out at thirty bar of oxygen (Souza et al., 2002). Miscanthus can be used as fuel for combustion in heating systems. Investigations were made in Denmark regarding combustion of Miscanthus Giganteus in farm heating plants. Full scale tests were carried out concerning combustion of Miscanthus Giganteus in the type of farm heating plant which is conventionally used for straw combustion. The combustion qualities were determined by means of fuel analyses and measurements of heating plant eciencies. In general, high softening, hemispherical and ow temperatures are considered to be advantageous (http://www.eeci.net/archive/biobase/B10367.html).
Biogas

air quality benets, studies also indicated that using biogas for transport, CO2 emissions could be reduced on a life cycle basis by between 65% and 85% on current fuels, depending on the feedstock used (http://www.ngvglobal.com/index.php?option=com-content&task=view &id=83&Itemid=2&lang=en). Compressed natural gas (CNG) comes primarily from fossil sources; although biogas, which is very similar to CNG, is produced from renewable sources. Biogas is examined in a separate entry, below. Three submissions were received that specically focused on promoting CNG, with a number of other submissions also mentioning its benets. Air quality benets are particularly signicant compared with heavy-duty diesel vehicles, and it is in these vehicles that CNG tends to be used. CNG engines are also signicantly less noisy than diesel engines. Again, this is a particular benet when CNG is used in heavy-duty vehicles (http:// www.defra.gov.uk/ENVIRONMENT/consult/greenfuel /response/03.htm). In addition to the animal and human wastes, plant materials can also be eectively used for biogas and biomanure production. For example, 1 kg of pre-treated crop waste and water hyacinth have the potential of producing 0.037 and 0.045 m3 of biogas, respectively. As dierent organic materials have dierent bio-chemical characteristics, their potential for gas production also varies. Two or more of such materials can be used together provided that some basic requirements for gas production or for normal growth of methanogens are met (http://www.fao.org/sd/EGdirect/EGre0022.htm).
Current and potential uses of corn and rice wastes

Biogas technology is a complete system in itself with its set objectives (cost eective production of energy and soil nutrients), factors such as microbes, plant design, construction materials, climate, chemical and microbial characteristics of inputs, and the inter-relationships among these factors. Biogas is about 20% lighter than air and has an ignition temperature in the range of 650 750 C. It is an odourless and colourless gas that burns with clear blue ame similar to that of LPG gas. Its caloric value is 20 Mega Joules (MJ) per m3 and burns with 60% eciency in a conventional biogas stove (http://www.fao.org/sd/EGdirect/EGre0022.htm). High energy yields were obtained from the production of upgraded biogas used for vehicle refuelling purposes. Comparisons indicate that energy yields from biogas derived from wheat are twice as high as wheat when used for ethanol production. As well as economic and

Biomass is considered to be a potential for the renewable energy sources in the future. It already supplies 14% of worlds total energy consumption. Biomass is also a source of a large variety of chemicals and materials. Biomass resources that can be used for energy production cover a wide range of materials such as forestry residues, energy crops, organic wastes, agricultural residues, etc. Agricultural waste, a readily available biomass, is produced annually worldwide and is vastly under utilised (Putun et al., 2004). Biomass is also a source of a large variety of chemicals and materials, and of electricity and fuels. About 60% of the needed process energy in pulp, paper and forest products is provided by biomass combustion. These processes could be improved to the point of energy self-suciency of these industries (Chum & Overend, 2001). Biomass fuels are the rst energy source harnessed by mankind. They remain the primary source of energy for more than half the worlds population and account for 14% of the total energy consumption in the world. Biomass is the most common form of renewable energy. The use of renewable energy sources is becoming increasingly important when it is

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considered to assist to alleviate global warming and provide fuel supply (Cuiping et al., 2004). Modelling and analysis of energy conversion processes require adequate fuel characteristics especially average and variations in elemental compositions. Knowledge of the concentration and speciation of alkali elements in fuels is useful for studies of Biomass Integrated Gasication Combined Cycle (BIGCC) or other biomass power generation topics (Cuiping et al., 2004). Development of biomass and other renewable power generation has distinct economic and environmental advantages. Despite this, the situation today in California is such that herbaceous fuels are virtually unusable by many existing biomass power generators using direct-combustion technologies (Thy et al., 2006). Using biomass as a source of fuel has little adverse environmental impact. The combustion of biomass produces signicantly less nitrogen oxide and sulphur dioxide than the burning of fossil fuels. Unlike fossil fuel combustions, the use of biomass fuels will not contribute to CO2 levels that cause global warming (Cuiping et al., 2004). Fuel ethanol plants are being commissioned and constructed at an unprecedented rate based on this demand, although a need for a more ecient and costeective plant still exists (Kwiatkowski et al., 2006). In recent years, research and development eorts directed towards commercial production of fuel ethanol from renewable resources as an alternative transportation fuel have increased. Currently, fuel ethanol is produced almost exclusively from corn starch. The economics of fuel ethanol production is signicantly inuenced by the cost of raw materials, which accounts for more than half of the cost (Krishnan et al., 2000). Even the reduction in cost of a few cents per litre of ethanol produced, is signicant when dealing with the dry-grind process, and the ability to accurately predict the costs of production prior to incorporating new technologies is highly desirable (Kwiatkowski et al., 2006). Todays corn renery industry produces a wide range of products including starch-based ethanol fuels for transportation. The biomass industry can produce additional ethanol by fermenting some by-product sugar streams. Lignocellulosic biomass is a potential source for ethanol that is not directly linked to food production. Moreover, through gasication biomass can lead to methanol, mixed alcohols and FischerTropsch liquids. The life science revolution we are witnessing has the potential to radically change the green plants and products we obtain from them. Green plants developed to produce desired products and energy could be possible in the future. Biological systems can already be tailored to produce fuels such as hydrogen (Chum & Overend, 2001). Ethanol is a renewable, bio-based oxygenated fuel. In the USA, the production of fuel ethanol from corn starch reached about 2.81 billion gallons in 2003. Developing ethanol as fuel, beyond its current role as

fuel oxygenate, will require developing lignocellulosic biomass as a feedstock because of its abundance and low cost. Previously, corn bre (obtained from corn wetmilling industries) was targeted as a model substrate for use as lignocellulosic biomass because of its high carbohydrate content (70%) containing 20% residual starch, 15% cellulose and 35% hemicellulose, and low lignin content (>8%) (Saha et al., 2005). The corn drygrind process is the most widely used method in the US for generating fuel ethanol by fermentation of grain. Increasing demand for domestically produced fuel and changes in the regulations on fuel oxygenates have led to increased production of ethanol mainly by the dry-grind process. Fuel ethanol plants are being commissioned and constructed at an unprecedented rate based on this demand, though a need for a more ecient and costeective plant still exists. The models were developed using software and they handle the composition of raw materials and products, sizing of unit operations, utility consumptions, estimation of capital and operating costs, and the revenues from products and co-products (Kwiatkowski et al., 2006). The production of bio-ethanol from corn stover using simultaneous saccharication and fermentation (SSF) at high dry matter content addresses both issues. Corn stover is an agricultural by-product and thus has a low economic value. SSF at high dry matter content results in a high ethanol concentration in the fermented slurry, thereby decreasing the energy demand in the subsequent distillation step (Ohgren et al., 2006). An economic analysis for ethanol production from glucose indicating that cost savings of 6 cents gal-1 could be achieved by using technology. These potential cost savings were realised because of higher ethanol yields, lower operating costs and lower capital costs for the continuous FBR process with an immobilised Z. mobilis biocatalyst compared with those for a conventional batch process using yeast (Krishnan et al., 2000). A by-product of the corn wet-milling industry consists of corn hulls and residual starch not extracted by the milling process. Conversion of the starch along with the lignocellulosic components in the corn bre would increase ethanol yields from a corn wet mill by 13% and is promising if the value of the corn bre as an animal feed product is not severely aected. Corn bre was obtained from a local corn wet mill and stored in a refrigerated trailer for no longer than a month. Usually multiple shipments (or lots) were required to supply the pilot plant with enough feedstock for operation during an extended run. The corn bre moisture content was 5560% (w w) as received (Schell et al., 2004). Rice (Oryza sativa L.) is an important crop in many areas of the world, and yields a large amount of rice straw residue. A major portion of this agricultural waste is disposed by burning or is mulched in rice elds (Abdelhamid et al., 2004). Rice straw has been described

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some potential uses. It is a marginal feed that would have to compete with other cereal grain straws such as wheat and barley. Most of the rice straw harvested went to animal feed. It has been reviewed with the use of agricultural residues, including rice straw, as a source of non-wood bres. It is most suitable for the production of corrugated medium and newsprint; however, the only commercial pulp mills using straw or bagasse exist in developing countries like India and China. It can be converted through bioconversion to ethanol, which is a clean-burning transportation-fuel oxygenate. Direct combustion of rice straw in a utility boiler of a biomass power plant is also an alternative for utilising rice straw, but leaching is required to avoid slagging and fouling (Kadam et al., 2000). Preparing compost from rice straw enriched with rock phosphate using cellulose degrading micro-organisms and phosphate dissolving ones may not only compensate for the higher cost of manufacturing fertilisers in industry but also provide the growing plants in alkaline soils with available phosphorous. Use of phosphate dissolving fungi in production of compost oers a solution to the waning interest of farmers in the use of organic phosphatic fertilisers in alkaline soils. The composts obtained were evaluated as organic phosphatic fertilisers in pots cultivated with cowpea plants. The eect of the composts on the microbial community structure of rhizosphere soils was also studied (Zayed & Abdel-Motaal, 2005). However, an attractive alternative usage of rice straw is composting. This process has many advantages including sanitation, mass and bulk reduction, and decrease of carbon (C) to nitrogen (N) ratio (C N). Rice straw is rich in C and poor in N. Its C N can vary from 50 to 150, which limits seriously the composting process. This high C N can be decreased by increasing the basal N content of rice straw by adding oilseed rape cake and poultry manure. The employed mixtures of Rice straw and N materials (cow dung + soybean plants) ranged at ratios from 70% to 100% rice straw. The mixture containing 70% rice straw produced the most suitable compost in terms of maturity and nutrients (Abdelhamid et al., 2004). Rice straw is commonly burnt in many of the developing countries. Burning rice straw has harmful environmental implications through global addition of carbon dioxide, a gas contributing to the greenhouse eect, and likely high health costs through increase in respiratory problems in the local population. The conversion of rice straw into value-added compost may have the potential to improve productivity of the crops and reduce environmental pollution. However, rice straw is among certain organic materials which are resistant to microbial attack (Zayed & Abdel-Motaal, 2005). The PY of rice straw was studied to estimate the eect of PY conditions on product yields and bio-oil composition when the heating rate was 5 K min-1. Liquid products obtained from PY, inert atmosphere

PY and steam PY were then fractionated into aspalthanes and maltanes. The chemical characterisation has shown that the oil obtained from rice straw may be potentially valuable as fuel and chemicals feedstocks (Putun et al., 2004). The addition of rice straw to wood fuels is expected to decrease both solidus and liquidus temperatures (i.e. the classic freezing point depression), but the magnitude of the depression cannot be predicted based on the available experimental data. In addition to the strong compositional eects on melting temperatures, the severity of slag formation and its ease of removal will depend on the amount of melt present as well as its composition and polymerisation. It is plausible that typical boiler conditions during combustion are within the melting temperature of slag from blended wood and straw fuel and, therefore, that melt will be present in the slag (Zayed & Abdel-Motaal, 2005). The traditional disposal method for rice and wheat straw in many parts of the world is burning. The burning of wheat straw is popular in China because of the short turnaround time between the wheat harvest and rice transplanting in ricewheat rotations. Estimated losses are up to 80% of N, 25% of P and 21% of K in addition to the problem of air pollution. Furthermore, declining or stagnating yield have been observed in rice-based cropping systems. Improvements are, therefore, required in the management of soil, water and straw (Fan et al., 2005). A change from traditional ooding (anaerobic) to nonooded mulching (aerobic) and the eects of nonooded mulching cultivation on soil temperature are likely to exert large inuence on N forms and availability and N cycling. Return of straw can also lead to temporary nutrient limitation because of microbial immobilisation. It is therefore important to test interactions between varying N inputs and non-ooded mulching cultivation and their eects on productivity and N cycling in ricewheat systems. As part of our evaluation of non-ooded mulching cultivation, the objectives of the present study were to determine the eects of non-ooded mulching cultivation and fertiliser N application rate on crop yield, N uptake, residual soil Nmin and the net N balance (Fan et al., 2005). Treatment methods, physicochemical characteristics, substrate to be applied and nal product uses of corn and rice wastes are given in Table 4.
Conclusions

The traditional disposal method for rice and corn straw in many parts of the world is burning which involves harmful environmental implications through global addition of CO2. A change from traditional ooding (anaerobic) to non-ooded mulching (aerobic) and the eects of non-ooded mulching cultivation on soil temperature are likely to exert large inuence on N

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forms and availability and N cycling. However, an attractive alternative usage of rice straw is composting. This process has many advantages including sanitation, mass and bulk reduction, and decrease of carbon (C) to nitrogen (N) ratio (C N). Using biomass (properly treated rice and corn waste) as a source of fuel has little adverse environmental impact. The combustion of biomass produces signicantly less nitrogen oxide and sulphur dioxide than the burning of fossil fuels. Unlike fossil fuel combustions, the use of biomass fuels will not contribute to carbon dioxide levels. Therefore, the three main axes of potential uses of treated corn and rice are biomass, composting, and biofuel in order of increasing potential.
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International Journal of Food Science and Technology 2008

2007 The Authors. Journal compilation 2007 Institute of Food Science and Technology Trust Fund

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