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A report for the Rural Industries Research and Development Corporation by Wondu Business and Technology Services
2006 Rural Industries Research and Development Corporation. All rights reserved. ISBN 1 74151 390 1 ISSN 1440-6845 Furfural chemicals and biofuels from Agriculture Publication No. 06/127 Project No. WBT-2A.. The information contained in this publication is intended for general use to assist public knowledge and discussion and to help improve the development of sustainable industries. The information should not be relied upon for the purpose of a particular matter. Specialist and/or appropriate legal advice should be obtained before any action or decision is taken on the basis of any material in this document. The Commonwealth of Australia, Rural Industries Research and Development Corporation, the authors or contributors do not assume liability of any kind whatsoever resulting from any person's use or reliance upon the content of this document. This publication is copyright. However, RIRDC encourages wide dissemination of its research, providing the Corporation is clearly acknowledged. For any other enquiries concerning reproduction, contact the Publications Manager on phone 02 6272 3186. Researcher Contact Details Wondu Business and Technology Services (Level 31, ABN AMRO Tower, 88 Phillip Street) Sydney, NSW, AUSTRALIA Phone: 61 2 93692735 Fax: 61 2 93692737 Email: infor@wondu.com In submitting this report, the researcher has agreed to RIRDC publishing this material in its edited form. RIRDC Contact Details Rural Industries Research and Development Corporation Level 2, 15 National Circuit BARTON ACT 2600 PO Box 4776 KINGSTON ACT 2604 Phone: Fax: Email: Web: 02 6272 4819 02 6272 5877 rirdc@rirdc.gov.au. http://www.rirdc.gov.au
Disclaimer Following half a century of development of the chemical industry with hydrocarbons as the feedstock, there is now renewed interest in using carbohydrates as the feedstock, mainly because of concerns about emissions and declining levels of non-renewable resources. Much of the viability of biorefineries depends on the price and expected price of oil, gas and naptha, which are used as the feedstock in traditional chemical plants to produce substitute products. Predictions about when a carbohydrate economy might emerge, and in what form, are subject to high levels of uncertainty. Increased funding for research into ways of improving the efficiency of traditional chemical refineries adds to this uncertainty. This report aimed to present an accurate picture of the situation and outlook for furfural, its associated products and its underlying technologies and raw materials. We were constrained by access to reliable data about different furfural technologies, and we invariably rely on claims by the owners of patents and technologies. The report aims to present an accurate picture of the situation and outlook for furfural and associated products, but, in an industry in which there is considerable research into developing new biorefineries, it is important to recognise that data can quickly become outdated. We also used a number of publications from other research to improve our understanding of particular developments and while we took care to ensure the authenticity of the publications we are not responsible for their errors and omissions, if any. Published in 2006 Printed on environmentally friendly paper by Canprint
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Foreword
The aim of this project was to examine the marketing potential for producing the chemical input, furfural, from Australian agricultural waste material, energy crops and hardwoods. Furfural is an intermediate product used by the chemical industry for making a range of chemical products. Furfural is one of the product possibilities from a biomass-based chemical refinery, which is viewed as having the potential to improve environmental performance and sustainability of chemical production. The study also examined new extraction technologies that may give higher furfural yields and lower processing costs. This technology could be able to use the relatively abundant supply of low-quality wood and waste from wood and other agricultural processing operations in Australia. While Australian rural industries are typically based on primary crop and animal products, there is an increasing market for co-products and, in some cases, the co-product can emerge as the main source of revenue. Growing incentives for greater use of renewable materials with fewer emissions in production and processing suggest an increasing role for agricultural materials being used in industrial products providing they are cost competitive. A key factor in cost competitiveness is full use of the material entering the processor and a full exploitation of the possibilities of adding value. Although furfural is essentially a commodity chemical it can also create increased demand at the farm gate for selected crops or to reduce processing costs. This report examines the market potential for furfural and it looks at some of the features of new processing technologies. It analyses data from the Australian and international markets and technologies that have been developed in eastern Europe to increase processing yields and reduce costs. This project was funded from RIRDC Core Funds, which are provided by the Australian Government The following report, an addition to RIRDCs diverse range of over 1500 research publications, forms part of our Environment and Farm Management R&D program, which aims to support innovation in agriculture and the use of frontier technology to meet market demands for accredited sustainable production. Most of our publications are available for viewing, downloading or purchasing online through our website: downloads at www.rirdc.gov.au/fullreports/index.html purchases at www.rirdc.gov.au/eshop Peter OBrien Managing Director Rural Industries Research and Development Corporation
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Acknowledgments
In conducting the study, we received support from a number of staff at the Latvian State Institute for Wood Chemistry, including Professor Nicholay Vedernikov and Dr Janis Gravitis; Maris Puke; Dr Janis Zandersons; Dr Aivars Zhurinsh; and Irena Vedernikov. We also met with Dr Martin Patel and Manuela Crank who are managing the European Commissions BREW project on the biotechnological production of bulk chemicals from renewable resources. Dr Branco Hermescec provide some comments on furfural technology and a fast pyrolysis technology that he is developing with the University of Melbourne. Paul Bennett edited the report and provided valuable advice on formatting and the general layout of content.
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Contents
Foreword ................................................................................................................................................ iii Acknowledgments .................................................................................................................................. iv Contents................................................................................................................................................... v Tables, Figures and Charts ..................................................................................................................... vi Abbreviations and Glossary .................................................................................................................. vii Executive Summary ............................................................................................................................... ix 1. Introduction ......................................................................................................................................... 1 1.1 Relevance and potential benefits ................................................................................................... 1 1.2 Objectives and scope of the study ................................................................................................. 2 1.3 Approach and method ................................................................................................................... 2 1.4 Outline of the report ...................................................................................................................... 2 2. Furfural Production Possibilities and Markets .................................................................................... 3 2.1 Furfural prices ............................................................................................................................... 6 2.2 The Australian market ................................................................................................................... 7 2.3 Phenol............................................................................................................................................ 7 3. Processing Technologies ..................................................................................................................... 9 3.1 Quaker Oats technology ................................................................................................................ 9 3.2 SupraYield................................................................................................................................... 10 3.3 Vedernikovs single-step furfural solution.................................................................................. 10 3.4 University of Melbournes process for recovery of furfural and phenols ................................... 10 4. Raw Material Sources ....................................................................................................................... 13 5. Discussion of Results ........................................................................................................................ 15 6. Conclusions and Recommendations.................................................................................................. 20 Appendix ............................................................................................................................................... 21 A verbatim reproduction of New technology for furfural and bioethanol production from lowquality foliage wood, by Nikolay Vedernikov, Laboratory of Polysaccharides, Latvian State Institute of Wood Chemistry ............................................................................................................. 21 Abstract ............................................................................................................................................. 21 Introduction ....................................................................................................................................... 21 Experimental ..................................................................................................................................... 22 Results and discussion....................................................................................................................... 22 Conclusions ....................................................................................................................................... 23 References (for this appendix only) .................................................................................................. 26 References and further reading.............................................................................................................. 27
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Acetone
Aldehydes
Benzene
Carbohydrate
FF
Hydrolysis
Hydroxyl Ketone
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Phenol
Toxic, white, soluble, crystalline, acidic derivative of benzene, used in manufacturing solvents, disinfectants and antiseptics. Class of carbohydrates that contains chains of monosaccharide molecules. Gaseous hydrocarbon (C3H6)(Chem.) from the ethylene group, produced by cracking petroleum Polytetramethylene ether glycol, a family of linear diols in which the hydroxyl groups are separated by repeating tetramethylene ether groups [HO (CH2 CH2 CH2 CH2-O-)nH] Transformation of a substance produced by the action of heat. Tetrahydrofuran Tetrahydrofurfural alcohol C6H5CH3, aromatic hydrocarbon, occurs naturally in crude oil and, less known, in the balsam-yielding tolu rainforest tree (Myrospermum Toluiferum), used to boost fuel, paints, and to make polyurethane and other products. Gum from the woody tissue of pentosan that produces xylose on hydrolysis.
Polysaccharide Propylene
PTMEG
Xylan
viii
Executive Summary
What the report is about This research concentrates mainly on the market potential for furfural and phenolic compounds and examines some of the features of new processing technologies that offer cost advantages. It analyses data from the Australian and international markets and technologies that have been developed in Eastern Europe to increase processing yields and reduce costs. Background Furfural (FF) is an intermediate commodity chemical used in synthesising a range of more specialised chemical products, starting mainly with furfural alcohol (FFA), which also has many derivatives. Furfural is used mainly in the production of resin, which is then used as a binding agent in foundry technologies. The second main use is as a selective solvent in petroleum production of lubricants. There are many other uses (adhesive, flavouring and as a precursor for many specialty chemicals (see figure 2.1)), but resins account for over 70 per cent of the market. Furfural is highly regarded for its thermosetting properties, physical strength and corrosion resistance. Furfural is important in terms of its presence, as a carbohydrate, in a chemical industry dominated by hydrocarbons. It seems to be one of the few renewable carbohydrate biomass products that can compete with hydrocarbon chemicals and without recourse to subsidies. Furfural is derived from the pentosan in the cellulose of plant tissues, the most prominent sources of which are corn/maize cobs, bagasse, paper-pulp residue, bamboo, kenaf, grain hulls, wheat and rice straw, nut shells, cottonseed and wood (soft and hardwood). Most furfural that is being produced today is derived from bagasse and corncobs. The best raw material prospects for Australia are bagasse, rice hulls and timber-processing residues. Bagasse, which is currently used mainly for energy in sugar mills, rice hulls and timber waste and sawlogs all have the volume available to provide feedstock for a small furfural plant of 5,000 tonnes/year. Target audience RIRDC supports the development of new industries and furfural and the associated products derived from carbohydrates fits within the mission of the corporation. This study is seen to be of use to chemical companies, agricultural processors, other R&D corporations (such as those dealing with sugar, rice, agro-forestry and timber) and producers of agricultural products. It is also of use to other researchers working in this and related fields. Objectives The scope of this report covers: identifying and examining product applications that can be made from furfural, and the associated local and export markets for them describing furfural processing technologies examining the raw material procurement options. The study does not extend to an economic/financial feasibility evaluation or to regional impacts. These concepts could be undertaken later. Methods This is the report of a concept study, not a detailed feasibility study. The concept being evaluated is new furfural processing technology, which is claimed to enable higher yields and improved productivity from a given level of inputs. Data for the study has been collected from the new technology originators, the Latvian State Institute ix
of Wood Chemistry, and other technology sources. Market data came from the Australian Bureau of Statistics, other statistical agencies and general providers of information about biomass-based chemical products, as well as the traditional petrochemical industry. The raw material sources are identified in the context of an Australian operation, but because furfural is an internationally traded commodity, chemical data on raw materials from other suppliers is also collected as a benchmark. Results The viability of furfural is sensitive to the cost of raw materials and, because of this, materials that are already assembled as waste, with potential negative costs at processing sites, have a significant cost advantage over materials that involve cash costs. The use of agricultural materials to make industrial products like furfural would add competition to the current supply chains, which are dominated by food uses. This competition would improve farm-gate prices for agricultural materials. Agricultural materials also offer the potential to improve environmental performance in the chemical industry, which currently have a heavy reliance on nonrenewable energy. In 200203, Australia imported about 500 tonnes of FF, valued at $1000/tonne, and 1100 tonnes of FFA valued at $1170/tonne. China, Thailand and South Africa are major suppliers. The world market for FF and FFA is around 300, 000 tonnes/year. World markets are not all free, and anti-dumping duties apply to imports from China into the USA and EU. These duties would probably not apply to imports from Australia into the USA. A minimum-sized furfural plant needs an output of at least 5,000 tonnes of furfural or derivatives, suggesting the need for exports from a plant based in Australia (which uses just 1600 tonnes of FF and FFA), or development of other derivative products. Phenol, which could be produced, along with furfural at the same plant, could be another option, with Australia consuming about 100 000 tonnes/year, most of which is imported. Phenol today, however, is a product of the major chemical companies, which have large, efficient-sized plants and low unit costs. There are also new technologies coming on stream, which will reduce costs and prices of phenol made from the traditional propylene and benzene feedstocks. Researchers need to factor-in the impact of new chemical industry technologies on future costs and prices of chemicals produced by the traditional hydrocarbon feedstock stream. A furfural plant with capacity of 5,000 tonnes/year would generate revenue of at least $5m/year, with potential to increase this to $10m depending on the extent to which further value adding takes place through development of products like phenol derivatives. The overall Australian market for phenol products is estimated to be more than $100m/year, with imports accounting for over 85 per cent. Biochemical production is attracting increasing interest as the price of oil approaches $US50/barrel. Research organizations in both North America and the EU are investigating new ways of making biochemicals from carbohydrates with a view to reducing dependence on fossil fuels. In addition, biochemical production offers the potential for impact mainly at the regional level. This is because a biochemical refinery would need to be located near the supply of carbohydrate materials to achieve the cost competitiveness necessary to operate in world markets. Conclusions Furfural, along with many products and co-products of biorefineries, requires more detailed technical, environmental, economic and institutional analysis. From this study it is clear that economic outcomes surrounding furfural are subject to major assumptions about the cost and availability of raw materials, processing yields, unit prices for products sold, capital investment required for commercial operations, and economies of scale and use of capacity. A small, independent start-up biorefinery faces significant risks because of both its small size and lack of distribution network for sales. This structure would probably need to demonstrate a return on invested capital of more than 20 per cent to compensate
investors for these and other risks, compared to 10 per cent if it were associated with an established, larger chemical company. This underlines the importance of strategic alliances in developing biorefineries. In their present state the technologies examined here lack detailed and robust links between technical and economic measures of performance and this limits the analysis necessary to enable selection and testing of different material inputs, different costs and product possibilities. It is generally agreed, however, that the chemical industry is vulnerable to environmental impacts and public perceptions about those impacts, as well as exposure to oil price increases. For this reason further research into products like furfural and other biorefinery co-products is likely to continue. To achieve useful results from further research into furfural and other biochemicals, it is important to have sufficient resources to systematically take a program of research through development, beyond laboratory scale results, then through a pilot plant to the commissioning of a small commercial plant. There is a lot of research into technical discovery at the theoretical and laboratory level, motivated in part by the benefits that might flow to the holders of the intellectual property. In reality, however, there are great risks in commissioning of plants and associated requirements for commercialisation. More attention is needed to deal with requirements of biochemicals along the whole supply chain, including measuring the environmental effects. International collaboration in research and development is essential, but inclusion of chemical industry partners is equally important if biorefineries are to move from a position of technical curiosity to even minimal commercial reality. The next step should be a detailed feasibility study into establishing a biorefinery, producing a range of chemical products, one of which would be furfural. This study should be undertaken in collaboration with one or more European and/or USA research institutes, and a chemical company with an interest in this area. The IP for making the furfural and related products such as phenol could be from the two technologies examined in this study, although this also needs to be kept under review as there are new discoveries being made with the considerable level of research going into this area.. It would also be useful to undertake this study with a pilot plant being established to enhance confidence in subsequent developments and commercialisation. In addition, end users of the materials made from biochemicals should be brought into the stakeholder network.
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1. Introduction
Furfural (FF) is a solvent produced from plant pentosans (xylan, arabinan and polyuronids), the complex carbohydrates contained in the cellulose of plant tissues. The product has attracted some interest because it helps in the feasibility of converting the relatively abundant supplies of lignocellulose feedstocks (that is, the materials used for transformation in processing) into ethanol and higher-valued co-product chemicals (Van Dyne, Blas and Clements 1999). Ethanol has faced viability problems with fluctuations in oil prices and occasionally very low oil prices in particular. Furfural and its derivatives have attracted interest because they are higher-valued co-products that could make an ethanol plant viable. Common sources of pentosans are corn/maize cobs (the main source), bagasse, paper-pulp residue, bamboo, kenaf, grain hulls, wheat and rice straw, nut shells, cottonseed and wood (soft and hardwood). Industrial product supply chains tend to be more sensitive to price levels than food supply chains and therefore access to a reliable, low-cost supply of raw materials is often a requirement for viability, not simply the presence of raw materials with a technical property that is used to make a particular chemical product. Furfural is consumed by the chemical industry as an intermediate product in synthesising chemical products such as nylons, lubricants and solvents, adhesives, medicines, and plastics. It is produced mainly by acid hydrolysis of cellulose or hemicellulose materials using acid solutions (usually mineral acids) to break down the polysaccharides into sugars. A major use (perhaps 65 per cent or more of world consumption) is for urea furan resin synthesis, a binding material used in metallurgy, precision casts and dies.
China has emerged as the dominant supplier of furfural and in 2001 accounted for over 70 per cent of world supplies. There are about 200 furfural producers in China, with an average production of 1000 tonnes/year. Linzi Organic Chemical Inc. claims to be the largest producer of FFA in Asia with annual output of 15 000 tonnes. Xing Tai Chunlei Furfural Alcohol Ltd is also among the largest with annual capacity of 10 000 tonnes of FF and 10 000 tonnes of FFA. Tieling North Furfural Group Co. is made up of 33 furfural factories in north-east China, with the capacity to produce 50 000 tonnes/year of furfural. The Dominican Republic (through Central Romana Corporation) is also a large supplier and accounts for about 11 per cent of world supplies (see table 2.2). Penn Specialty Chemicals at Memphis in the USA was a major supplier of furfural for that market and also produces PTMEG and THF and a range of other specialty chemicals derived from these products. Current production of furfural from Penn Specialty Chemicals appears to be negligible. Penn Specialty Chemicals purchased the furfural plant from Great Lakes Chemical Corporation and Quaker Oats 3
Chemicals in 1999 at a time when Great Lakes divested its furfural investments in both the USA and Belgium. In Germany, NC-Nature Chemicals in Hamburg is a major producer. In Spain the Furfural Espanol S.A. company has furfural capacity of about 5000 tonnes/year. In India, KRBL, India's leading rice exporter, has recently announced it will be producing 3000 tonnes/year of furfural from rice husks. India has been importing FFA from China to make high-value derivatives.
Chart 2.1: Furfural and selected derivative specialty chemical products
Figure 2.1: Furfural application scheme (reproduced, verbatim, from the newspaper Darba Partijas Avize, cited in Vedernikov 2000)
Rubber (divinylethylene) Perfume FURFURAL Flavouring agents Sintane
Paints & varnishes Sulphuric dyes for photography Dilute dyes Liquid for dyes washing away Dye stuffs
Plastics, resins, synthetic fibre Nylon (2 amino enanthic acid) Polymers of furanol Phenol-furfural resins Polymers of furyacrylic acid Pasting compositions
Agriculture
Medicine
Selective dissolvents
Herbicides
Nitrofuran
Dihydro pyrane
Fungicides
Furamone
Tetrahydropyran
Insecticides
Pyridine
Bactericides
Pentane diols
Disinfectant
Varnishing stuffs
Lubricating oils
Preservant
Valerian lactone
Hydrogenated fats Separation of different molecular weight molecules Engine cleaning fluids Isolation of butadiene from cracking gases Concentration of vitamin A
Piperylene
Butanol
Furan
2000 1800 1600 1400 1200 1000 800 600 400 200 0
1997-98
1998-99
19992000
2000-01
2001-02
2002-03
6-year average
Furfural
Furfural alcohol
2.3 Phenol
Phenol is another product that could be produced alongside furfural in a biorefinery, or as a valueadding option (see later comments connected with Hermescec 1999). The global supply of phenol is expected to be around 7.5 million tonnes in 2004 (Takeno 2004). Phenols are similar to alcohols, but more soluble, more acidic and with higher boiling points. They are synthesised by either the hydrolysis of chlorobenzene or the oxidation of cumene in air to form hydroperoxide. The main reaction of phenol is its condensation with formaldehyde. The main product derivatives from phenol are bisphenol A (BPA) (for polycarbonate and epoxy resins), phenolic resins (for moulding binders and insulation wool), cyclohexane (for caprolactam), alkylphenols (for surfactants), and salicyclic acid (for pharmaceuticals) (www.chemicalLand21.com). More technical details about BPA, and a defence of claims about adverse health side effects can be found on http://www.bisphenol-a.org. BPA is used to make polycarbonate plastics (a substitute for glass) and epoxy resin (for coatings and liners in metal containers). Huntsman produces a range of phenolic resins at their chemical plant in Footscray, Victoria. Phenolic resins are used in wood products, in electrical, automotive, and thermal insulation products, and in building and construction. Cyclohexane is produced from benzene and used mainly to make nylon 6 and nylon 6,6. Furfural was previously the main material used to make nylon 6,6 but cheap oil substitutes resulted in its replacement. Alkylphenols and its derivative, alkylphenol ethoxylates, are used mainly to produce surfactants and cleaning compounds. They are used in pulp and paper, textiles, pesticides for agriculture, lubricating oils, metals and plastics. Nonylphenol is a major derivative of the alkylphenols group and accounts for 85 per cent of the alkylphenols product group (http://www.aperc.org). The phenol ester, phenyl salicylate or salol,, is used in medicine as an antiseptic or antipyretic (http://www.bartleby.com/65/sa/salicyli.html).
Chart 2.3: Furfural and furfural alcohol imports, Australia, 199798 to 200203 (tonnes)
1800 1600 1400 1200 1000 800 600 400 200 0 1997-98 1998-99 1999- 2000-01 2001-02 2002-03 2000 Furfural-Ex China Furfural total FA ex Thai Furfural-Ex RSA Furfural alcohol ex China Furfural alcohol total
In 200203 the value of imports of FF and FFA into Australia was estimated to be $1.6m. Local production is negligible, as are exports, and therefore apparent consumption is also $1.6m.
The overall Australian market for phenols is estimated to be around $116m in 2004, with imports accounting for over 85 per cent of the market, some of which is re-exported. The main domestic supplier is Huntsman with sales of around $20m/year.
Table 2.3: Phenol consumption, Australia, 2004 ($Am)
January Imports Production Exports Apparent Consumption 7 2 2 7 February 13 2 2 13 March 9 2 3 8 Estimated total for year 2004 120 24 28 116
Source: Australian Bureau of Statistics, Cat. 5368.0, International Trade in Goods and Services.
In the global market, production of phenol is expected to be around 7 million tonnes in 2004 (Takeno 2004). Shell Chemicals, Aristech, Phenolchemie, Enichem and Ertisa are major suppliers.
3. Processing Technologies
Furfural is a liquid aldehyde with its typical CHO structure (figure 3.1). It is produced from the dehydration of pentoses, typically produced after an initial hydrolysation stage, with acid catalysts (e.g. sulphuric or phosphoric acid) used to intensify the extraction process. Furfural has derivatives, including FFA (and its derivative furfuralamine), furoic acid, furanacrylic acid, furylidene ketones, furan, and tetrahydrofuran (Lichtenthaler 2002).
Figure 3.1: Furfural: formula: C5H4O2
Source: Department of Biochemistry and Molecular Biology, University College, London (http://www.biochem.ucl.ac.uk/bsm/pdbsum/1qxd/main.html)
Both batch and continuous processing methods are used, but batch processing is mostly used nowadays. Previous manufacturers of the plant for the continuous process include Defibrator and Rosenlew (Sweden and Finland), Societa Italiana Furfurola (Italy), and Escher Wyss (Germany), but these manufacturers now have either stopped production or scaled back. Batch plants are available from China and possibly South Africa. The option to engage in further processing of the lignocellulose residue or use it as an energy source for the initial furfural process is available in both methods. In each of the methods there is different emphasis on the yield and recovery of co-products, raw material inputs and their prices, plant size and capital investment, and product quality.
the technology has been shown to work and produces furfural for sale in world markets. Huaxia Technology, a subsidiary of Westpro Company in California, is using a variation of the Quaker Oats technology to produce furfural in China.
3.2 SupraYield
SupraYield was developed from patented technology owned by Karl Zeitsch, a pioneer in furfural technology, and it has been taken up by a South African group. SupraYield claims higher yields (50-70 per cent furfural) and lower operating costs. This technology does not appear to be in commercial use, although Queensland sugar producers are evaluating a form of it.
Figure 3.2: Furfural pilot plant at the Latvian State Institute for Wood Chemistry
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fluidised bed pyrolysis reactor used here has smaller feedstock particle sizes and claims relatively low energy requirements. The process seems to make full use of all residues. The main outputs are furfural alcohol and phenols. This technology appears, however, to be at a very early stage, little beyond research and facing investment in product development and a pilot plant for testing before it goes any further. A summary of some key differences between technologies is shown in table 3.1. These estimates are very broad guidelines and should be treated with extreme caution as they are often from pilot plant operations or small laboratory-scale experiments or just straight guesstimates. Huaxia is a more reliable estimate because they are actually in production. Vedernikov has undertaken a quite comprehensive costing and has the benefit of a pilot plant experience (figure 3.1). Vedernikovs technology is also understood to be applied commercially in a Russian plant producing 8000 tonnes/year of furfural, though we were unable to verify this. Both SupraYield and University of Melbourne/Hermescec are at a concept stage.
Table 3.1: Comparison of furfural processing technologies
Vedernikov Technology Pilot & at least semi-commercial 6 900 100 10 000 22 69 Furfural +75 1 650 650 ***0.22 NA 850 University of Melbourne & Hermescec Laboratory 6 500 100 10 000 22 65% Phenols NA NA NA 0 NA 234
Variable State of development Capacity (tonnes/year of total product) Assumed capacity utilisation (%) Materials used (tonnes of dry mass) Pentosan content of dry mass * Total product recovery (% of dry biomass) Product focus Yield of furfural (% of theoretical) Furfural production (tonnes) Power (kWh/tonne of furfural) Sulphuric acid (t/t of furfural) Emissions Capital investment ($/tonne of product sales) **** Co-products
Huaxia Technology Commercialised 4 500 100 10 000 22 45 Furfural 35 770 400 **0.55 NA 405
NA
Furfural, cellulose
* Depends on raw material and its pentosan and moisture content ** Dilute sulphuric acid *** Concentrated (93%) sulphuric acid **** Cannot be compared because of different measurement methods and different products
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Comparing the different furfural processing technologies is constrained by lack of detailed results from the providers, except for that of Vedernikov who has published his results widely and openly. The owners of patents are often unable to answer important questions about their technology, perhaps because of confidentiality or a desire to not expose technologies to detailed scrutiny by competitors. In this context the Latvian technology has an edge over competing technologies, which make claims for higher yields without publishing technical details supporting those claims, and in testing the technology, which Vedernokov has been able to do at the Latvian pilot plant.
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Source: International Furan Technology, and Latvian State Institute of Wood Chemistry
Bagasse and corncobs are the two most common materials used in furfural processing plants, and together they account for more than 98 per cent of all furfural produced, with corncobs dominating the material supply in China, the largest producer. The potential yields of pentosan depend on the extraction technology used. This can range from 25-75 per cent or more. Huaxia Furfural Technologies claim to be achieving the following yields: corncobs 1012 per cent, rice hulls 57 per cent, bagasse 811 per cent, and wood 48 per cent, which translates to about 30 per cent of the theoretical potential for these products. The other key feature of the currently available furfural is that it is derived almost entirely from residues, that is, bagasse from sugarcane processing and corncobs from processing. This means there are no expensive direct costs in procuring raw materials, which is already assembled at central points in relatively large volumes. In Australia the raw materials that have relatively high pentosan content and that may be available in central locations and at reasonable volume include bagasse, rice hulls and wood-processing residues. Eucalyptus plantation wood could also be competitive provided it is already assembled at a central site and in sufficient volume. Table 4.2 shows some of the resources that could be used for furfural production in Australia. While maize is listed here as a source of input for furfural, it is an unlikely
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commercial candidate because, unlike China, most maize in Australia is harvested by machine for the grain, and there is little centralised collection of cobs.
Table 4.2: Australian raw materials for furfural: by plant origin
Plant origin Rice (t) Rice hulls (%) Rice hulls quantity (t) Sugarcane Bagasse (%) Bagasse quantity (t) Maize Cobs (%) Cobs quantity (t) Timber (million m of hardwood) Sawlogs (%) Pulp (%) Residuals (%) Share of timber products for furfural Sawlogs (%) Pulp (%) Residuals (%) Timber for furfural Sawlogs (M m3) Pulp (t) Residuals (t) 80 000 121 600 296 000 16 000 24 320 59 200 2 2 5
3
Output 1 200 000 20 240 000 40 000 000 25 10 000 000 *450 000 25 112 500 16 25 38 37
Pentosan %
17 40 800
24 2 400 000
35 39 375
20 20 20
*Most of Australias maize crop is mechanically harvested and cobs are left behind as residue. Collection of this residue would involve significant cash costs, as well as a reduction in soil quality, caused by removing organic matter.
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5. Discussion of Results
To improve our understanding of the main differences between Vedernikovs technology and the traditional Quaker Oats two-step process, we invited Dr Branco Hermescec to comment on the results. This section describes, first, Dr Hermescec assessment (quoted verbatim).
The Vedernikov technology is viewed as still being at the experimental stage, though it appears innovative and if sufficient investment of capital, expertise and engineering is applied, a promising technological development is possible. However, the paper does not go far enough on the processing of solid residues at the end of the processing stage. Granulated lignin in the context of the overall utilisation is a low-valued fuel product. Further processing of lignin could yield substantial quantities of low molecular weight phenols, such as vanilan, guaiocol and syringol. There also may be some irregularities with the base calculations in regard to the mass balances, with 1000 kg of raw material yielding 690 kg of various products. The mass estimated for CO2 is probably too low as the fermentation process should yield alcohol and CO2 in about the same amounts. (This suggests the alcohol yield may be overstated). Costs of the Vedernikov technology would need to be completely reviewed for another time period (originals for 1999) and another country (originally applied to Latvia) where labour, capital, land, environmental regulations and other operating costs would be quite different. High returns are also ascribed for thermal energy, a byproduct of the manufacturing process. In practice, however, most energy from the process would be used in situ for heating the reactor, preheating of materials and drying processes. The feedstock is likely to contain high levels of water. Therefore, fuel (that is, thermal energy), should not be presented as a negative cost in the budget. At face value there is little likelihood of the proposed manufacturing plant based on Vedernikovs technology achieving financial viability because: the plant size of 5000 tonnes of furfural and 8000 tonnes of ethanol appears to be too small to achieve cost economies against larger plants the lignin component remains under-utilised engineering tasks could be complex and commissioning procedures would be risky and expensive
Responding to these questions Vedernikov accepts that furfural by itself is not viable without very low-cost feedstock and that higher-value chemicals need to be produced, and more use made of the residual lignin (15 per cent of the dry matter in corncobs) to make, for example, phenols and cellulose (31 per cent of the dry matter in corncobs) and ethanol. There are several key factors that can significantly influence the viability of a furfural processing plant: 1. Raw material access, volume and cost McArthur and Frolich (1996) in a study of biomass pyrolysis processes to produce furfural, formic acid and levulinic acid found, like Himmelblau (1995), that the cost of biomass materials had a significant impact on returns, and that woodchips would have to be free of cost to achieve viability, unless the products and yields are high, and high unit values are ascribed to sales. There also needs to be access to a reliable and continuous stream of raw materials. It is the access to a reliable and continuous stream of oil, gas and naptha that provides the traditional petrochemical industry with its long-standing cost advantage. 2. High yields and relatively high average unit values for the output The underlying yields of the biomass and the actual recovery levels in processing have major effects on viability. One of the reasons for the relatively high projected IRR from the technology of Melbourne University and Hermescec is the recovery of saleable high-valued products, which are projected to translate to 0.325 tonnes/tonne of wet hardwood sawdust used. It is estimated that 80 per cent of the dry weight of the sawdust biomass can be converted to phenols, cellulose and 15
furfural. This recovery rate, however, appears to have been achieved in the laboratory only. Also the prices for phenol products may be overstated. Current phenol prices are around $US700/tonne, which is 25 per cent less than that assumed for this technology. Moreover, the phenol market is dominated by some very large companies like Shell Chemicals, which exploit the economies of scale in processing and distribution. The prices for chemicals reflect market demand and the underlying variable and fixed costs of processing and distribution. In the long term prices reflect total costs. The Institution of Chemical Engineers identify four broad groups of chemicals that have different processing and distribution costs, giving a hierarchy of total costs and ultimately a hierarchy of prices: basic chemicals and minerals, supplied by pipe or bulk cargo, with prices around $275/tonne (including crude oil and naptha) common intermediate chemicals, with prices around $800/tonne (this group includes products like furfural, acetic acid, benzene, phenol) monomers or less common intermediates, with prices around $2400/tonne (this group includes products like acrylic acid, dichlorobenzene) specialty chemicals, with prices around $4500/tonne (this group includes styrene and silica gel). Selection of the group of chemicals on which to focus is one of the most important strategic decisions in establishing a biorefinery. Management must consider, among other things, the level of current and future competition, access to materials and quality of the product.
Chart 5.1: Chemical price points: by broad group and selected products: $A/tonne
Specialty chemicals
Monomers
* Note: These prices are volatile. For example, FFA in July 2004 is trading for closer to $1500/tonne. Lichtenthaler (2002) observes that furfural appears to be the only unsaturated large-volume organic chemical that is able to compete with low-cost fossil-fuel-based materials. 3. Capital investment and returns required The capital investment required for any of these technologies is uncertain and could undermine returns to investors. Commissioning costs, especially for unproven technologies, are likely to be high and the
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threat of environmental constraints is another source of uncertainty. These risks would mean that investors would expect higher returns than would be available from other, less risky investments. Many assessments of the advisability of setting up a biorefinery fail to consider the likely returns an investor would expect for an investment in a biorefinery, which has features of both the chemical and biotechnology sectors. In addition, there is often the added complexity of the investment being a startup operation, without commercial links to markets and raw materials. This adds to the risk. The cost of capital for any business can be estimated from the weighted average cost of equity and debt capital (Brealey and Myers 1981): Cost of capital = cost of equity (E/D+E) + after-tax cost of debt (D/D+E) Where E = the value of equity funds, and D = the value of debts to be used. Debt is usually cheaper to access than equity, as long as the lenders are willing to lend for the investment. This usually presents a problem for start-up companies, and biorefineries are no exception. The typical biotechnology company listed in the USA has a market debt : equity per cent of just four per cent compared to the chemicals group of around 30 per cent (Stern 2004). It is probably reasonable to say that if the investor in the biorefinery were a business like Shell Chemicals, the debt : equity ratio would be closer to the chemicals group as a whole, but if it were a start-up company, the ratio would be closer to four per cent. That is, for large companies like Shell, there is a better chance of obtaining a loan than there would be for a small company, which might actually have to fund everything from relatively high cost equity. The cost of equity comprises the risk-free rate, plus a premium for risk: Cost of equity = risk free rate + beta (risk premium) (2) (1)
The long-term government bond rate is used for the risk-free rate (currently 5.9 per cent in Australia) and the typical risk premium over the long term is 5.5 per cent. Beta is derived from a regression of monthly returns on stocks or stock groups against a composite of stocks. The beta for biotechnology stocks in the USA is 1.2; for basic chemicals it is 0.88; for diversified chemicals it is 0.83; and for specialty chemicals it is 0.8. The after-tax cost of debt = pre-tax cost of debt (1-tax rate). The pre-tax cost of debt requires a risk premium to be added, and this would be around 12 per cent for a small company starting up in Australia. From the above, the estimated cost of capital for a biorefinery entering a commercial stage would be around 13 per cent. Cost of equity = 5.9 + (1.2)(5.5) = 12.5 Cost of debt = 12%(1-0.3) = 8.4 Cost of capital = cost of equity (E/D+E) + after-tax cost of debt (D/D+E) = 12.5(0.96) + 8.4(0.04) = 12.4%. This is the estimated cost of capital (12.4%) for a biorefinery that has proved itself through to, say, a commercialised plant stage and has an effective structure that investors would have reasonable confidence in. If the biorefinery were owned by a larger chemical company, the debt is likely to be higher, the betas lower and the overall cost of capital closer to 10 per cent. For a small start-up, without any external backing, the cost of capital for the biorefinery is likely to be above 20 per cent.
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The required rates of return also decrease as risk is reduced with progress through the research, development and commercialisation stages. At the research stage the probability of a particular research project reaching commercialisation is less than five per cent; at the development stage it could be 20 per cent; and at the pilot stage it could be 50 per cent. After the pilot stage there are still significant risks in commissioning and organisation. At the research stage it would not be unusual for investors to require a return of 50 per cent; at the development stage 40 per cent; and at the pilot stage 30 per cent. These differences in required rates of return have a major impact on viability. It is also very clear that an investment is more likely to proceed if a large chemical or biotechnology company becomes part of the project.
Chart 5.2: required rates of return: furfural and biorefineries
ROI [%]
50 45 40 35 30 25 20 15 10 5 0
Research
Pilot plant
4. Economies of scale, new technology and use of capacity There are economies of scale in furfural production and biorefineries generally. One of the first facts to consider with biorefineries is that the more they develop their product range the more likely they are to come into competition with the traditional chemical companies. Shell Chemicals, for example, is building a new phenol-acetone production plant in Singapore with annual capacity of 330 000-440 000 tonnes/year (Takeno 2004). Economies of scale will enable this plant to be among the lowest-cost producers of phenol in the world. Moreover, the plant embodies new technology that will reduce variable costs (which include propylene and benzene) of producing phenol by more than 50 per cent. These extraordinary improvements in technology pose enormous threats for biorefineries waiting to see the price of oil rise to make them competitive. The traditional economies of scale in manufacturing have not been tested with biorefineries, mainly because of feedstock limitations. According to the standard scaling law, when a plant doubles in size its cost increases by a factor of (2/1)0.6, which is about 52 per cent. Of course, the plant has to be able to operate at full capacity to achieve the cost advantage. More generally, as processing technologies improve and raw material feedstocks become more reliable and integrated with processing, it seems reasonable to expect economies of scale to assert themselves on the structure of biorefining in the same way they have governed the structure of the traditional chemical industry. The new cellulosebased ethanol plant at Iogen in Canada (a subsidiary/associate of Shell) is being built to produce 170 million litres of ethanol/year from 1500 tonnes/day of wheat, oats and barley straw. Biorefineries 18
of this scale will almost certainly emerge with major positions in the biochemical market, as well as being more significant competitors to the traditional chemical market. 5. Aesthetics, product differentiation and the end market for products from a biorefinery Its a long way from waste and agricultural materials through furfural and pentosans to end products that might include plastics, cleaners, glues, inks etc. In the end, it is the end-product user who drives demand and chemical demand is derived from it. For this reason it would be useful in any future research work to establish contact with the end-user product groups: resins, paints, flavouring agents, pharmaceuticals etc. (refer to figure 2.1).
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Appendix
A verbatim reproduction of New technology for furfural and bioethanol production from low-quality foliage wood, by Nikolay Vedernikov, Laboratory of Polysaccharides, Latvian State Institute of Wood Chemistry
Dzerbenes 27, LV-1006, Riga, LATVIA Email: ved@edi.lv Fax: +371-7310135
Abstract
In the near future foliage wood may be as a real alternative to oil as raw material for production of chemicals and motor fuel. A new approach to solve this problem consisting of differential catalysis of hydrolysis and dehydration reactions has been found. The aimed change of the mechanism of the process has permitted to solve two problems simultaneously: to make increase the furfural yield from 55 per cent up to 75 per cent from theoretical and to diminish 5 times degree of the cellulose destruction. On the basis of theoretical studies a new technology including two-step hydrolysis of foliage wood and other pentosan containing raw material has been elaborated. Since 1997 for the first time in the worlds industrial practice this technology yielding furfural and fermentable sugars further processed into bioethanol has been realised in Russia with capacity 4.300 t/a of furfural and 8.800 t/a of bioethanol. The degree of raw material utilization has grown 3 times, the total yield of furfural and fermentable sugars 4 times when compared to the only furfural production.
Introduction
The oil is the main chemical raw material now, but following the forecast of leading geologists (Science, 1998) the oil obtaining already in 10 years will rapidly decrease and its price would increase, correspondingly. Therefore, following forecast of USA specialists, almost 30 per cent of all the production of organic chemistry already in 25 years would be produced from biomass, and it would be more than 100 million tons per year. The plant biomass formed in the process of photosynthesis in amounts of 21011 tons per year exceeds 20 times the summary output of all non-renewable organical raw materials (coal, oil and gas). The low-quality foliage wood and agricultural wastes prove as cheapest and most available from all the photosynthesised biomass for chemical processing. Using 3 main intermediates furfural, ethanol, and phenol obtained from corresponding wood components (pentosans, cellulose, and lignin), 95 per cent of all synthetic materials actually obtained from oil could be produced. Forests in Latvia cover 43 per cent of all the state territory. There is big amount of low-quality foliage wood (aspen, alder) and also wood wastes having no economically effective application. The furfural and bioethanol production proves as perspective trend of application of such a wood. Already now furfural is produced in more than 100 plants in 19 countries, and the total production amount is 300 000 t per year. Ethanol is produced from wood in 18 plants (120 000 t per year), and scientists in USA, Canada, Sweden, and other developed countries work to elaborate new technologies to obtain this product from biomass. But, simultaneous obtaining of these two products till nowadays was considered as theoretically impossible because of near values of kinetical parameters of furfural formation and cellulose
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destruction. This results in the 4050 per cent cellulose destruction during the furfural-obtaining process and the residue of the raw material may be therefore used only as fuel and fertilizers. The other problem, which has not been solved during 77 years of the industrial furfural production, was a comparatively low yield of furfural not exceeding 55 per cent from theoretical. The mechanism of the process was to be changed in order to solve both problems simultaneously. It was done on the basis of a new non-traditional approach theory of differentiated catalysis of the hydrolysis and dehydration reactions done simultaneously in one apparatus.
Experimental
The experimental researches in an original pilot plant with reactor of 10 l volume and 2 m height have been done. This pilot plant allows modelling of the industrial process changing the main parameters in a large interval. Special methods to detect main kinetical parameters relating not laboratory, but industrial conditions have been elaborated. It gave possibility to optimise the technology applying the kinetical parameters obtained.
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decreases about 20 times reaching 1:500. According to the theory of differentiated catalysis this condition enhances a reduction in the furfural loss due to the side reactions and secondary conversions. The fundamental regularities were first discovered in the furfural formation from birchwood (tables 2, 3) and other pentosan-containing raw materials in the presence of small amounts of concentrated catalyst solutions. Certain kinetical properties and activation parameters of the process were determined, effective catalyst concentration values were calculated, and regularities of its conversion within process were defined according to the conditions of the process. A quantitative evaluation of the degree of influence of moisture, the type of raw material, amount and concentration of catalyst, temperature and duration of processing, the rate of steam and other factors upon the furfural yield were compared. Regression equations enabling an optimization of process were obtained. As result of this research the furfural yield increased from 55 per cent up to 7080 per cent from theoretical. The application of small amounts of concentrated sulphuric acid also prevents the destruction of cellulose to be used in the further processing. Thus it was shown that contrary to the conventional theory, a higher concentration of the catalyst solution and a reduced volume of it to the raw material, significantly reduced the cellulose destruction. The amount of cellulose destroyed is approximately five times less. Further, the degree of polymerization, the cristallinity index and the molecular homogeneity of cellulose tend to grow. Beside the furfural formation process the kinetics of polysaccharide hydrolysis were studied enabling a choice of an optimum technological variant according to the raw material and the type of processing, including two-step hydrolysis. The research has resulted in a new technology for the furfural obtaining from foliage wood and other pentosan-containing plant raw materials in the presence of small amounts of concentrated acid and salt solutions as catalysts. The test of this method in pilot and industrial conditions have confirmed the newly discovered regularities and proved the process to be easily modelled, even if the reactor volume is to grow several thousand times (from 10 to 60 m). The novel technology (2) has provided a possibility to solve two technical problems simultaneously: to increase the furfural yield for 2025 per cent and to preserve the cellulosic part of the raw material for a further chemical processing. As a result, for the first time in the worlds industrial practice, the problem of complete utilization of foliage wood polysaccharide complex yielding furfural and fermentable sugars to be used subsequently for the production of bioethanol and other microbial synthesis products has been solved. To realise this process an original construction of two-shaft helix-shaped blade mixer of a continuous action and air disperser have been developed. When modelling the mixing processes of raw material with catalyst, diffusion model parameters of hydrodynamic structure of the material internal flows, depending on the length and equivalent diameter of the mixer have been determined. The optimum layout diagram of blades on the mixer shafts, their configuration, shaft distance as well as the number of their revolutions, have been experimentally determined. The optimum combination of these parameters has provided the uniform distribution of the catalyst in the raw material mass. The equipment of various capacities for the raw material mixing with catalyst solutions is being currently manufactured.
Conclusions
For the first time in the worlds industrial practice, the new technology allows to obtain furfural from pentosans and fermentable sugars from cellulose in one two-step process. Since 1997 this new
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economically feasible process has been successfully applied in Russia with capacity 4.300 t/a of furfural and 8.800 t/a of bioethanol production from foliage wood. The degree of raw material utilization has grown three times, the total yield of furfural and fermentable sugars four times when compared to the only furfural production. The solution of the problem of simultaneous obtaining of furfural and bioethanol would permit in the near future to use the low-quality foliage wood and agricultural wastes as alternative to oil as chemical raw material and motor fuel.
Table A1: Changes in the constants of pentosan hydrolysis (k1) to furfural formation (k2) ratio in dependence on concentration of sulphuric acid
Concentration of H2SO4, % 10 20 30 60 90 k1102, min-1 14.58 15.76 16.50 15.84 16.17 k2102, min-1 0.251 0.816 1.024 1.450 1.954 k1/k2 58.1 19.3 16.1 10.9 8.3
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WOOD
25% Pentosans 40% Cellulose 25% Lignin
FURFURAL
ETHANOL
PHENOL
95 per cent of all now-produced synthetic materials may be obtained from these three products
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Figure A2: The principle scheme of manufacture of furfural, bioethanol and other products from foliage wood.
Foliage wood
1000 kg*
42 kg
92 kg
Ligno-cellulose
Depolymerization of cellulose
172 litres
70 kg
Fuel granules
320 kg*
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Huntsman Chemicals 2004, Phenol, acetone and cumene hydroperoxide, http://www.huntsman.com Hyundai Heavy Industries 2003, Furan resin for propeller casting, New Horizons (webzine), http://webzine.hhi.co.kr/english/200311/engine.htm Iogen Corporation 2004, Corporate Information, http://www.iogen.ca Lichtenthaler, F., 2002, Unsaturated O- and N-heterocycles from carbohydrate feedstocks, Accounts of Chemical Research, vol. 35, no. 9. Lichtenthaler, F. W., and Peters, S. 2004, Carbohydrates as Green Raw Materials for the Chemical Industry, Elsevier SAS McArthur, K.A., and Frolich, M. 1996, Financial Feasibility Analysis of Alternative Potential Biomass-Based Products, University of Nevada, USA. Official Journal of the European Communities, 18 December 2003, Notice of initiation of an expiry review of the antidumping measures applicable to imports of furfuraldehyde originating in China. Shukla T. 2004, Global Corn and Starch Conversion Business, T.Shukla Consulting Services, Mumbai. SRI Consulting 1998, Chemical Economics Handbook, SRI Consulting, cited in personal communication from N. Vedernikov. Stern N. Y. 2004, Beta Data List and Variables Used in Data Set, New York University Takeno K. 2004, Phenol and acetone market outlook and investment update in Asia, Presentation by the President of Shell Chemicals to the Centre for Management Technology Forum, Bangkok, 12 February. United States Patent Office 1936, Method for the Production of Furoic Acid, no. 2 041 184, application no. 608 417, Lloyd L. Isenhour, Chicago, assignor to The Quaker Oats Company. Van Dyne, D. L., Blas, M. G., and Clements, D. L. 1999, A Strategy for returning agriculture and rural America to long-term full employment using biomass refineries, in Janick, J. 1999, Perspectives on new crops and new uses, ASHS Press, Alexandria, VA. Vedernikov, N. 2000, Production of Furfural and Ethanol from Deciduous Wood, Latvia State Institute of Wood Chemistry, Riga. Vedernikov, N., Kruma, I,. Zandesron, J., Zhurinsh, A., Tardenaka A., Spince B., & Chirkova J. 2003, Production of furfural and carbon materials from deciduous tree wood wastes, paper for the Seventh European Workshop on Lignocellulosics and Pulp, Latvian State Institute of Wood Chemistry. Westpro Chemicals 2004, Huaxia furfural technology, http://www.westprochem.com/
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