Survey of Future Biofuels and Bio-Based Chemicals

International Centre for Science and High Technology United Nations Industrial Development Organization
SURVEY
OF FUTURE BIOFUELS AND BIO-BASED CHEMICALS
Prepared by a group of ICS-UNIDO experts Gabriele Centi, Paolo Fornasiero, Martin Kaltschmitt, Stanislav Miertus, Franziska Mller-Langer, Stefan Rnsch, Arumugam Sivasamy, Daniela Thrn, Alexander Vogel, Sergey Zinoviev
May 2008
Contributors
Gabriele Centi, University of Messina, Italy Paolo Fornasiero, University of Trieste, Italy Martin Kaltschmitt, The Leipzig Institute for Energy (IE Leipzig), Germany Stanislav Miertus, ICS-UNIDO Franziska Mller-Langer, IE Leipzig, Germany Stefan Rnsch, IE Leipzig, Germany Arumugam Sivasamy, Central Leather Research Institute, Adyar, India Daniela Thrn, IE Leipzig, Germany Alexander Vogel, IE Leipzig, Germany Sergey Zinoviev, ICS-UNIDO
ICS-UNIDO Publication: finalized within ICS-UNIDO Work Program 2008, Area of Pure & Applied Chemistry
Opinions expressed in the present publication do not necessarily reflect the official views of UNIDO or ICSUNIDO. Mention of the names of firms and commercial products does not imply endorsement of UNIDO or ICSUNIDO.
This text can be used for non-commercial needs only. No selling, distribution, modification, reproduction, transmission, publication, broadcasting, posting or other use of its contents can be made without prior permission from the ICS-UNIDO
This is not a formal document and has been produced without formal editing.
II
Preface
One of the key issues of sustainable industrial development is the conversion from fossil feedstocks to renewable feedstocks in various sectors such as energy and fuel production, chemical and related industries. This conversion is driven by several factors, such as fossil feedstock depletion, need of diversification of feedstocks, abundance of renewable resources in many countries of the world, CO2 neutrality of renewable feedstocks, concerted potential development of both industry and agriculture, new openings for green chemistry and related industries development, etc. Obviously, many problems have to be solved for further development of the biofuel sector. One is the generally insufficient state of development of conversion technologies and missing full-scale experience. Others include availability of feedstocks and land competition between biofuels and food, and, therefore, uncertainty of feedstock supply and prices, risk of misconception in designing bio-fuel strategies. It is essential to promote, firstly through related R&D and capacity building, the adoption of sound biofuel concepts. In this process, an integrated approach has to apply, so that suitable technologies and sustainable feedstock exploitation practices be identified and implemented. The first step in this process is a careful analysis and forecast of advantages, consequences, and concerns from the point of view of technical feasibility, economic, and environmental impact. The International Centre for Science and High Technology of the United Nations Industrial Development Organization (ICS-UNIDO) promotes a programme on the knowledge transfer and capacity building to developing countries in the field of renewable resources and renewable energies. As the UNIDO activities are generally aimed at promotion of the industrial growth of developing countries, the relevant biofuel and biomassto-energy programmes are given specific focus because of their importance as of a potential driver of industrialization for many developing countries. In synergy with UNIDO efforts, the Area of Chemistry of ICSUNIDO implements a series of technical activities related to biofuel production technologies (focus on emerging technologies) including selected lab based research in chemical sciences, assessment of technologies and preparation of related decision support tools, training and fellowship programmes, organisation of specialized events, preparation/publication of scientific issues, project preparation and promotion, networking, etc. The survey is dedicated to technologies for production of second-generation bio-fuels including their technical, economical and environmental aspects. It also gives an overview of various bio-based products outlining their current state of industrial production and prospective applications and a brief introduction to the concept of biorefineries. The present publication can be used as a technical guideline in the preparation, development and implementation of various initiatives related to technology transfer, as well as for educational purposes. This document has been prepared within the ICS-UNIDO Work Programme 2007 in the Area of Pure and Applied Chemistry by a group of ICS-UNIDO experts. Contributions of a team of experts from Italian and German institutions to the content and editing of this publication is very much appreciated. Stanislav Miertus Chief of Area of Pure and Applied Chemistry, ICS-UNIDO
III
CONTENT
CONTENT
Part 1: 1.1 1.2 INTRODUCTION..........................................................................................................1 BACKGROUND................................................................................................................ 1 OBJECTIVES .................................................................................................................... 2
1.3 BIOMASS AS A RESOURCE .......................................................................................... 2 1.3.1 Characteristics ............................................................................................................. 2 1.3.1.1 Classification ........................................................................................................ 2 1.3.1.2 Properties.............................................................................................................. 3 1.3.2 Technical biomass potentials....................................................................................... 5 1.3.3 Biomass provision ....................................................................................................... 7 1.3.3.1 Regional biomass provision.................................................................................. 7 1.3.3.2 Transregional supply of biomass and bioenergy ................................................ 10 1.4 FUTURE BIOFUELS ...................................................................................................... 11
Part 2: TECHNICAL, ENVIRONMENTAL, AND ECONOMIC PROFILES OF FUTURE BIOFUELS............................................................................................................14 2.1 Production Technologies .................................................................................................. 14 2.1.1 Advanced biodiesel ................................................................................................... 14 2.1.1.1 Feedstock pre-treatment ..................................................................................... 14 2.1.1.2 Hydrotreating...................................................................................................... 15 2.1.2 Bioethanol.................................................................................................................. 15 2.1.2.1 Feedstock pre-treatment ..................................................................................... 16 2.1.2.2 Hydrolysis........................................................................................................... 16 2.1.2.3 Fermentation....................................................................................................... 17 2.1.2.4 Distillation / Rectification .................................................................................. 17 2.1.2.5 Absolutation ....................................................................................................... 17 2.1.3 Fischer-Tropsch fuels ................................................................................................ 17 2.1.3.1 Biomass pre-treatment........................................................................................ 18 2.1.3.2 Gasification......................................................................................................... 18 2.1.3.3 Gas cleaning ....................................................................................................... 19 2.1.3.4 Gas conditioning................................................................................................. 20 2.1.3.5 Product upgrading............................................................................................... 22 2.1.4 Methanol.................................................................................................................... 22 2.1.4.1 Biomass pre-treatment / Gasification / Gas cleaning / Gas conditioning ........... 23 2.1.4.2 Synthesis............................................................................................................. 23 2.1.4.3 Product separation .............................................................................................. 24 2.1.5 Dimethylether ............................................................................................................ 24 2.1.5.1 Synthesis............................................................................................................. 25 2.1.5.2 Product separation .............................................................................................. 26 2.1.6 Biomethane................................................................................................................ 26 2.1.6.1 Biogas ................................................................................................................. 26 2.1.6.2 Bio-SNG ............................................................................................................. 28 2.1.7 Biohydrogen .............................................................................................................. 30 2.1.7.1 Gas conditioning................................................................................................. 31 2.1.7.2 Hydrogen cleaning.............................................................................................. 31 2.1.7.3 Hydrogen treatment ............................................................................................ 32 2.1.8 System-technological comparison of biofuel options ............................................... 32 2.1.9 Overview of major demonstration projects ............................................................... 33
IV
CONTENT
2.2 ECONOMIC AND ENVIRONMENTAL ASPECTS ..................................................... 38 2.2.1 Economic aspects ...................................................................................................... 38 2.2.1.1 Capital investment requirements ........................................................................ 38 2.2.1.2 Biofuel production costs..................................................................................... 40 2.2.1.3 Well-to wheel costs ............................................................................................ 41 2.2.2 Environmental aspects............................................................................................... 42 2.2.2.1 Basics on life cycle assessment .......................................................................... 42 2.2.2.2 Comparison of international results.................................................................... 46 Part 3: 3.1 TECHNICAL PROFILES OF BIO-BASED CHEMICALS ...................................49 GENERAL ASPECTS ..................................................................................................... 49
3.2 PLATFORM CHEMICALS............................................................................................. 60 3.2.1 Carbohydrates............................................................................................................ 60 3.2.2 Fatty Acid Esters and Fatty Alcohols ........................................................................ 67 3.2.3 Terpenes .................................................................................................................... 69 3.2.4 Glycerol ..................................................................................................................... 71 3.3 HIGH VALUE CHEMICALS ......................................................................................... 74 3.4 BIOBASED OLEOCHEMICALS ................................................................................... 77 3.4.1 Life cycle assessment ................................................................................................ 77 3.4.2 Industrial uses of natural oils and fats ....................................................................... 78 3.4.3 Oleochemicals for Polymer Applications.................................................................. 79 3.4.4 Dimer Diols Based on Dimer Acid ........................................................................... 80 3.4.5 Polyols Based on Epoxides ....................................................................................... 80 3.4.6 Biodegradable Fatty Acid Esters for Lubricants ....................................................... 81 3.4.7 Surfactants and Emulsifiers....................................................................................... 81 3.5 Part 4: 4.1 4.2 CONCLUSIONS .............................................................................................................. 83 TECHNICAL PROFILES OF BIOREFINERIES ...................................................85 THE CONCEPT ............................................................................................................... 85 BIOREFINERY FEEDSTOCKS ..................................................................................... 86
4.3 BIOREFINERY TYPES ACCORDING TO FEEDSTOCK AND TECHNOLOGIES .. 88 4.3.1 Whole crop biorefinery.............................................................................................. 89 4.3.2 Green Biorefinery...................................................................................................... 89 4.3.3 Lignocellulosic feedstock biorefinery ....................................................................... 90 4.3.4 Biochemical pathway ................................................................................................ 92 4.3.5 Thermochemical pathway ......................................................................................... 93 4.3.6 Hybrid thermochemical/biochemical ........................................................................ 94 4.4 CURRENT BIOREFINERIES AND OUTLOOK/DEVELOPMENT TRENDS............ 95
REFERENCES ..............................................................................................................................97
INTRODUCTION
Part 1:
INTRODUCTION
1.1 BACKGROUND
Currently approx. 10 % of the global primary energy demand (in 2006 approx. 505 EJ) is covered by biomass /1/. All over the world, an increasing number of countries define declarations on bioenergy use (e.g. biomass action plans, biofuel directives). The demand on biofuels to meet the specific biofuel targets are summarised in Fig. 1-1.
Biofuel demand meeting target in 2015/2020 [PJ/a] 5.000 110 mn t 4.000 3.000 2.000 1.000 0 USA EU25 China Brazil India Australia
10% 15% 20% 10% 5%
Fig. 1-1. Biofuel demand to meet the defined targets in selected countries in 2015/2020.
These political targets are the main drivers for the development of biomass usage for energy production. In view of the bioenergy use and energy crop production, various political sectors with different objectives interact. The points of departure of various policies for both systems within the context of renewable energies as well as implements of instrumentation, representative for e.g. Germany are shown in Fig. 1-2. Internationally the climatic agreement with the minimum objectives of the Kyoto Protocol and relevant agricultural policy agreements of GATT and the WTO constitute the framework for the expansion of bioenergy and the production of renewable raw materials. Among others, environmental and climatic protection demands the expansion of renewable energies and influences the bioenergy and energy crop systems only indirectly normally no decisive objectives for bioenergy are in existence. /2/ Taking into account technical options, fuels are based entirely and heat is based primarily on biomass raw materials, while a mix of energy sources can be found in the sector of electricity. This results in different degrees of general promotion of renewable energies for the energy sources, electricity, heat and fuel, on the bioenergy system. Thereby, cultivation of energy crops is influenced directly by agricultural policy. Moreover, the implementation of the objectives of the energy policy results in a promotion of fuel provision, which currently due to technical reasons can only be implemented through the utilisation of energy crops; i.e. the promotion of biofuels represents a strong promotion of energy crops./2/
INTRODUCTION
Fig. 1-2. Influence from international, European and national politics on the production of bioenergy and energy crops.
1.2 OBJECTIVES
Against the shown background, this survey deals with the future biofuel options for transportation purposes and chemical industries. Therefore based on the characteristics of biomass as a multipurpose resource technical profiles are shown for the different future biofuel options (e.g. synthetic biofuels based on lignocelluloses, biomethane and biohydrogen) and selected bio-based chemicals. Furthermore, these technologies are considered concerning there economic aspects (e.g. capital investment requirements, costs of production and use) as well as there environmental aspects (e.g. global warming effects).
1.3 BIOMASS AS A RESOURCE

Biomass refers to material of biological origin excluding material embedded in geological formations and transformed to fossil /3/. Biomass can be converted directly or indirectly to biofuels, which can be of solid, liquid or gaseous forms. Major sources of biomass for energy purposes are various types of woody and herbaceous biomass, biomass from fruits and seeds (e.g. energy crops) as well as biomass mixtures like animal or horticultural by products etc. Within these products solar energy directly or indirectly (in terms of biomass of animal by-products) by the process of photosynthesis is stored which enables the plants to produce biomass. In the following sections, characteristics and technical biomass potentials as well as basics on biomass logistics are introduced.
1.3.1 Characteristics 1.3.1.1 Classification Biomass resources can be classified into the following groups
energy crops (i.e. biomass that is produced solely for the energetic use),
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INTRODUCTION
by-products (i.e. residues and waste derived from biomass processing activities), end use material (i.e. biomass that is recovered after its use elsewhere within the society). According to the FAO UBET biomass resources can be divided into four categories: (i) woody biomass from trees, bushes and shrubs, (ii) all types of biofuels originating from herbaceous biomass, (iii) biomass from fruits and seeds, (iv) others/mixtures /4/. For instance, in Europe solid biofuels are specified according to the CEN standards CEN/TS 14588 (Solid biofuels. Terminology, definitions and descriptions) and CEN/TS 14961 (Solid biofuels. Fuel specification and classes) /3//5/. A brief overview of biofuels classification according to UBET is shown in Tab. 1-1.
Tab. 1-1. Classification of biofuels sources by different characteristics /4/.
Woody biomass Energy crop Direct WOODFUELS Energy forest trees Energy plantation trees Thinning by-products Logging by-products Herbaceous biomass AGROFUELS Energy grass Energy whole cereal crops Crop production byproducts Straw Biomass from fruits and seed Energy grain Others (incl. mixtures)
By-productsa
Animal by-products Stones, shells, husks Horticultural byproducts Landscape management byproducts Biosludge Slaughterhouse byproducts MUNICIPAL BYPRODUCTS Kitchen waste
Indirect
Wood processing industry by-products Black liquor Used wood
Fibre crop processing by-products
Food processing industry by-products
End use materials
Recovered
Used fibre products
Used products of fruits and seeds
Sewage sludge includes the improperly called solid, liquid and gaseous residues and wastes derived from biomass processing activities
1.3.1.2 Properties As follows, the basic properties of lignocellulosic and other energy crops and residues are considered. More detailed information can be gathered e.g. from /6//7//8//9//10//11/.
Woody and herbaceous energy crops, by-products and end use materials Solid biofuels (so called lignocelluloses) comprise depending on the biomass of different shares of celluloses (i.e. linear polymers of glucose, share approx. 40 to 60 wt.-% of dry biomass), hemicelluloses (i.e. complex polysaccharides, about 20 to 40 wt.-%) as well as lignin (complex polymer chains of phenyl propane, about 10 to 25 wt.-%) /8//10/. Quality-dominating properties of solid biofuels comprehend several characteristics that are relevant in practice depending on the kind of biomass use. This concerns particularly assuring and improving biofuel quality with regard to increasing technical and environmental standards and the therewithassociated compliance with regulations and specifications for biofuels (e.g. test methods, sampling, classification and quality management).
INTRODUCTION
Like solid fossil fuels also solid biofuels can be characterised by energy source relevant parameter, such as chemical properties (based on the chemical composition), combustion performance properties as well as physical-mechanical properties. Tab. 1-2 shows these properties for selected solid biofuels in comparison to solid fossil fuels.
Tab. 1-2. Properties of solid biofuels in comparison to solid fossil fuels /12//6//10/.
Solid biofuels Wood Chemical compositionb C [wt-% (d)] H [wt-% (d)] O [wt-% (d)] N [wt-% (d)] S [wt-% (d)] Cl [wt-% (d)] Properties of combustion Lower heating value [MJ/kg (d)] Water content [wt-%] Ash content [wt-% (d)] Ash melting point [C] Volatiles [wt-% (d)] Physical-mechanical properties (Typical) fuel formd (Typical) particle size Storage density [kg/m]c Energy density [kWh/m] a b c d d dry basis (water free) at 15 % water content RW round wood, WB wood bundles, WC wood chips, RB rectangle bales, RB round bales, CB chaffed biomass, C Coke, P powder RW, WC, WB 5 1.000 mm 195 460e 900 1,700 RB, RB, CB 0.1 3.7 m 10 200 mm 65 160 560 780 RB, RB 0.1 3.7 m 10 200 mm 150 190 708 930 C, P < 1 50 mm 562 3,900 C, P < 1 50 mm 826 7,690 18.4 18.8 12 50 0.6 3.8 1,265 1,426 83 15.8 17.5 8 20 5.2 12.2 980 1,120 76 16.9 26.5 15 22 2.1 4.6 687 730 78 22 27 45 60 1.3 15.0 1,120 52 32 35 5 14 1.0 15.0 1,300 35 47.1 49.8 6.1 6.3 43.2 45.2 0.1 0.5 0.02 0.05 0.004 0.006 45.0 47.7 5.9 6.0 39.1 43.8 0.5 0.9 0.06 0.27 0.20 0.81 43.6 60.5 6.4 7.2 23.8 46.4 1.68 3.94 0.10 0.12 0.04 0.07 63.0 74.0 4.9 6.0 15.4 26.0 0.7 1.9 0.39 < 0.13 73.0 92.0 4.0 5.6 1.4 11.1 1.2 1.7 0.94 < 0.1 Straw Graina Solid fossil fuels Lignite Hard coal
here: grains of wheat, triticale and rape seeds, also used as whole cereal crop
Other energy crops, by-products and end use materials Different to solid biofuels other biomass sources (typical pasty or liquid) have a wide spectrum on properties. This especially concerns the physical-mechanical properties, such as the consistence and the therewith-associated requirements on logistics (i.e. storage, cargo handling and transport) as well as the treatment of biofuels (e.g. animal excrements and fats, heterogeneous industry waste). In the following exemplarily the properties for selected biogas substrates are summarised in Tab. 1-3. The most important properties are the dry substance (DS), the organic dry substance (oDS), typical contents of nutrients (e.g. nitrogen N, ammonia NH4 and phosphor P) as well as the biogas yield and the specific methane content.
INTRODUCTION
Tab. 1-3. Properties of biogas substrates /7/.

Manurea DS [%] oDS [%DS] N [%DS] NH4 [%DS] P [%DS] Biogas yield [m/tFM] Biogas yield [m/toDS] Methane content [vol.-%]
a b
Maize silage 20 35 85 95 1.1 2 0.15 0.3 0.2 0.3 170 200 450 700 50 55
Rye silageb 30 35 85 95 4.0 0.57 0.71 170 220 550 680 ~ 55
Grass silage 25 50 70 95 3.5 6.9 6.9 19.8 0.4 0.8 170 200 550 620 54 55
Biowaste 40 75 50 70 0.5 2.7 0.2 0.8 80 120 150 600 58 65
7 11 75 86 2.6 18 1 17 0.5 10 20 35 200 700 60 70
e.g. from cow and pigs (higher value for nutrients, biogas yield and methane content) Of whole cereal crops
1.3.2 Technical biomass potentials

The potential of the different bioenergy sources to be used for energy can be categorised as theoretical, technical, economic and realisable potential. Thereby the technical biomass potential refers to the percentage of theoretical potential that can be used given current technical possibilities. Calculating the technical potential takes into account the available utilisation technologies, their efficiency, availability of sites also in terms of competing uses, as well as insurmountable structural, ecological (e.g. nature conservation areas) and other non-technical restrictions /13/. The options for supplying energy from biomass are determined primarily by the potential of the usable biomass as well as by the available conversion technology. This technical fuel potential refers to the share of the total available biomass that can be used taking into account given technical restrictions /14/. At a worldwide level, huge technical biomass potentials have been identified especially for woody byproducts as well as energy crops /10/, which is shown in Fig. 1-3.
Former Soviet Union Middle East
Woody by-products Herbeaceous by-products Manure Energy crops
Europe
36% 40% Worldw ide (2000) approx. 104 EJ/a
Afica
Asia Latin America + Caribbean North America 0 5 10 15 20 25
7% 17%
Technical biomass potenial (base case 2000) [EJ/a]
Fig. 1-3. Technical biomass potential worldwide /10/.
INTRODUCTION
For the future, it is expected that especially energy crop potentials will increase significantly. When comparing different studies, which deal with worldwide potential for agricultural biomass production (i.e. the potentials of residues and energy crops) one can reveal also that the energy crop potential is the most important but also a variable biomass fraction. On a worldwide level ongoing breeding activities and the establishment of advanced agricultural management systems might have the potential to increase the yields of about 150 to 200 % during the next 50 years1 /2//15/. Thus, especially in the field of energy crops the available studies on the long-term biomass potential vary widely (20 to 500 EJ/a; Fig. 1-4); this is due to the described uncertainties. Some newer studies (e.g. /16//17//18/) expect even a higher biomass potential of 500 up to 1,500 EJ/a.
Technical biomass potential worldwide bandwidth of different studies [EJ/a] 600 500 400 300 200 100 0 2000 2010 2025 2050 2075 2100 Primary energy demand 2006: 505 EJ/a Current biomass use: approx. 50 EJ/a
Fig. 1-4. Bandwidth of technical biomass potentials given by different studies (data base /19/).
Depending on the biomass resources (i.e. energy crops) applied for biofuel production and the specific biomass conversion efficiency into the biofuel different specific yields per hectare agricultural land arise (Fig. 1-5). According to this, biofuel options are the most promising that can be produced by using the whole crop or a high share of the plant respectively with a high yield per hectare (e.g. willow, sugar cane, palm oil) and at high biomass to biofuel conversion rates (e.g. lignocellulosic based biofuels such as biomethane).
It is considered that yield increase by breeding and assimilation of agricultural systems in practice often are strongly connected (and the effects cannot be fully added); additional effects of GMO are not considered.
INTRODUCTION
Biomethane BtL
Willow Willow Maize silage Soja oil Rape oil Palm oil Willow
Biodiesel Bioethanol
Sugar cane Sugar Beet Maize Corn 0 conv. biofuels min conv. biofuels max future biofuels min future biofuels max 50 100 150 Specific biofuel yield per agricultural land and year [GJ/ha a] (i.e. energy crop yield incl. biofuel specific biomass conversion efficiency) 200
Fig. 1-5. Specific biofuel yield per agricultural land and year /20/.
1.3.3 Biomass provision

As one can reveal from the outline of technical biomass potentials, biomass is a limited resource that need to be provided from the place of origin (e.g. as cultivated energy crop or by-product) to the biomass conversion plant. Therefore, two options will be briefly discussed: (i) regional biomass supply with regard to increase the local added value and (ii) transregional supply of biomass and bioenergy.
1.3.3.1 Regional biomass provision Many of the concepts for biofuels and bio-based chemicals production are subject of the systeminherent trade-off between preferably medium to large-scale plants with regard to economy of scale and thus a high biomass demand (see Fig. 1-6) and a relatively small catchment area for the supply of this feedstock demand. This is particularly true for so far not matured concepts that are designed for large-scale conversion of biomass (e.g. energy crops, straw and forestry wood).
INTRODUCTION
Technology availability - term
short
1
medium
long
10
100
1.000
10.000
100.000
1.000.000
10.000.000
Fig. 1-6. Biomass demand of current and future biomass applications.
Depending on regional conditions, the overall biomass supply chain (i.e. starting from biomass production over biomass provision and biomass conversion) is coupled to different aspects on biomass site and demand site (Fig. 1-7). At both sites aspects of biomass treatment, storage and transport as well as handling are relevant. /21/
biomass
requirements on biomass site
harvesting / production
pretreatment storage transport
provision on biomass site
treatment/ refinement
storage/ drying
transport
provision on demand site
treatment
storage
biomass conversion plant

IE Leipzig, 2007
requirements on demand site
Fig. 1-7. Overall biomass supply chain.
No defined chain (e.g. transport distance of biomass production and biomass demand of about 150 km) is conferrable to different regions, because of e.g. (i) different distribution and size of biomass growing areas as well as their ratio to land area and (ii) different infrastructure in terms of transport and ownership structure of growing areas /22/. Thus, for the analysis of biomass logistics following specific criteria are of importance such as: the area or region specific potential (i.e. the technical biomass potential per ha total area land of a region or country; in other words the density of biomass potentials),
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INTRODUCTION
the biomass assortment and their treatment, the plant site and local infrastructure (e.g. detour factors, connection points, available land), the means of transport (e.g. semitrailer, train or navigation vessel) and depending on the potential density and local infrastructure the transport distance, storage technology and storage demand according to the specific annual biomass demand of the biofuel production plant. Based on that criteria there are a multitude of conceivable routes for biomass provision from biomass site to the plant gate of the biomass conversion facility. With regard to different concepts two main approaches are relevant: (i) direct biomass provision and (ii) provision including decentral biomass conversion plants (e.g. pyrolysis or torrefaction2). The direct transportation (i.e. using semitrailer or lorry respectively) is the simplest way of biomass provision. Though to include decentralised provision steps increase the complexity of the biomass provision chain, it offers, however, to uncouple the respective requirements on biomass and demand site (see Fig. 1-7). Thus, preliminary and downstream provision steps can be targeted to these requirements. In particular the intermediate step (e.g. pyrolysis) can be targeted to the requirements on biomass demand site as well as on specific biofuel plant requirements (e.g. concerning the biomass quality). A survey of optional provision chains is shown in Fig. 1-8. These pathways are structured into sections (alphabetical) and routes per section (numerical). Gathering points, such as for decentral or central storage, cargo handling (e.g. at a harbour or rail station) or decentral conversion plant for biomass pre-conversion to e.g. pyrolysis slurry are indicated as white rectangle; means of transportation are indicated orange.
Provision on biomass site A1 lorry B1 local storage C1 train D1 central storage B2 bimodal transport C2 inland nav. vessel D2 bimodal transport
E1 lorry F1 decentralised plant (e.g. pyrolysis) G1 lorry H1 combined transport I1 train I2 inl. nav. vessel Gathering point (e.g. storage, cargo handling, pyrolysis) Means of transport K1 lorry Biomass conversion plant (biofuels, biorefinery)
IE Leipzig, 2007
J1 combined transport
Fig. 1-8. Optional provision chains from biomass to plant site.
Both options are currently at R&D level and need to be demonstrated in an industrial level. This is true for the production as well as for the transportation (especially for pyrolysis slurry).
INTRODUCTION
Depending on the kind and complexity of the different biomass provision chains specific benefits and drawbacks occur. Some of the most important characteristics are exemplarily shown in Tab. 1-4. While direct road provision is highly flexible with regard to the infrastructure due to the high road density (especially e.g. in Western Europe) the transport efficiency is comparably low due to the limited payload of semitrailers. These effects can be compensated when using means of transport with a higher allowed payload as well as when transporting biomasses with a higher energy density (e.g. pyrolysis slurry). However, infrastructure flexibility is decreasing.
Tab. 1-4. Logistic concepts examples and their characteristics at European conditions /23/.
Provision chain from biomass site to biofuel production plant Direct biomass provision Road (semitrailer) log wood, 88 to 96 ++ +++++ ++++ + wood chips, straw bales Road (semitrailer) storage (indoor) inland water way (navigation vessel) road (semitrailer) log wood, 85 to 95 +++ ++ +++ ++ wood chips Provision including decentral biomass conversion plants Road (semitrailer) pyrolysis plant railway (tank train) wood chips, 69 to 77 ++++ +++ + +++++ straw/triticale bales Legend: + less promising, +++ promising, +++++ very promising a starting from LHVbiomass at biomass site to LHVbiomass at plant gate incl. losses during storage, transport, handling b transport distance that need to be covered to transport one td of biomass under typical frame conditions in Europe Typical assortment (e.g.) Overall efficiencya [%] Transport efficiencyb [km/td] Infrastructure flexibility Current development stage Further R&D potential
1.3.3.2 Transregional supply of biomass and bioenergy In addition to biomass provision at a regional level, the demand for biomass and bioenergy sources will be met transregionally in the market if the bioenergy sources are worthy to transport, i.e. if they have an high energy density (e.g. cf. Tab. 1-2), shelf life (e.g. moderate water content) and availability of defined quantities and qualities. In Tab. 1-5 an overview of the properties relevant to transportworthiness for biomasses and the resulting transregional supply options is provided.
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INTRODUCTION
Tab. 1-5. General tradeability of different biomass sources /14/.

High specific heating value Options of trade No / limited tradeability Availability of defined quantities & qualities
High density
Woody biomass
Forestry wood / SRC Logging residues Industrial wood / pellets Waste wood
x x x x x x x X
x x x
x x x x x x x
x x x x x x x x x x
x x x x x x x x x x x x x
Herbaceous biomass
Straw Cereal plants (whole plant) Grain and oil seeds Sugar beets / cane
Other biomass Bioenergy
Industrial residues / organ. waste Silage Heat from biomass Electricity from biomass Liquid biofuels
x x x x x
Because of the relevant properties, a considerable development of global biofuel markets can be expected in the years to come, also today a market is still established. Specially the U.S. and China will use high quantities of biofuels in the near future, but have only sparsely possibilities for own production. In Europe, biomethane might become a relevant bioenergy carrier additionally, because of the far-reaching European natural gas grid and the possibility to use biomethane for the transport sector too. Outside Europe biomethane is of less importance. /2/
1.4 FUTURE BIOFUELS

Before technical profiles of the different biofuel options that might be promising in the future are explained in detail, a short introduction is given in order to outline the future options compared to the conventional biofuel options. Advanced technologies are now under development to convert biomass into various forms of secondary energy including electricity, gaseous and liquid biofuels, and even hydrogen. The purpose of biomass conversion is to provide fuels with clearly defined fuel characteristics that meet given fuel quality standards. In general, there are various options to produce alternative transportation fuels based on biomass. Biogenous energy sources can be converted by means of highly different supply chains into gaseous and liquid biofuels that can be used for transportation purposes. Depending on the conversion of biomass in principal three main pathways come into consideration: (i) the thermochemical pathway, (ii) the physical-chemical conversion pathway, (iii) the bio-chemical conversion pathway./10/ Biofuels can be grouped into 'generations', according to the type of technology they rely on and the biomass feedstocks they convert into fuel. An overview of promising conversion chains is presented in Fig. 1-9.
11
Tradeable
Shelf life
INTRODUCTION
Biomass energy sources

Energy crops, e.g. Lignocellulose Oil seeds Starch plants Sugar plants Manure Residues Biogas substrates, e.g. Org. waste Grass land Food industry Straw SRC Solid biofuels, e.g. Forestry wood Logging residues Used wood
Electricity from biomass
Physical-chem. processes
Bio-chem. processes
Thermo-chem. processes
H2 O
electrolysis
Biogas Gas treatment / upgrading
BCO
Syngas / product gas (H2/CO)
O2
H2
Oils
Fats
Gasification / reforming
Fuel synthesis from syngas
MeOH
EtOH
(Trans)esterification
Hydrotreating/ -cracking
COShift
MtG-Process
H2
Veg.oil
FAME
ETBE
EtOH
FAEE
BtOH
Biogas
SNG
HTU
Hyd. oil
DME
MeOH
MTBE
MTG
FT-fuels
Hythane
H2
Current biofuel generation
Future biofuel generation
Veg.oil vegetable oil, FAME fatty acid methyl ester, FAEE fatty acid ethyl ester, BtOH butanol, ETBE ethyl tertiary butyl ester, EtOH ethanol, Biogas form of biomethane, SNG synthetic natural gas (biomethane), HTU hydro thermal upgrading (diesel), Hyd.oil hydrogenated vegetable/animal oil /fats, DME dimethylether, MeOH methanol, MTBE - methyl tertiary butyl ester, MTG methanol to gasoline, FT Fischer Tropsch, H2-hydrogen, SRC short rotation coppice
IE Leipzig, 2007
Fig. 1-9. Overview of biomass conversion processes into biofuels for transportation purposes3.
Current generation biofuels are biofuels, which are on the market in considerable amounts today. The most important biofuels are bioethanol or ETBE (worldwide production in 2006 approx. 45 mn.t) and biodiesel (worldwide production in 2006 approx. 5.5 mn t) using the well established processes for their production. For these types of fuels, only easily extractible parts of plants are used, such as starch-rich corn kernels, grains or the sugar in canes or oilseeds are used. Bioethanol is produced by fermenting sugars from starch and sugar biomass (e.g. cereal crops such as corn or maize and sugar cane or beets). It can be used in pure form in specially adapted vehicles or blended with gasoline, provided that fuel specifications are met. Ethyl-tertiary-butyl-ether (ETBE) is synthesised from bioethanol and isobutylene. It is used as additive to gasoline. Biodiesel (FAME) made from vegetable oils primarily based on rapeseed, soya or palm fruits from the reaction of methanol in a catalysed transesterification process. It can be used in pure form in specially adapted vehicles or be blended with automotive diesel. /24/ Different from that future biofuels can be produced (i) from wider range of feedstocks as well as (ii) from the whole plant, including biomass waste streams that are rich in lignin and cellulose, such as wheat straw, grass, or wood. In order to breakdown this biomass, two main conversion pathways come into consideration /24/: Firstly via bio-chemical processes that e.g. consists of using specialty enzymes that succeed in breaking down the lignocelluloses and release the sugars, which can then be fermented into alcohol. Moreover, biogas which have been derived by anaerobic treatment of biogas substrates and then upgraded to biomethane that can be feed-in into the natural gas grid and e.g. used in natural gas vehicles. Secondly the thermo-chemical processes based on gasification consists of using high temperatures to turn biomass to a raw gas that is treated and conditioned into a synthetic gas ('syngas'), consisting mainly of carbon monoxide and hydrogen. This gas can further be processed into different types of liquid and gaseous fuels via different fuel syntheses. Fuels from
3
Without entitlement of completeness
12
INTRODUCTION
this route are then called 'synthetic biofuels'. Most promising liquid synfuels (also BtL, biomassto-liquids) are e.g. biomethanol and Fischer-Tropsch fuels. Gaseous synfuels are e.g. dimethylether (DME) and Bio-SNG, which is also a form of biomethane and can be similarly used as natural gas substitute like biogas. Alternatively, the cleaned and conditioned product gas can be converted into hydrogen. Furthermore, available vegetable oils or animal fats can be treated by hydrogenation processes into so called NextBtL, a biodiesel with comparably more favourable properties that conventional biodiesel. These named biofuel options will be considered in the following technical part of this survey.
13
TECHNICAL, ENVIRONMENTAL, AND ECONOMIC PROFILES OF FUTURE BIOFUELS
Part 2: TECHNICAL, ENVIRONMENTAL, AND ECONOMIC PROFILES OF FUTURE BIOFUELS

2.1 Production Technologies
2.1.1 Advanced biodiesel
In order to produce a biodiesel with more favourable properties than biodiesel based on the (trans)esterification of vegetable or animal oils and fats (i.e. conventional biodiesel production) conventional refinery processes can be also applied to convert the same feedstocks into a advanced biodiesel. Properties that are similar to petroleum diesel can be achieved by blending vegetable oils with mineral oil previous to their upgrading to diesel in mineral refineries by using the existing refinery infrastructure including energy, blending facilities, logistics and laboratories /25//26/. For example, PETROBRAS (Brazilian mineral oil company) uses this production pathway in four Brazilian refineries in 2006 and 2007 /27/. The mineral oil company BP forces on the hydrogenation technology and therefore uses experiences made in the VEBA refinery in Gelsenkirchen (Germany) during the oil crisis in the 1970 /28/. In the following, the production process of the so-called NExBtL will be considered in more detail. The NExBTL process (developed by the finish company NESTE OIL) is a catalytic hydrotreating process that is integrated into a mineral oil refinery /29/. The principle is shown in Fig. 2-1.
Vegetable oil / animal fats
Overall process
Pretreatment
(Degumming)
Sludge
Pure Oil Fuel Gas Hydrotreating Biogasoline
NExBTL
Fig. 2-1. Principle of advanced biodiesel production.
2.1.1.1 Feedstock pre-treatment For the pre-treatment of the feedstock (e.g. vegetable oils as crude oil, animal fats) conventional degumming technology known from vegetable oil processing or conventional biodiesel production are used to remove undesired impurities /30/. The vegetable crude oil is degummed to remove phospholipids or lecithin. The phospholipids are removed since they are strong emulsifiers, which can lower the yield through the acid neutralization and can also have partially effects on the technical usefulness of the oils/fats. /10/ A commonly used technology is the multi-step chemical degumming using caustic soda and phophoric acids /31/.
14
2.1.1.2 Hydrotreating After degumming the feedstock is heated and pumped into the hydrotreating reactors. Hydrotreating is one of the most commonly used refinery processes, that is designed to remove contaminants (e.g. sulfur, nitrogen, condensed ring aromatics or metals).
The hydrotreating process typically takes place in fixed bed reactors at temperatures of approx. 350 to 450 C, at a partial hydrogen pressure of 48 to 152 bar. For that standard catalysts are applied (such as CoMo and NiMo). /32/ During hydrotreating oxygen is removed by adding hydrogen. Vegetable oil or animal fats (i.e. triglycerides) are converted into three separate branched chain paraffins. Oxgen in the triglyceride is removed as water and carbon dioxide. Side products of the process are fuel gas which can be used for energy and a small amount of biogasoline. /33/ Firstly, the feedstock is filtered before combining with hydrogen (demand approx. 0.09 GJH2/GJbiodiesel, /33/) and passing through the catalyst beds at elevated temperatures and low space velocities. Due to the relatively low reactivities of the feedstocks often several reactors are required in series. The reactor effluent containing the products, recycle gas and by-products (e.g. biogasoline) is then separated into the desired products through a combination of separators, flash stages, and eventually, fractionation equipment. Depending on the feedstock, the hydrogen recycle gas requires scrubbing to remove H2S. Afterwards it is mixed with makeup gas before being recycled to the reactors. /34/ Since acids are generated during the process hydrotreating reactor need to be corrosion-resistent. /32/ The main product NExBtL (i.e. non-oxygenated hydrocarbon biodiesel, a mixture of n- and isoparaffins) has similar chemistry and properties to the synthetic BtL fuels (e.g. Fischer-TropschDiesel, cf. chapter 0) /35/. The mass specific biomass conversion rate is depending on the feedstock approx. 1.23 tfeedstock/tbiodiesel /33/.
2.1.2 Bioethanol
In principal, bioethanol production is based on bio-chemical conversion processes (i.e. fermentation by micro-organism), which is also considered in the following (Fig. 2-2). Moreover, bioethanol can be produced as synthetic fuel as well (see chapter xyz).
15
Lignocellulosic Feed Stock
Processing of raw materials (mechanical preparation, grinding) Biomass conversion 1st step Hydrolysis (heat, compression) 2nd step Hydrolysis (enzymatical) Decantation Fermentation
biochemical biomass conversion
Electricity / Steam generation solid residues (ligning etc.)
Overall process
mash Ethanol conditioning Destillation / Purification distillation Concentration residues
Absolutation
absolute Ethanol
Fig. 2-2. Principle of bioethanol production based on lignocelluloses.
2.1.2.1 Feedstock pre-treatment For the following process stages, the lignocellulosic feedstock is pre-treated and grinded to a small particle size of approx. 1 to 3 mm. Depending on the kind of hydrolysis used in the following procedure, a pre-desiccation of the treated material to a humidity of less then 10 wt.% may be necessary. /36/
2.1.2.2 Hydrolysis Cellulose is the primary structural component and furthermore the most produced metabolite of green plants /10/. Its suitability for the production of bioethanol derives from its composition of glucose molecules. A strong linkage of crystalline cellulose to other plant constituents like lignin, pectin and hemi cellulose hinders the extraction of cellulose. On this account miscellaneous pre-treatment procedures have been developed. The first step Hydrolysis (i. e. saccharification) contains the release of fermentable monosaccharides C5 (i.e. xylose, arabinose) and C6 (i.e. hexose, glucose) from cellulose and hemi cellulose. The following second step Hydrolysis is based on an enzymatic decomposition of the cellulose molecules. Alternatively, a single step process using concentrated hydrochloric respectively sulphuric acid, could be used for cellulose extraction. Moreover, enzymatic procedures are still in the progress of development.
In the next step, the cellulose gained from hydrolysis is used as feed for the following process of fermentation. The separated lignin could be used as fuel for the production of process energy.
16
2.1.2.3 Fermentation In absence of oxygen, a few microorganisms (e.g. bacteria, yeasts and fungi) ferment hydrocarbons producing ethanol and CO2. The theoretic rate of yield for this fermentation process can be calculated as 0.51 kg Ethanol and 0.49 kg CO2 per kg sugar /8//37/.
Perfect living conditions (including the precaution of an infection with lacto bacteria) for the used microorganisms are essential to reach a maximum ethanol yield. General process parameters are a temperature of 34 C, an airtight fermenter, a pH-value of 4.2 to 5.2 and a sugar content of the used mash up to 250 g/l /10/. Depending on the plant used, the process of fermentation takes between two and five days. Afterwards the used mash contains 10 to 15 vol.% of ethanol. For process control, the used auxiliary materials are important. Acids (e.g. hydrochloric, sulphuric acid) can reduce the pH-value and Ammonia is needed for the nutrient supply of yeast. These requirements in connection with an appropriate temperature are the basis of the yeast enzyme production and therewith of the glucose conversion to ethanol and carbon dioxide. For the fermentation of lignocellulose common yeast is suitable to only a limited extent. From the contained sugar spectrum only glucose, as a monomer component of the cellulose molecule, can be fermented to bioethanol. In assistance of biotechnology, new methods for the fermentation of the whole sugar spectrum of lignocellulose have been developed over the last years /8/.
2.1.2.4 Distillation / Rectification In the process of distillation alcohol contained in the mash, (mash from the fermentation of cellulose contains a comparatively small ethanol concentration of 5-wt.% /8/) is separated due to a multi stage distillation / rectification using steam. Beside water, several other substances are removed from the Ethanol. These are forerun fractions with lower boiling points than Ethanol as well as fusel oils (i.e. upper alcohols with boiling points above ethanol). Furthermore, the co-product mash is gained as distillation residue. After conditioning, this mash could be sold as DDGS (Dried Distillers Grains with Solubles). The main product of the distillation process is azeotrope Ethanol with a max. purity of 97 vol.% entering the final process of purification.
2.1.2.5 Absolutation The process of absolutation is used for the further concentration of ethanol (to archive at least 99.8 vol.%). For this process, the method of the molecular sieve distillation has detached the older membrane and entrainer distillation. Plants for molecular sieve distillation normally contain of two columns with zeolites (usually synthetic crystalline aluminium silicates). The compression of vaporous ethanol and the associated adsorptive accumulation in the first column causes a regeneration of the used zeolites due to a subsidence partial pressure and a washout of pure ethanol in the second column. The use of the molecular sieve distillation also allows the absolutation of ethanol with a purity of down to 85 vol.%. Thereby its possible to save energy in the process of thermal rectification /36//38//39/.
2.1.3 Fischer-Tropsch fuels

The production of FT-Diesel bases on one of the oldest methods to substitute fossil fuel: the FischerTropsch-Synthesis. The Fischer-Tropsch-Synthesis was developed in 1925 at the Kaiser-WilhelmInstitut (KWI) to generate liquid hydrocarbons out of syngas from gasified coal /40/. Today the Fischer-Tropsch process becomes more and more important as the syngas can be produced through
17
biomass gasification, too. However, this process still is not state of the art and there are a lot of challenges in improving the process steps shown in the Fig. 2-3 below.
Fig. 2-3. Principle of FT fuel production.
2.1.3.1 Biomass pre-treatment To ensure a high gasification efficiency under an energetic and exegetical point of view the biomass has to be pre-treated before entering the gasifier. Important for an accurate gasification process is (i) the particle size and (ii) the water content of the used biomass. To adjust these two factors of influence to the gasification demands there are different treatment methods available and state of the art (e.g. rotary drum dryers) /41/.
2.1.3.2 Gasification After being pre-treated the biomass is fed into a gasifier. In the gasifier the biomass is converted into a product gas under sub-stoichiometric conditions (0.3 < < 0.5) and high temperatures (700 to 1,500 C). The oxygen demand for this thermo-chemical process is delivered by gasification agents as technical oxygen, water-steam, carbon dioxide and air /42/.
The whole gasification process can be subdivided into four different parts: (i) drying, (ii) pyrolytic decomposition, (iii) oxidation and (iv) reduction. Within the drying the biomass is heated up and dried. Afterwards during the pyrolytic decomposition the solid biomass is decomposed into solid (pyrolytic coke), liquid and gaseous components. Subsequently within the oxidation the pyrolytic coke and higher hydrocarbons are broken up into gaseous molecules (e.g. CO, H2, H2O, H2O, CO2, CH4).
18
Within the last step the reduction the remaining coke and parts of the produced CO2- and H2Omolecules are reduced into CO and H2. The result is a producer gas with a comparatively high heating value containing CO, CO2, H2, CH4 and H2O as main components and different impurities. The exact compositions depends on manifold parameters within the gasification as pressure, temperature, gasifier type and gasification agent. Gasifier types can be distinguished in the face of their dynamic flow behaviour /43/: Fixed-bed gasifier. These gasifiers are commonly used for local applications due to their simple build-up. However, the up-scaling possibilities are limited and they tend to incomplete material conversion such as to high tar building rates. Fluidised-bed gasifiers. They contain a bed out of small inert particles (e.g. sand) lying on the gasifiers injection ground. The injected gasification agent disperses this inert bed material and the continuous fed in fuel (biomass). Due to this procedure there is a homogenous fuel allocation in the gasifier, which avoids the building of different temperature zones and ensures reaction temperatures of 700 to 900 C, which are good to handle. So, fluidised-bed gasifiers have an advantage due to better heat- and material transformations. However, caused by their complex process control and plant effort they are used primary for a fuel power input of at least 10 MW. Special technologies. One mentionable special gasification technology is the so called entrained flow gasification. In this gasification method fuel of small size is gasified at a temperature level of 1200 to 2000 C within only few seconds. Pressures up to 100 bar and high carbon transformation rates (> 99 %) are possible. The entrained flow gasification leads to a nearly tarfree producer gas and almost all kinds of biomasses can be handled. But, the high temperature level such as the complex biomass pre-treatment to a pumpable fuel lead to high costs /44/ /10/. As almost all gasification reactions occur endothermic and heat has to be supplied. Depending on the heat supply gasifier can also be differed as follows: Autothermic gasification. Heat is supplied by a partly oxidation of the fuel. Oxygen as oxidation media is supplied through the gasification agent. Allothermic gasification. The necessary reaction heat is supplied by heat exchangers or by a circulating heat transfer medium (e.g. circulating bed material). As an adequate heat transfer is necessary the heat transfer is arranged with help of internal heat exchangers or bed material that is circulating between a combustion- and a gasification chamber. At present biomass gasification is not state of the art but there exist a lot of promising test facilities (e.g. the plant Gssing, Austria).
2.1.3.3 Gas cleaning The use of the producer gas leaving the gasifier requires special purity grades depending on the application in which the gas shall be used for. Especially catalysts used for synthesises require high gas purity grades. In the following, the impurities that should be removed from the gas to avoid e.g. catalyst deactivation or component damage are listed /43/:
Tars (in general hydrocarbons with a molar mass greater than the molar mass of benzene (78 g/mol)) Particles (inorganic ash, coke and bed material abrasion) Nitrogen compounds (ammonia NH3, hydrocyanic acid HCN) Alkalines (sodium- and potassium-compounds) Sulphur compounds (hydrogen sulphide H2S, carbon sulphide COS)
19
Halogen compounds (hydrogen chloride HCl, fluorinated hydrocarbon HCN) The removal of the impurities listed above can be done with help of manifold process components. Below the most common components are listed and described: The use of cyclones today is state of the art in a wide temperature range, low costs and small pressure drops. They are mainly used after fluidised gasification to separate the producer gas from bigger particles (> 5 m /43/) as dust, bed material and slight tar impurities by centrifugal forces. To achieve higher purity grades (up to 99,99 %) and separate the producer gas from smaller particles (> 0,5 m /43/), alkalines and tar fractions filters are used. Today different filter types (bag-, candle-, ceramic- and electric-filters) are state of the art but they differ in their costs, temperature level, separation rate and technical effort. To separate many different impurities within one process step physical gas washings are used. The impurities are absorbed by injecting a washing media into the gas stream under special temperatureand pressure conditions. According to the impurities that shall be washed out manifold washing media are in use (e.g. water, RME). To improve the effect of physical washings so called chemical gas washings are used. Instead of working with ordinary washing media chemical washings work with washing media (e.g. Selexol, Rectisol) that react with the impurities The compounds of washing media and impurities can be drawn of easily with remaining washing media. Another option to remove tars from the gas are tar crackers. With help of oxygen addition and high gas temperatures are achieved (around 1200 C) and about 90 % of the tars are converted. Adsorptive methods are mainly used to remove sulphur from the gas to avoid catalyst deactivation. They can achieve high grades of purity and are located in general after raw upstream sulphur removals. Zinc-oxide, iron-oxide and activated carbon beds are state of the art /45//46//8//47/.
2.1.3.4 Gas conditioning After the gas had been cleaned from different impurities the gas stream has to be adapted to the synthesis demands. Therefore (i) the H2/CO-ratio has to be adjusted, (ii) CO2 has to be removed from the gas and (iii) hydrocarbons have to be reformed.
In general the H2/CO-ratio is too low for the synthesis demands. To adjust this ratio to the synthesis demands two possibilities are state of the art: With water-steam CO can be converted into CO2 and H2 (water-gas-reaction). The reaction occurs under temperatures of 300 to 500 C and pressures up to 30 bar with help of Fe2O3/CrO catalysts. However, it has to be taken into account that the CO2 has to be removed afterwards. H2 can be added directly. One option to satisfy the H2 need is to draw of H2 from the synthesis gas that is not converted within the synthesis. The H2 separation from the synthesis gas can be arranged by the PSA (pressure swing adsorption). At present three methods to remove CO2 from the gas are common: Within the PSA (pressure swing adsorption) CO2 is discontinuous adsorbed under comparatively high pressures by active carbon or zeolites. To clean the active carbon or zeolites from the CO2 they are flushed from time to time by producer gas/raw gas at a low pressure level. Within the Rectisol-washing CO2, H2S, COS, HCN, NH3, organic sulphur compounds and hydrocarbons are absorbed by cold methanol (-30 up to -45 C, 30 to 60 bar). The methanol can be regenerated by reducing the pressure and increasing the temperature.
20
Within the Selexol-washing CO2 and H2S are absorbed by a washing media containing 95 % Dimethylether at pressures up to 30 bar and temperatures from 0 to 170 C. The regeneration of the washing media occurs by reducing the pressure and increasing the temperature as within the methanol regeneration. To reform the light fractions of hydrocarbons in the gas the following concepts are commonly used: The hydrocarbons react together with water-steam and a nickel catalyst to H2 and CO. The reaction heat is supplied externally by the water-steam (steam reforming). As in the steam reforming concept the hydrocarbons react to CO and H2. However, the heat is supplied by a partial oxidation in the first part of the reactor (autothermal reforming). FT-Synthesis The Fischer-Tropsch-Synthesis (FT-synthesis) is a polymerisation process whereby the cleaned and upgraded gas is liquefied into hydrocarbon chains of different length according to the general reaction equation (Equ. 2-1). It can be modelled as a chain grow reaction of H2 and CO on the surface of a cobalt- or iron-catalyst (Equ. 2-2). This reaction is strongly exothermal, about 25% of the chemical energy is converted into heat and has to be removed and used somewhere else (e.g. steam production) to maintain high efficiency and optimum catalyst life.
n CO + (n + 1 m) H 2 C n H m + n H 2 O n 2
CO + 2 H 2 CH 2 + H 2 O
H = -165 kJ/mol
Equ. 2-1
Equ. 2-2
The main performance parameter of the FT synthesis is the `chain growth probability or liquid selectivity` which is the chance that a hydrocarbon chain grows with another CH2`building stone, instead of terminating. The higher , the longer the respective hydrocarbon chains. A raw product spectrum is built out of light hydrocarbons (C1 C4), benzenes (C5 C10), diesel oils (C11 C20) and waxes (C21+), whereby chain lengths are a varying in literature. This selectivity, the distribution of raw products, depends on and is determined by several parameters like temperature, pressure, applied catalyst, reactor type and H2/CO-ratio of the syngas. The following applies in general: increases by decreasing H2/CO-ratio, decreasing reactor temperature and increasing pressure. In general the different process possibilities for the production of FT-Diesel are distinguished by three main categories: (i) the synthesis operation temperature, (ii) the synthesis operation mode and (iii) the synthesis reactor type. Considering the synthesis operation temperature FT processes can be distinguished into two operation temperature levels: high temperature processes (HTFT; temperatures of 300 to 350 C) and low temperature processes (LTFT; temperatures between 200 and 240 C). Higher temperatures reduce the average chain length and support the formation of methane, light hydrocarbons and aromatics. Therefore, the low temperature processes are preferred for Diesel production. The operating pressure of FT synthesis ranges generally from 20 to 40 bars. Higher pressure leads to higher selectivity. Further, there are two main operation modes (as mentioned above) applied in FT synthesis reactors: In full-conversion operation mode, unconverted syngas is looped back to the syngas stream which is increasing the overall syngas to FT raw product conversion rate. Also, hydrogen and CO from reforming of light hydrocarbons can be looped back (recycled) to the FT reactor input.
21
Such a looping is not done in once-through operation mode, where the surplus- and unconverted gas streams are used for heat and power generation in a gas and steam cogeneration plant /48/. Finally the used synthesis reactor type differs in two different designs for low temperature FTsynthesis /3//48/: Tubular Fixed Bed Reactor (TFBR). The TFB reactor consists of a vessel with long thin tubes which are vertically aligned in bundles. The syngas is entering on top of the reactor and flowing very fast through the tubes to create high turbulence which is good for an efficient conversion. The liquid raw products are withdrawn from the bottom of the reactor. On the outside of the tubes the reaction heat is withdrawn by generating steam which can be used in the plant. Advantageous is the fact that catalyst poison can be adsorbed at the entrance of the reactor avoiding its deactivation. A clear disadvantage is the long standstill periods of the reactor while the catalyst is renewed. This results in a big maintenance effort. Furthermore the investment costs of TFB reactors are higher than of the SBC reactor. Slurry Bubble Column Reactor (SBCR). The SBC reactor is built of a reactor coat which contains a cooling coil. Syngas is fed in at the bottom of the reactor and bubbles through a suspension (wax and catalyst particles). Unconverted syngas, light hydrocarbons and water are withdrawn at the top of the reactor body. Like in TFB reactors, surplus heat is withdrawn by steam generation for further use in other processes. The catalyst is in the suspension and can be exchanged during operation. This exchangeability of the catalyst leads to lower standstill times of the reactor, which is an advantage of the SBC reactor. Further advantages are lower investment costs and high conversion rates in once-through operation mode. A disadvantage of this reactor type is the hazard of catalyst deactivation by the entrance of a catalyst poison in the syngas stream. Hence, the SBC reactor requires very clean syngas quality for a safe operation. Further the separation of waxes and catalyst particles is sophisticated, which is another disadvantage of this reactor type.
2.1.3.5 Product upgrading The gaseous hydrocarbons in the FT raw products are volatile and therefore easy to separate. Water is separated conventionally by a condensate trap. The separation of the particular fractions is done via rectification (repeated distillation) in various columns.
Cracking of long chained hydrocarbons is done in a hydrocracker. Due to extreme reaction parameters (high temperature, high pressure), expensive special hardened steel is used. For the sake of FT products upgrading, Shell has developed a so called heavy paraffin conversion process (HPC) which combines the hydrocracker with an isomerisation unit over the same catalyst. Both processes run simultaneously. /49//45//47/
2.1.4 Methanol
The application of methanol in Otto engines bases on manifold experiences and is one option to become independent of fossil energy resources. In principle Methanol can be produced out of natural gas, coal gas and bio-gas. However, at present only the production of methanol out of natural gas is state of the art. But, the production of methanol out of biomass is under investigation and there exist a lot of laboratory tests that confirm the possibility to produce methanol out of biomass. In the following, the conversion of biomass into biomethanol will be described from a technical point of view. Fig. 2-4 below shows the main parts of the conversion process.
22
Fig. 2-4. Principle of methanol production.
2.1.4.1 Biomass pre-treatment / Gasification / Gas cleaning / Gas conditioning As the biomass treatment and gasification for the methanol production uses the same technical components and follows the same conditions as the biomass pre-treatment and gasification of the FTDiesel production this chapter focuses on the methanol synthesis and product upgrading.
The components of the producer gas cleaning and subsequent gas conditioning are also the same as the components used in the FT-Diesel production. However, the gas purity demands depend on the used catalyst. So, the purity demands within the methanol production differ from the purity demands for the FT-Diesel production as long as different catalysts are in use. Within the gas conditioning section of the methanol process the adaptation of the H2/CO-ratio and the hydrocarbon reforming take centre stage. However, they are using the same methods as the FT-Diesel process does.
2.1.4.2 Synthesis The methanol synthesis takes place according to Equ. 2-3 and Equ. 2-4: Hydrogen, CO2 and CO are converted into methanol; water is a by-product. The operating pressure of methanol synthesis ranges from 45 to 100 bar and temperatures of about 220 to 280 C. Catalysts based on copper (Cu), zinc (Zn) and aluminium oxide (Al2O3) are applied /50/. The chemical reaction is exothermic and occurs with a certain volume contraction.
3 H 2 + CO2 CH 3 OH + H 2 O
2 H 2 + CO CH 3 OH
H = -49 kJ/mol H = -91 kJ/mol
Equ. 2-3
Equ. 2-4
Considering different methanol process schemes the synthesis can be distinguished by (i) the reactor type and (ii) by the operation pressure level.
23
As in the FT-synthesis in the methanol synthesis there are two reactor types in common use: Fixed Bed Reactors (e.g. ICI-Quench reactor, Isothermal reactor, Linde-isothermal-reactor and multiple-bed reactor) Slurry Reactors (e.g. suspension/slurry-reactor) The operation pressure can be subdivided into three main pressure levels: The high pressure operation occurs within pressures of 250 to 350 bar, temperatures of 590 to 650 K and with Zn/Cr2O3 catalysts. The used catalysts are very resistant against catalyst poison like sulphur and show up a good thermal stability. The medium pressure operation occurs within pressures of 100 to 250 bar, temperatures up to 620 K and Zn/Cr2O3- or Zn/Cu-catalysts. However, in literature there is only little information about medium pressure operation processes within large scale production. The low pressure operation occurs within pressures of 50 to 100 bar, temperatures of 493 to 553 K and catalysts out of Cu, Zn and Al2O3 with high activity and selectivity. For industrial purposes almost only the low pressure operation is important as the pressure- and temperature-levels are good to handle and the used catalysts show up high activity and good product selectivity.
2.1.4.3 Product separation Within the synthesis several by-products as dimethylether, alkalis (CH4, CnH2n+2) and higher alcohols (ethanol, propanol, butanol) are generated in addition to the methanol fraction. In general these byproducts appear gaseous together with unconverted syngas fractions.
To separate higher hydrocarbons from the product gas stream first of all the gas is conducted into an oil separator. Afterwards the raw methanol is separated by condensing, storaged and upgraded in a distillation column (< 2 Vol. % H2O). The remaining gas stream is separated in a separator into two gas streams. One stream is recycled into the synthesis and the other part with huge CH4 content commonly is used in gas turbines.
2.1.5 Dimethylether
Another liquid fuel is dimethylether (DME) that has similar characteristics as Diesel fuel and liquefied petroleum gas (LPG). Hence, it is highly suitable for the substitution of fossil fuels within car engines. The synthetic production of dimethylether is possible in two ways: (i) it can be produced directly via synthesis or (ii) by the intermediate step methanol. For large-scale production, it has been shown that the integration of the two process steps, methanol and DME synthesis, is very advantageous and the best choice for DME production in terms of efficiency. As the process steps up to the DME synthesis are the same as within the methanol production this chapter focuses on the subsequent work steps (DME synthesis, product separation). In Fig. 2-5 below a process scheme of the DME production with the intermediate step methanol production is shown that today is state of the art.
24
Fig. 2-5. Principle of DME production.
2.1.5.1 Synthesis Methanol is an intermediate product. The methanol synthesis takes place according to Equ. 2-5 and Equ. 2-6: Hydrogen, CO2 and CO are converted into methanol; water is a by-product. The operating pressure of the methanol synthesis ranges from 45 to 100 bar and temperatures of about 220 to 280 C. Catalysts based on copper (Cu), zinc (Zn) and aluminium oxide (Al2O3) are applied /49/.
3 H 2 + CO2 CH 3 OH + H 2 O 2 H 2 + CO CH 3OH
H = -49 kJ/mol H = -91 kJ/mol
Equ. 2-5
Equ. 2-6
Then methanol is converted to DME whereby water is separated chemically. (Equ. 2-7). The reaction takes place at temperatures of about 250 to 300 C. This three reactions (Equ. 2-5, Equ. 2-6 and Equ. 2-7) are exothermal and the heat can be further used, e.g. for steam production /49//51/. For the DME synthesis commonly fixed-bed reactors without any special internal heat exchangers are used. Stoichiometric efficiencies of about 86 to 88 % referring on the raw methanol can be reached. The remaining 12 to 14 % can be subdivided into 7 to 8 % unconverted methanol, 3 to 4 % water such as carbon dioxide that is adsorbed by the dimethylether.
2 CH 3 OH CH 3 OCH 3 + H 2 O
H = -23 kJ/mol
Equ. 2-7
25
2.1.5.2 Product separation The product separation after the DME synthesis is less extensive than the separation of the FischerTropsch products. Besides water and unsolved gases the generated raw DME contains little amounts of ether compounds and alcohols.
The gases can easily be removed by reducing the pressure. Subsequently follows the final product cleaning by distillation. First higher ether compounds and other light fractions are removed afterwards higher alcohols and water. To separate amines from the raw DME ionic exchangers are used. Finally, the treated DME stream undergoes a low temperature separation where further residues are removed and fed into a distillation column. In the distillation column the residues are separated into burnable gas and synthesis raw fractions.
2.1.6 Biomethane
A comparatively new, promising option in decreasing the dependency on fossil fuels and reducing the greenhouse gas emissions is the substitution of natural gas with help of biomethane. Biomethane identifies a synthetic gas that can be fed into the natural gas grid. This gas is produced either through (i) the bio-chemical conversion of biomass with a subsequent gas cleaning process or through (ii) the thermo-chemical conversion of solid biomass via gasification with subsequent gas cleaning, methanation and product gas upgrading. In the following, these two processes are described briefly.
2.1.6.1 Biogas First, the production path via bio-chemical conversion will be described. An exemplary process scheme can be seen in Fig. 2-6 below:
Substratum (Maize, Manure)
Pre-treatment Fermentation residue treatment
Biogas production anaerobic fermentation

Raw biogas (50 60 % CH4)
Biogas upgrading (desulphurisation, methane enrichment)
Biomethane
Fig. 2-6. Principle of bio-chemical biomethane production.
Substrate pre-treatment On their way into the fermenter the substratum undergoes the following treatment steps: (i) the delivery to the plant, (ii) the storage, (iii) the upgrading and (iv) the transportation from the storage to
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the fermenter. Within these steps there is one of the highest optimisation potentials of the overall process./7//52/ The storage depends on the substratum type. In general caverns/cavities and storage silos are used. For liquid substratum manure storage tanks are in use. The size differs among other things with the plant size and the delivery contracts and has to compensate operation failures. The substratum upgrading has a strong influence on the fermentation process concerning the methane building process. The upgrading can be subdivided into the following aspects: Separation (e.g. separation of stones and metal) Thermal treatment (from a hygienic point of view a thermal treatment is necessary to avoid epidemics; in addition a thermal treatment improves the fermentation conditions) Milling (a previous milling improves the possibility to pump the biomass and improves the biologic decomposition process) Mashing (mixing liquid biomass with solid biomass to improve the possibility to pump the biomass) Homogenising of the solid-liquid mixture (the homogenising occurs e.g. with help of an agitator to improve the process stability) The transportation of the substratum into the fermenter can be subdivided in pumping of almost liquid substratum and the transportation of stackable substratum. The transportation process should be continuous, however, a continuous transport is hard to realise from a technical point of view. In addition the transported substratum should have the same temperature as the fermenter to improve the process biology what seems to be problematic in winter. Biogas production by fermentation The biogas production by fermentation follows a bio-chemical conversion process of several kinds of biomass. The fermentation is a complex metabolism chain which can be divided into four sub steps: (i) the hydrolysis, (ii) the acidification phase, (iii) the acetic acid phase and (iv) the methanation building phase. Each step is characterised by the attendance of special bacteria. Even though there are different plant set ups in principle all processes follow the anaerobic fermentation scheme. The heart of each biogas process is the fermenter. At present there are two types of biogas fermenters in use: Wet fermenter: Wet fermenters use wet substratum for the conversion process (e.g. Navaro mixed with manure). They can be subdivided into two different fermenter types again: (i) the lying wet fermenter and (ii) the upright wet fermenter. The size of lying fermenters is limitated by approximately 800 m and they are used for smaller biogas plants or as pre-fermenters. Upright fermenter are limited by approximately 6.000 m of size and in general they are constructed at the plant itself. Dry fermenter: Dry fermentation processes do not use biomass mixed with manure or other liquids nor agitate the biomass during the fermentation. This allows the use of stackable biomass and reduces the pre-treatment effort. With help of Perkolat-liquid the bacteria life conditions are hold up and the substratum is kept at a constant moisture level. The heat management is done by the circulating, pre-heated Prekolat-liquid and external heating of the fermenter. Biogas upgrading The biogas leaving the fermentation section has to be cleaned and adjusted the natural gas grids specifications (c.f. Wobbeindex specifications of the DVGW-working sheet G263). The major tasks in adjusting the biogas to the wobbeindex specifications is the removal of sulphur (mainly H2S), CO2 and
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H2O. For this purpose many of the procedures mentioned in the chapters above are in use (PSA, ZnObeds, water washings, amine washings, Selexol- and Rectisol washings). However, two methods to remove sulphur within the fermentation process itself shall be described in the following /20/: Sulphide precipitation: Within this method iron-salts (e.g. FeCl2 or FeSO4) are added to the substratum or fed into the fermenter. Thereby, the sulphur-ions are bond to the iron-ions and the H2S building is reduced. However, a finer desulphurisation has to be done afterwards and this method is primarily applicated at smaller plants Integrated biologic desulphurisation: Within this desulphurisation method air (8 to 12 % of the biogas volume flow) is fed into the gas room of the fermenter. However, this desulphurisation method is insufficient, the biogas quality is declined by inert gases, the fermenter can be damaged by corrosion and explosive gas mixtures can be produced.
2.1.6.2 Bio-SNG After the bio-chemical conversion path of biomass into biomethane within the following chapter the thermo-chemical conversion path will be described. The process scheme can be seen in Fig. 2-7 below.
Fig. 2-7. Principle of thermo-chemical biomethane production.
It can be seen in Fig. 2-7 above that the first process steps (biomass treatment, gasification, gas cleaning and gas conditioning) are similar to many other biomass conversion paths (c.f. FischerTropsch fuels). As the first process steps are described in detail within the previous chapters this chapter focuses on the subsequent steps (methanation, product upgrading). However, it should be
28
mentioned that the first process steps have to be adjusted to the following. Especially the methanation requires high gas purity grades (nearly sulphur free gas) and a fix H2/CO-ratio. Methanation At present, only the methanation of cleaned and conditioned gas out of coal is state of the art. However, the methanation of gas generated out of biomass is under investigation in several test facilities and show up good results. Methanation can reach energetic efficiencies of round about 80 %, occurs strongly exothermic and follows the following chemical equation (Equ. 2-8):
3 H 2 + CO CH 4 + H 2 O
H = -206 kJ/mol
Equ. 2-8
For a fast and effective conversion Nickel- or Copper-based catalysts are used. The Nickel-based catalysts work at a temperature level of 200 to 400 C and pressures up to 10 bar. However, a pressure higher than 1 bar is advisable due to higher catalyst activity, shifting of the reaction equilibrium in direction to higher CH4 rates and higher mass flow rates at constant volume flows (allows smaller reactor sizes). The Copper-based catalysts work at temperatures up to 450 C. Pressures up to 50 bar are advisable /53/. For managing the heat currently several reactor concepts are in use or under investigation. Multiple fixed-bed reactors in one row with intermediate cooling Fluidised-bed reactors with internal heat exchangers Another heat management option is to recycle cold gas and to re-feed it into the methanation. Product upgrading To feed the gas generated within the methanation into the natural gas grid several gas purity demands have to be met (c.f. Wobbeindex specifications of the DVGW-working sheet G263). As the raw biomethane has a comparatively high H2O and CO2 content, these components have to be reduced within the product upgrading section before feeding the biomethane into the gas grid. To remove CO2 from the raw biomethane stream in the following two processes are described as an example: the rectisol process developed by Lurgi and Linde and the selexol process developed by Dow Chemical. Both processes are gas-liquid scrubbing processes using different solvents and process conditions /54/: Rectisol Process: Cold methanol (-30 to -45 C) is used in this process as physical solvent. High pressures are positive for the absorption ability of the solvent, thus pressures of 30 to 60 bars are applied and contaminants like CO2, H2S, COS, HCN, NH3, sulphur compounds, hydrocarbons and others are absorbed. By releasing the pressure, the contaminants are desorbed and undergo further treatments. During reactivation of the solvent some gases are set free (H2, CO) which are recycled back to the synthesis unit. Selexol Process: A special mixture is used in this process as solvent, consisting of 95 % dimethylether (DME) based on polyethylene glycol. The process takes place at pressures of 10 to 30 bar and in a temperature range of 0 to 175 C. The spectrum of absorbed contaminants is similar to the spectrum mentioned in the rectisol process. Raw gas and solvent are brought into contact in a counter flow absorption column whereby impurities like H2S or CO2 are absorbed. Subsequent these impurities are desorbed by pressure release in an expansion vessel. Residue CO and H2 can be recycled back to the synthesis unit. Both processes Rectisol and Selexol are highly sophisticated, yet their big advantage is the removal of many other impurities beside CO2 from the gas stream favouring them as scrubber process. In addition two other methods are common to remove CO2 from a gas stream: (i) the pressure swing adsorption (PSA), which is mentioned in the chapters above and (ii) amine washings.
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The PSA is characterised by a simple design and high methane co-adsorption in comparison with the Selexol- or the Rectisol-washing. The amine washings using monoethanolamine (MEA) or Diethanolamine (DME) as washing media achieve very high gas purity grades. However, these methods have a comparatively high energy demand to regenerate the loaded washing media. To remove H2O from the raw biomethane commonly the gas stream is first cooled down to separate parts of the water fraction by condensing. Afterwards the following two methods are used in general: Glycol washing: Within the glycol washing primarily Triethylenglycol (TEG) is used as absorption media. The grade of absorption is comparatively high, however, there is a high energy demand to regenerate the TEG solution. Adsorptive methods: Beside using condensing- and glycol washing methods the gas drying can be achieved by adsorptive methods. A common adsorptive procedure is the pressure swing adsorption (PSA) mentioned in the foregoing chapters. Another option is the temperature swing adsorption (TSA) whereby the adsorbed water is desorbed by a hot (120 to 150 C) counter flow.
2.1.7 Biohydrogen
In general, hydrogen is used as raw material in chemical industries. Due to increasing environmental requirements and consumption of this industry (especially the petrochemistry and the refinery industry) the world wide hydrogen demand is forecasted to increase about 5 to 7 % While currently the hydrogen economy bases on the hydrogen production out of fossil energy sources in the long run renewable energy shall be the fundament of the hydrogen production. Thereby the hydrogen production via bio-thermal biomass conversion seems to be one promising perspective. At present, this process is under investigation at the state of pilot plants /55/. One process scheme of this bio-thermal conversion of biomass into hydrogen can be seen in Fig. 2-8 below.
Fig. 2-8. Principle of biohydrogen production.
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As the process steps biomass pre-treatment, gasification and gas cleaning are similar to the process steps of the biomass conversion concepts described above, in this chapter the subsequent process steps (gas conditioning, hydrogen cleaning and hydrogen treatment) are the focal points of this chapter. However, it has to be mentioned that the gasification and the gas cleaning have to be adjusted to the hydrogen generation process. So, the gasification should produce a gas with high H2/CO-ratio.
2.1.7.1 Gas conditioning As within the conversion of biomass into hydrogen there is no synthesis, the gas conditioning is one of the most important parts of this process. So, the general aim of the gas conditioning is to increase the hydrogen content of the producer gas. For this purpose two process steps can be applied: (i) an optional reforming step and (ii) a water-gas-shift step. Within the optional reforming step two different methods are common:
Within the endothermic steam reforming method hydrocarbons are converted into CO and H2 with help of water-steam, temperatures of 800 to 900 C, pressures of approximately 26 to 40 bar and a catalyst (nickel-aluminium or noble metals on carrier material). The gas is mixed with process steam, pre-heated and fed into parallel reforming tubes filled with catalyst material. The heat can be supplied by the oxidation of methane or rest gas from the gas cleaning. The final H2/CO-ratio can be adjusted by varying the process parameters. A typical gas composition is: H2 (70 to 75 vol. %); CO (8 to 18 vol. %); CO2 (10 to 12 vol. %); CH4 (2 to 5 vol. %). The chemical reactions of the autothermic reforming are similar to the chemical reactions of the steam reforming. However, the heat supply differs. Within the autothermal reforming the heat is supplied through partial oxidation of the gas stream itself with help of air or oxygen. Within the used reactor a mixing facility allows fast mixing of the gas-steam compound with the fed in, preheated oxygen/air. The combustion- and reaction zone is located directly above the catalyst bed. The process pressure is about 70 bar, the temperature between 800 and 1100 C. However, the produced gas has a comparatively low H2/CO-ratio. After the reforming follows a water-gas-shift reaction for further increase of the H2-ratio. Thereby, parts of the CO are converted into H2 and CO2 by addition of water-steam. In general, this conversion occurs in two reactors: (i) a high temperature reactor with approximately 350 C (iron-chromium catalyst: CO conversion rate of 80 to 90 %) and (ii) a low temperature reactor with approximately 190 to 210 C (copper catalyst). Within this conversion nearby 90 to 97 % of the CO is converted. An alternative is the use of a single medium temperature reactor. The capital costs are comparatively low due to the very simple reactor design /56//57//58//50/.
2.1.7.2 Hydrogen cleaning In general, the first gas cleaning step is the water removal through condensation. In the following, the gas is cleaned by the so called pressure-swing-adsorption (PSA). The PSA uses the different partial pressures of the gas components to adsorb undesired components. The PSA operates with temperatures of about 40 C and leads to purity grades up to 99,999 vol. % (chemical and physical absorption methods do not lead to such purity grades). To adsorb the gas impurities active carbon or zeolite is used as adsorption material. The desorbtion is done by reducing the pressure and flushing the adsorbtion material with inert gas. The desorbed rest gas contains CO2, CH4, CO, N2, water-steam and little amounts of H2. The rest gas can be used for the process heat supply /59//60/.
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2.1.7.3 Hydrogen treatment For the final use of the produced hydrogen the energy density has to be increased. For this purpose there exist two common possibilities: (i) hydrogen compression and (ii) hydrogen liquefaction.
The hydrogen compression is done by several stages. The costs depend on the volume flow of the hydrogen and the intake-/outlet-pressure. The intake-pressure is about 13 to 30 bar and the outletpressure is at least around 250 bar. The liquid hydrogens density is notable higher than the density of compressed hydrogen. The hydrogen is liquefied by cryogenic procedures. In large scale processes the liquefaction is done by the Claude-process: Within the Claude-process the gas is first compressed and cooled down with liquid nitrogen up to -196 C. Further cooling is done by hydrogen-expansion turbines and expanding at a choke valve. The hydrogen has a final temperature of -253 C and a pressure of 1,2 bar. The theoretical energy demand of the liquefaction is 3 kWh/kg H2, practical 10 kWh/kg are needed. Even though the hydrogen has a comparatively high purity grade after the gas cleaning it has to be cleaned a second time (up to 1 ppm impurities) before being liquefied. At present liquefaction plants have a scale of 4 to 54 t/d H2 /61/.
2.1.8 System-technological comparison of biofuel options

Based on the technology characteristics, the biofuel options have been compared by means of biofuel production (i.e. stage of development, technical effort in terms of system complexity, expected plant capacity and overall efficiency) and the biofuels suitability concerning current fuel distribution systems as well as current use in vehicle fleets. With regard to European conditions a summary is shown in Tab. 2-1.
Tab. 2-1 Comparison of biofuel specific system technology aspects
Biomass conversion to biofuel State of technology Conventionell Biodiesel Bioethanol Future Advanced biodiesel Bioethanol (Ligno.) Biogas FT-fuels Biomethanol Dimethylether Bio-SNG Biohydrogen Legend
a b c
Biofuel option
Infrastructure and use of biofuels Overall efficiency +++ ++(+) +++(+) ++ +++ +(+) ++ ++ +++ ++ Availability distribution +++++ ++ +++++ ++ +++ +++++ ++ + +++ + Blend to fossil fuels ++++ ++++ +++++ +++ +++++ +++++ ++ + +++++ + Availability vehicles ++++(+) ++++(+) +++++ +++(+) +++(+) +++++ ++ ++ +++(+) +
Technical effort ++++ +++ +++ ++ +++ + ++ ++ ++ ++
Plant capacity ++++ +++ ++ ++(+) ++(+) + ++ ++ +++ ++
+++++ +++++ ++++ ++ ++(+) ++ +(+) ++ ++ +(+)
+++++ very promising, +++ promising, + unfavourable in terms of complexity of biofuel production (i.e. from biomass treatment to final product) in terms biomass input and flexibility regarding capacity as indicator for suitable plant locations (concept specific) energetic netto efficiency (base current development stage, theoretical considerations)
Therefore, it can be revealed that the different concepts for biofuel options of the future generation are associated with appropriate benefits and bottlenecks along the pathway. While e.g. FT fuels are less promising concerning the technical effort, the range of capacities (with regard to suitable plant locations) and the overall efficiency, it seems to be very promising regarding the implementation into the current distribution and use infrastructure.
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2.1.9 Overview of major demonstration projects

An overview of major demonstration project is summarised in the following (Tab. 2-2), whereby the focus is laid on European experiences.
Tab. 2-2. Overview of major projects of future biofuel options /62//63//20//64//30//65/.
Projects NExBtL Porvoo, Finland

Characteristics / Status of technology
developed by Neste Oil 1st plant (capacity of 170 kt/a) at the refinery Porvoo was commissioned in summer 2007, 2nd plant is planned for end of 2008 TOTAL: give up built up after comprehensive feasibility study for plant at refinery Dunkirk (F) due to costs reasons, OMV: feasibility study for plant (capacity 200 kt/a) at refinery Schwechat (A)
Bioethanol Ottawa, Canada
Fuel capacity:3,000 m/a (2.4 t/a) using wheat, oat, and barley straw Start up in 2004, upgrading in 2006 Modified steam explosion pretreatment and patented enzyme Use of lignin in a CHP that generates the energy needed to run the demonstration facility Use of cellulosic EtOH for its own fleet of 13 vehicles and fleet vehicles of two Canadian government departments
Plan to license its technology for first commercial plant of expected fuel capacity of 75,000 m/a (approx. 60 kt/a) using corn stalks and cereal straws; potential sites: north central Saskatchewan, east central Alberta, and southeast Idaho
Bioethanol Royal Nedalco, the Netherlands
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Nedalco has announced to build a bioethanol plant in Sas van Gent, Netherlands; operational end 2008 Running on wheat residues containing C5 sugars and using a patented yeast that it has developed itself that can convert xylose (hemicellulose) into bioethanol Plant capacity: 200 mn l/a (158 kt/a)
Investment: 150 million
Bioethanol Abengoa, Spain
Pilot scale plant in York, (Nebraska, US) for evaluation of novel biomass fractionations, processes and valorisation of all process streams Demonstration plant in Babilafuente (Salamanca, Spain) for evaluation of the upscaling to commercial stage Focus on enzymatic hydrolysis technology R&D on biological deconstruction of biomass to produce defined enzyme mixes for each specific case Advance in the sugar fermentation to ethanol through the engineering of microbial systems
Development on thermo-chemical bioethanol production via gasification and synthesis; focus on synthesis catalysts development
Bioethanol EPAB / ETEK / SEKAB, Sweden
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Pilot plant demonstrating the complete process from forestry residues to ethanol built on rnskldsvik within the frame of the EU-project NILE New Improvements for Lignocellulosic Ethanol Capacity: 300 to 400 l/d (approx. 2 t/d dry matter) Start up end of 2006 continues operating ethanol production inclusing two-steps dilute acid- and/or enzymatic hydrolysis Investment: 22 Mio. Owned by holding companies of Ume University and Lule University of Technology (EPAB)
Use of ethanol in bus fleets
Fischer-Tropsch-Fuels Choren, Germany
Worldwide the first commercial BtL demonstration plant (Choren Industries) is expected to start operation in 2008 at Freiberg (Germany); 15000 t/a fuel output; 45 MW fuel power input; 68000 t/a biomass input (50 % of the biomass are foreseen to be used wood of the categories A I/A II and 50 % are foreseen to be logging residues; gasification according to the Carbo V method Plans for a second plant of 200000 t/a fuel output
Synthetic fuels FZK, Germany
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Test facility for slurry production (10 kg/h) BtL pilot-plant (500 kg/h) at FZK in cooperation with Lurgi and Siemens Fuel Gasification Technology (in former times Future Energy): 1. Biomass conditioning (fast pyrolysis, slurry production) 2006 2. Gas production (entrained flow gasification under pressure) 2007
3. Gas cleaning, fuel synthesis 2008
Synthetic fuels Chrisgas, Sweden
Plans for test facility for fuel production (DME, methanol, FT-fuel, hydrogen) production; 18 MW fuel power input IGCC plant in operation from 1994 2000; 18 MW fuel power input Plans to re-build the plant with addition of section for automotive fuel production (DME, methanol, FT-fuel, hydrogen) End 2007 Re-build plant commissioning January 2009 Start test programme 2009
DME Chemrec, Sweden
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BtL-production from black liquor (residue of pulp mill) Fuel production as an alternative (new infrastructure and usage systems needed) for Diesel market integrated processes for high fuel conversion (energetic integration in pulp mill) 1. Plant commissioning of the syngas production at Pite (Sweden) 2005; pressurized black liquor gasification with oxygen 2. Start test program 2006 3. Plans for DME and methanol production pilot plant
Bio-SNG TU Vienna, EEE, Austria

Test facility for Bio-SNG (biomethane) production 1. Start of plant construction (gasification, gas cleaning, gas engine) 2000 (8 MW fuel power input) 2. Start of operation (gasification, gas cleaning, gas engine) 3. Start of construction of the methanation section 2007 (1 MWfuel) 4. Start of operation of the methanation section At present 34,000 operation hours for a fluidised-bed gasifier with steam as gasification agent and 8 MW fuel power input Test facility for different research projects (e.g. Bio-SNG production, BtL production)
Biogas diverse, Sweden
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Natural gas substitution by upgraded biogas Biogas is generated via fermentation of different biomass types Example: Plant Stockholm-Henriksdal: Biogas is produced by clearing sludge fermentation 1. Succesful operation since 2003; Production of 600 mSTP/h raw gas of natural gas quality plus covering of the own energy consumption 2. Plans for plant expansion of 800 mSTP/h
2.2 ECONOMIC AND ENVIRONMENTAL ASPECTS

Referring to the targets in context of sustainability biofuels and biorefinery products need to be economic efficiency (here i.e. production and use of transportation biofuels and biorefinery products at competitive costs) and environmental friendly (here especially with regard to the global warming effect). Both aspects are considered in the following.
2.2.1 Economic aspects

With regard to requirements, for a successful market implementation of future biofuel options the consideration of economic aspects include the investigation of capital investment requirements, biofuels production costs and well-to-wheel (WTW) costs at European conditions. This is done for the different future biofuel options in comparison to costs for the conventional biofuels (i.e. biodiesel and bioethanol).
2.2.1.1 Capital investment requirements Total capital investment (TCI) requirements of biofuels production plants are highly important with regard to financial risks on the on hand side and as it is the case for more complex biofuel concepts regarding the biofuel production costs.
The determination of TCI costs is based on study estimation (accuracy of approx. 20 to 30 %) including the method of additional or overhead costs. According to this, plant equipment costs have been determined by up- or downscale (typical scale factor of approx. 0.7) of existing costs data for similar devices. Moreover, component specific installation factors (e.g. 1.54 to 1.66) have to be taken into account /20/. Thereby for some components literature data are available; for some components (e.g. that are currently in pilot stage) only rough estimations of technology developers are available. The investment cost figures given were calculated with references from literature dating from 2005 or before. An overview of rough estimations on TCI for future biofuel production plants is summarised in Tab. 2-3.
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Tab. 2-3. Overview of TCI for selected biofuel options /49//51//66//8//20//52//38/.

Biofuel option Basic plant equipment Typical (expected) plant size [MWbiofuel] 4 to 190 TCI [mn EUR] Specific TCI [EUR/kWbiofuel]
Conventional options Biodiesel Feedstock refinery, trans-/esterification, biodiesel washing, by-product cleaning and upgrading (e.g. glycerine, sulphates, methanol recovery), auxiliaries Bioethanol Feedstock pretreatment, hydrolysis / saccharification, fermentation, distillation/rectification, final upgrading, byproduct treatment (e.g. DDGS, bagasse), auxiliaries
0.9 to 65
190 to 340
7 to 220
16 to 300
1,360 to 2,290
Future options NExBtL Feedstock refinery, hydrogenation, product separation, auxiliaries Bioethanol Feedstock pretreatment, hydrolysis / saccharification, fermentation, distillation/rectification, final upgrading, byproduct treatment (e.g. lignin), auxiliaries Feedstock pre-treatment (e.g. mechanical, pyrolysis, torrefaction), gasification, gas cleaning and conditioning, FT synthesis, FT upgrading (e.g. hydrocracking), by-product treatment (e.g. naphtha), auxiliaries Feedstock pre-treatment, gasification, gas cleaning and conditioning, methanol synthesis, product upgrading (e.g. separation), auxiliaries Feedstock pre-treatment, gasification, gas cleaning and conditioning, DME synthesis, product upgrading (e.g. destillation), auxiliaries Feedstock pre-treatment, gasification, gas cleaning and conditioning, methanation, final gas upgrading, auxiliaries Feedstock pre-treatment, digestion, final gas upgrading, auxiliaries Feedstock pre-treatment, gasification, gas cleaning and conditioning, final upgrading, auxiliaries
> 260
> 100
390
15 to 185
30 to 325
1,800 to 2,000
FT-fuels
> 130 to 220
430 to 500
2,300 to 2,600
Biomethanol
126 to 270
232 to 330
1,200 to 1,800
DME
130 to 340
290 to 350
1,030 to 2,200
Bio-SNG
23 to 170
30 to 170
1,000 to 1,300
Biogas
5 to 15
7.5 to 23
1,500 to 3,000
Biohydrogen
140 to 450
220 to 450
1,000 to 1,600
With regard to economy of scale specific TCI typically decrease with increasing plant capacity. However, there is a continuous cost increase in the engineering and construction industries, which cannot be reflected at all. The price development of chemical plants and machinery (that also refers to biofuel production plants) is commonly indexed by means of the so-called Klbel-Schulzemethodology. According to this price index, the TCI for chemical plants has been increased by approx. 35 % in the period from 2000 to 2007.
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2.2.1.2 Biofuel production costs Production costs of future biofuels have been analysed for exemplary concepts at a data base of the time horizon of 2005. The results are summarised in Fig. 2-9. As the results of the economic analysis reveal, biofuel production costs show significant differences. Based on GJ fuel equivalent (FE) biomethane options (SNG and biogas) are the most favourable. The sensitivity analyses carried out for the determination and optimisation of influencing cost components to the total biofuels production costs show that besides the annual full load hours of the plant, feedstock costs and capital requirements are strongly important. It is expected that biofuel production costs will moderately increase in future due to rising energy prices with expected price effects for feedstocks during broad implementation of biofuel strategies.
Biofuel production costs vs. product costs fossil fuels [/lFE] 1,50 Feedstock 1,25 1,08 1,00 0,96 0,82 0,75 0,66 0,62 0,67 0,68 1,01 0,93 0,90 Plant operation Capital related costs By-products (credits) Total
1,13 0,97
1,13
0,50 0,37 0,31 0,25 0,21
0,00
MeOH ind (SRC)
DME ind (SRC)
EtOH ind (Lig.Res)
SNG ind (SRC)
GHyd. (SRC)
FT ind (SRC)
-0,25 NExBtL (palm oil) NExBtL (rape oil)
SNG ind (Lig.Res)
BG ag (Glle)
BG ag (Maize)
FT ind (Lig.Slurry)
LHyd. (SRC)
Diesel
Gasoline
Fig. 2-9. Biofuel production costs vs. fossil fuels (German product costs) /20/.
Based on literature and study survey the bandwidth of available production costs of biofuel options is presented in Fig. 2-10. Also the international studies show that no significant cost reduction can be expected compared to biofuels of the current generation.
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Natural gas
Biogas - Residues Biogas - Maize silage Bio-SNG - Lignocelluloses Liq.Biohydrogen - Lignocelluloses Gas.Biohydrogen - Lignocelluloses Biomethanol - Lignocelluloses DME - Lignocelluloses FT-fuels - Lignocelluloses Bioethanol - Lignocelluloses Bioethanol - Sugar cane Bioethanol - Sugar beet Bioethanol - Maize Bioethanol - Wheat Biodiesel - Grease Biodiesel - Soja Biodiesel - Rape 0 10 20 30 40 50 60 70
Bandw ith biofuel production costs [/GJ]
Fig. 2-10. International results on biofuel production costs /67//68//69//70//71//72//73//74/.
2.2.1.3 Well-to wheel costs However, for a market implementation not only biofuel production costs but also total driving costs relating to WTW are of importance for end users. Therefore, with regard to the WTW biofuel costs involving costs of fuel distribution (i.e. via pipeline or tank) and vehicles costs of new private cars (i.e. in combustion and hybrid engines, fuel cells, here estimated referring to /66/) the following results (Fig. 2-11) can be indicated per vehicle km.
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Bio-SNG (OE) Biogas (OE) GHyd./LHyd.(FC) GHyd./LHyd.(OE-Hyb.) GHyd./LHyd.(OE) future options DME (DE-Hyb) DME (DE) Biomethanol (OBR+FC) FT-fuels (DE-Hyb) FT-fuels (DE) Bioethanol (OM-Hyb.) Bioethanol (FFV) NExBtL (DE-Hyb) NExBtL (DE) Bioethanol - EU (FFV) for comparison Biodiesel - EU (DE) Natural gas (OE) Gasoline (OE) Diesel (DE) 0,00 0,10 0,20 0,30 0,40 0,50 0,60 Biofuel costs min Biofuel costs max Distribution min Distribution max Vehicle costs
WTW costs - passenger car [/km]
Fig. 2-11. WTW costs (passenger cars) of different biofuel options /20/.
According to this, the differences in biofuel production costs will be lowered in terms of total driving costs as except for fuel cell application there is a similar cost range for all biofuels, primarily dominated by vehicle use costs. The costs for biofuel distribution play only a minor role. For a number of reasons (e.g. immature large-scale production) the biofuels of the future generation are significantly more expensive when compared to conventional oil-derived fuels such as diesel at total driving costs of approx. 0.33 /km.
2.2.2 Environmental aspects

An expanding biomass usage should also always follow environmental criteria. Next to the impacts related to environment through the biofuel production and usage itself preserving diversity, conservation of ecosystems, avoiding negative impacts of fertiliser, avoiding water pollution and avoiding soil erosion are basic sustainability criteria. Within the international context, environmental impacts of any product (e.g biofuels) or services (e.g. driven kilometre) are often analysed by a so-called life cycle assessment (LCA). Both the basics on LCA and exemplary results of international studies are explained in the following.
2.2.2.1 Basics on life cycle assessment
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As the expression implicates does a life cycle assessment consider the full life cycle of a product from resource extraction to waste disposal (i.e. from cradle to grave). Its goal is to give an all inclusive picture of the environmental impacts of products or systems, by taking into account all significant upstream and downstream impacts. The assessment should include the production or extraction of primary sources (energy crops or residues), the processing, transportation and distribution of the fuels, building of conversion plants and other, the usage of the fuel in motor engines and waste disposal. Furthermore, by-products should appropriately be considered along the life cycle of the production of the fuel. All impacts are dependent on the global or regional system, where the production takes place or whose resources are used. Therefore, a detailed knowledge of the surrounding system is necessary to evaluate the environmental impacts of a product or system accordingly. The method of how to undertake a LCA is laid out in two international norms, the ISO 14040 and ISO 14044. According to these norms, a LCA is generally divided into four phases (Fig. 2-12). This also includes a balance of all in- and outputs according to defined system boundaries and functional unit and allows the improvement and the comparison of production processes.
Fig. 2-12. Framework of an LCA.
The goal depends on the exact research question, the target group and the application. The scope considers the time frame, the geographical locations and the state of the technology. In the goal and scope definition, the aim and the subject of an LCA study are determined, a functional unit is defined taking into account the primary pathway of biofuel supply and the secondary pathways of auxiliaries and utilities supply (Fig. 2-13). An example of a functional unit is the driven distance of one km of a passenger car with, for instance, the aim to compare the environmental impacts of different sorts of automotive fuels.
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PRIMARY PATHWAY Biofuel supply chain Cultivation / Biomass production
SECUNDARY PATHWAYS Auxiliary energy / utilities supply chains

e.g. land use (set aside, fallow) seeds, fertiliser, pesticides, diesel fuel land machinery
WELL-TO-TANK
Biomass residues
Energy crops
WELL-TO-WHEEL
Biomass provision
e.g. auxiliary energy collection / treatment / storage diesel fuel / auxiliary energy transport e.g. auxiliary energy / utilities plant(de-)construction/infrastructure e.g. surplus energy / by-products and their credits e.g. auxiliary energy treatment / storage diesel fuel / auxiliary energy transport e.g. engine manufactoring /infrastructure
Biofuel production
Biofuels 1st/2nd generation
Distribution to end user TANKTOWHEEL
Mobile use System boundary - LCA
Fig. 2-13. Process chain analysis with the inventory analysis.
In the inventory analysis, for each of the product systems considered data are gathered for all the relevant processes involved in the life cycle. A product system can be considered as a combination of processes needed for the functioning of a product or service. The outcome of the inventory analysis is a list of all extractions of resources and emissions of substances caused by the functional unit for every product system considered, generally disregarding place and time of the extractions and releases. As shown in Fig. 2-13 different secondary pathways have to be taken into account. Moreover, regarding the assessment of by-products within the LCA two accepted methodical approaches are applied (see Tab. 2-4). Both the allocation and the system extension methods are very realistic approaches to reality; however, they yield in different results.
Tab. 2-4. Methods for the assessment of by-products.
Allocation Fact The most valuable products can be held responsible for the largest environmental burden in a chain. Mass-, physical or economic value of byproducts brought out of the system as environmental value Distribution of environmental burden over two or more products System extension / Substitution By-products from a biofuel supply chain avoid the production of those products elsewhere in the society. Causality, by-products compansated within the system
Principle
Approach
Credit by subtracting burden of avoided system, quite complex
The impact assessment aims to improve the understanding of the inventory results. Firstly, it is determined which extractions and emissions contribute to which impact categories (Fig. 2-14, Tab. 2-5).
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An impact category can be defined as a class representing environmental issues of concern into which results from the inventory analysis may be assigned. The next step in the impact assessment is the characterisation. The aim of the characterization is to aggregate the releases of pollutants and the extractions of resources of a product system for a number of predefined environmental impact categories.
Fig. 2-14. Process chain analysis and impact assessment. Tab. 2-5. Impact categories of an LCA.
Impact Primary energy demand Global warming effect Indicator catagories Depletion of resources, focus on non-renewable sources (e.g. coal, natural gas, mineral oil, uran) Warming of global atmosphere due to anthropogenic climate relevant gases; most important green house gas emissions: CO2 and it equivalents CH4 (23 CO2eq), N2O (296 CO2eq) Shift of acid balance in soil and water through acid forming gases: SO2 and its equivalents, e.g. NOx (0.7 SO2eq), NH3 (1.88 SO2eq), HCl (0.88 SO2eq) Nutrient cycles in soil and water through PO43- and its equivalents NOx (0.13 PO43-eq), NH3 (0.35 PO43-eq) Forming of photo oxdidates (e.g. ozone) in atmosphere through interaction of sun radiation, NOx and CFC Destruction of ozone layer in the stratosphere by e.g. CFC, N2O Human toxic impact of fine dust (PM10) in the air due to e.g. NOx, CFC, NH3, SO2
Acidification
Eutrophication
Photo / summer smog
Ozone layer depletion Human toxicity
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The final phase in an LCA study is the interpretation of the results from the previous three steps, to draw conclusions and to formulate recommendations for decision makers.
2.2.2.2 Comparison of international results In most of the studies, the global warming effect and the primary energy demand are the focused impacts to the environment. Consolidated results of international studies for greenhouse gas (GHG) emissions per driven km (passenger cars) are shown in Fig. 2-15 for the conventional biofuel option as well as the considered future biofuel options (cf. chapter Error! Reference source not found.).
200 GHG emissions per vehicle kilometer private car [gCO2-eq./km]. 180 160 140 120 100 80 60 40 20 0 Rape seed oil Soya oil Biodiesel (rape) Biodiesel (soya) Biodiesel (palm) Biodiesel (sunflower) Biodiesel (tallow) Bioethanol (cereals) Bioethanol (maize) Bioethanol (sugar beet) Bioethanol (ligno. residues) Bioethanol (ligno. crops) EMPA/ESU, 2007 EUCAR/CONCAWE/JRC, 2007 IE, 2004-2007 IFEU, 2004-2007 VIEWLS, 2005 ZSW, 2004
NExBTL (rape seed oil) NExBTL (palm oil)
FT-fuel (ligno. residues) FT-fuel (ligno. crops) Biomethanol (lignocellulosic) DME (lignocellulosic) Biohydrogen (lignocellulosic) Bio-SNG (lignocellulosic) Biogas (energy crops)
Conventionell biofuel options
Advanced / future biofuel options
Fig. 2-15. International results on global warming potentials (average values) /20/.
As one can reveal there are partly large bandwidths of results for each of the different biofuel options. While current biofuel options do not promise high GHG mitigation potential (in some cases for biodiesel and bioethanol they GHG are even higher than for reference fossil fuels), results for advanced and future biofuels show the tendency to increasing GHG mitigation potentials. However, these results have been calculated for theoretical biofuel production concepts, since these options need to be demonstrated at commercial scale as a start. The main parameters with influence on the total LCA results along the WTW chain are shown in Fig. 2-16. It has to be noted that up to now the majority of the studies (cf. Fig. 2-15) do not include effects of land use change. Change of land use
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Natural gas Diesel Gasoline Fossil fuels
can have an effect on the in- or decrease of stored carbon; through changing of natural ecosystems (e.g. change of rain forests or grassland into agricultural land) existing carbon sink (or CO2 sink) can get lost. The consideration of these effects within a life cycle analysis typically will results in negative results and thus in decreasing potentials for GHG mitigation /75//76/.
Fig. 2-16. Influence of process steps on total LCA results.
Fig. 2-17 shows the main impacts on the overall results of GHG emissions for selected biofuels under European conditions. According to this, especially that biofuel options with promising GHG potentials, large biofuel yield per hectare (cf. Fig. 1-5) and a high biomass conversion efficiency (cf. Tab. 2-1) are the most promising regarding the area specific GHG mitigation potentials.
Bio-SNG / biomethane (lignocelluloses) Biogas / biomethane (maize/manure) BtL (lignocelluloses) Bioethanol (lignocelluloses) Bioethanol (cereals) Vegetable oil (rape) Biodiesel (rape) 0 5.000 10.000 Results international studies 15.000 20.000 25.000
Area specific GHG mitigation [kg CO2-equivalents/ha]
Fig. 2-17. Area specific GHG mitigation potential of selected biofuel options /20/.
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However, until now international support policies for transportation biofuels have made no or only minor differentiation according to how they have been produced (e.g. regarding environmental impacts). Thus, governments partly support biofuels has a higher negative environmental impact than its corresponding fossil product. For example in the U. S. the biodiesel excise tax credit that subsidises biodiesel produced from used vegetable oils (e.g. grease) at half of the rate it subsidises biodiesel produced from agricultural feedstock (e.g. vegetable oils). In Brazil a system has been created that discriminates in favour of local producers of biodiesel located in economically disadvantaged regions that procure their feedstocks from certified suppliers /67/. In Germany for future generation biofuels (i.e. synthetic fuels, biomethane or bioethanol from lignocelluloses) and ethanol as pure fuel (E85) there is a tax relief until 2015. Moreover, currently a draft version of a biomass sustainability regulation with special requirements on minimum GHG mitigation potentials for biofuels (i.e. vegetable oils, biodiesel, bioethanol) are under discussion that will be the base for future certification of biofuels.
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TECHNICAL PROFILES OF BIO-BASED CHEMICALS
Part 3:
The use of biomass for the production of chemicals and related materials (bio-polymers, for example) offers several potential advantages: - Bio-based resources are renewable and CO2 neutral, in contrast with fossil fuels. Owing to the rapid increase of oil price, the market price of crude oil may become higher than that of biomass-derived molecules such as sucrose or glucose. Also, the cost of molecules derived from carbohydrates or vegetable oils is more stable compared with that of fossil fuels. Government agencies or industrial organizations worldwide are actively promoting the use of renewables for energy and chemical production due to expected social and environmental benefits. Specific economic benefits in using biomass are thus existing or planned in several countries. The integration within biorefineries with the use of biomass to produce transportable energy products (bioethanol or biodiesel, for example) offers several opportunities to either recover some valuable chemical intermediates during the steps of transformation of biomass to energy products or to produce chemicals as a side stream of biorefinery to increase the added value of production. The molecules extracted from bio-based resources are already functionalized so that the synthesis of chemicals may require fewer steps than from alkanes, thereby decreasing the overall waste generated. Bio-based products may have unique properties compared with hydrocarbon-derived products, for instance biodegradability and biocompatibility.
However, various hurdles may hamper the development of renewables for bio-product production. The supply and composition of renewable raw materials vary with year and location of biomass. This could be solved by using genetically engineered plants, giving a more constant supply and suitable composition that matches the desired products. However, this creates additional serious problems to maintain the biodiversity in natural ecosystems. Intensive agriculture also creates problems for water shortage and secondary pollution due to fertilizers, nutrient losses and insecticides. From process side, biomass composition is far more complex than oil and it is thus necessary to develop new process technologies to make economic the production. The main issue is the high cost involved in processing renewable feedstock to chemicals. In general terms, bio-based starting chemicals are more rich in oxygen than the corresponding base chemicals from oil. Therefore, it is necessary to develop new process strategies to selectively remove hetero-atoms from starting biomolecules. A prerequisite for expanding the use of biomass-derived feedstocks is thus the development of alternative value chains. This can be achieved by designing processing routes and catalytic systems different from those employed from hydrocarbons and adapted to the specific molecular structure of biomolecules. An important issue is the need to assess the sustainability of these processing routes by life cycle analysis. Moreover, socio-economic life cycle assessment (LCA) rather than simple conventional LCA should be performed to assess the societal impact of intensive agricultural activities. 3.1 GENERAL ASPECTS
Although dedicated production of bio-based chemicals is already existing and will expand in the future, as commented later, the more effective push to increase this area is expected to derive from the progressive introduction of biorefineries. /77/ The biorefinery concept has been developed in food and paper industries and is now going to be applied for the production of energy, chemicals and materials from renewable feedstocks. /78//79/ A critical issue is the identification of the best suitable platform molecules. Although the variety of possible starting biomass indicates that it is not possible an unique approach, it is useful to cite the strategic criteria identified in a well-known study made by
49
US Department of Energy./80/ Table 3-1 summarizes the screening criteria used for this selection and which include the raw material and estimated processing costs, estimated selling price, the technical complexity associated with the best available processing pathway and the market potential for each of the candidate building blocks. Although the conclusions of this study are specific for US and can be different for other countries, the methodological approach is a good model. Table 3-1. Screening criteria used in the study by U.S. Dept. of Energy /80/ to identify top 30 building block candidates. Direct Product Building Block Novel Products Replacement Intermediates Possesses new Competes Provide basis and improved directly against of a diverse properties for existing products portfolio of products replacement of Characteristic and chemicals from a single existing derived from intermediate functionality or new petroleum applications Succinic, Polylactic acid Acrylic acid levulinic, glutamic (glucose via lactic obtained from either Examples acids, glycerol, acid is sole viable propylene or lactic syngas source) acid Product swing Novel products strategies can be with unique employed to reduce properties hence market risks cost issues less Market important Markets potential is No already exist expanded competitive Understand Capital petrochemical routes cost structures and Upside investments can be Differentiation growth potential spread across wider usually based on Substantial number of unit desired performance reduction in market operations New market risk Incorporates opportunities advantages of both Most effective replacement and use of properties novel products inherent in biomass Strictly competing on cost Market not Competing clearly defined against depreciated capital Capital risk is Identifying high Limited (green Downside where to focus R&D Time to label) market commercialization differentiation for may be long biobased vs. petrochemical based sources From a group of over 300 possible building block chemicals, selected on the basis of initial screening criteria which include the cost of feedstock, estimated processing costs, current market volumes and prices, and relevance to current or future biorefinery operations, 50 potential building block candidates
50
were identified taking into consideration the concepts employed in traditional petrochemical industry flow-charts, e.g. that all of the products from the petrochemical industry are derived from 8-9 foundation chemicals. This list (Table 3-2) was further shortened to 30 top candidates considering as criteria the direct replacement, novel properties, and potential utility as a building block intermediate. A candidate with one functional group will have a limited potential for derivatives where candidate molecules with multiple functional groups will have a much larger potential for derivatives and new families of useful molecules. Each candidate molecule may be then classified for its current utility to serve as a simple intermediate in traditional chemical processing, as a reagent molecule for adding functionality to hydrocarbons, or as byproducts from petrochemical syntheses. Examples of candidates that fell into this category included acetic acid, acetic anhydride, or acetone. Some of the candidate group for potential status as a super commodity chemical. Super commodity chemicals are derived from building block chemicals or are coproducts in petrochemical refining. Although the ability of biomass to serve as a source of these compounds is real, the economic hurdles of large capital investments and low market price competitors would be difficult to overcome. This list of 30 was ultimately reduced to 12 (see Table 3-2) by examining the potential markets for the building blocks and their derivatives and the technical complexity of the synthesis pathways. A second-tier group of building blocks was also identified as viable candidates. These include gluconic acid, lactic acid, malonic acid, propionic acid, the triacids, citric and aconitic; xylonic acid, acetoin, furfural, levoglucosan, lysine, serine and threonine. Table 3-2. 50 potential building block candidates identified in the study by U.S. Department of Energy /80/. Projected or Selected Known Use top 12 sugar(Building Nr. Selected Rationale based block - BB, Carbon Name for top 30 building Reagent - R, atoms blocks (*) intermediate I) Very limited BB, Formic Acid R N use mostly for adding C1 Super commodity Methanol BB (limited) N from syngas Carbon C1 Monoxide BB Y (+ H2 syngas) Thermodynamics Carbon dioxide R N barrier C2 Acetaldehyde I N Very limited BB. Limited BB, large commodity scale Acetic acid & R, I N anhydride today from syngas. Adds C2 Major use envisioned as fuel. Limited BB. Ethanol Fuel N Will become supercommodity Glycine R N V. limited BB.
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Oxalic acid Ethylene glycol Ethylene oxide Alanine Glycerol 3-Hydroxy propionic acid Lactic acid Malonic acid Serine Propionic acid Acetone Acetoin Aspartic acid
R BB & product BB, R I BB BB BB BB, R BB BB, R I BB BB
N N N N Y Y Y Y Y Y N Y Y
Few uses envisioned Used primarily as chelator and reagent Super commodity Super commodity Y Y
C3
Super commodity, byproduct from cumene to phenol synthesis Y Large commodity chemical, Not a good BB, but large intermediates market. No competitive advantage from biomass Y Y Y Y
Butanol C4 Fumaric acid 3-Hydroxybutyrrolactone Malic acid Succinic acid Threonine
I, possible fuel
BB BB BB BB BB
Y Y Y Y Y
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Arabinitol Furfural Glutamic acid Glutaric acid C5 Itaconic acid Levulinic acid Proline Xylitol Xylonic acid Aconitic acid Adipic acid Ascorbic acid Citric acid Fructose C6 2,5 Furan dicarboxylic acid Glucaric acid Gluconic acid Kojic & Comeric acid
BB BB BB BB BB BB BB BB BB BB I BB BB BB
Y Y Y N Y Y N Y Y Y N N Y N
Y Y Very limited market. Indeterminate set of derivatives Y Y Limited market. Indeterminate set of derivatives Y Super commodity. Limited market. Indeterminate set of derivatives. Other routes to the derivatives would be easier than from fructose Y Y V. limited market. Indeterminate set of derivatives
BB BB BB BB
Y Y Y N
Lysine BB Y Sorbitol BB Y Y (*) 1,4-diacids (succinic, fumaric and malic) and xylitol/arbinitol are have been grouped together because of the potential synergy related to their structures. These molecules can be 1) isomers, 2) interconverted to afford the same molecule, and/or 3) the derivatives pathway leading to essentially the same family of products. It may be noted that this selection was based mainly on the possible products deriving from starch and cellulose-based biomass and do not consider the potential of products from lignin (which conversion is actually difficult). Lignin is a potential source of several aromatic-based platform molecules. In addition, polysaccharides, proteins and oils were not considered. Finally, this selection is mainly based on actual status of technological processes of biomasses. It is thus necessary to further evaluate technical challenges related to chemical, catalytic and biological conversions in order to increase the suites of potential pathways to these candidates. This is particularly relevant when other biomass than those dominating US market are considered.
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A general scheme of the bio-based chemical industry flow chart is reported in Figure 2-1. In order to limit graph complexity, the further transformation of building blocks (platform molecules) to secondary products, intermediates ad final products has been omitted. This scheme may be find on the cited US-DOE report. /80/ The scheme briefly illustrates also some of the possibilities of producing chemicals passing through syn gas. This chemistry is well established and the bio-route only changes the way in which syn gas are produced, either directly or via intermediate fast pyrolysis. These thermochemical routes are discussed in other sections of this survey. It should be commented that obtaining simple alcohols, aldehydes, mixed alcohols and Fischer-Tropsch liquids from biomass are not economically viable actually and require additional development. Recent data /81/ show that biomass-derived ethanol from a thermochemical conversion process has the possibility of being produced in a manner that is cost competitive with corn-ethanol by 2012. However, there are still large debate on this possibility.
Biomass Feedstocks Starch Hemicellulose Cellulose Lignin Oil Protein
Intermediate Platforms
Biobased Syn gas
Sugars
Glucose,Fructose,Xylose Arabinose,Lactose,Sucrose,Starch
Aromatics
Gallic,Ferulic acid,
Direct Polymers & Gums C6
Building Blocks
Syn Gas
C2
C3
Glycerol,Lactic, 3Hydroxy propionate, Malonic acid, Serine
C4
Succinic,fumaric & malic acids, Aspartic acid,3 Hydroxy Butyrrolactone, Acetoin,Threonine
C5
H2,methanol &higher alcohols,oxo andiso synthesis products, FischerTropsch chemicals
Itaconic acid, Citric/Acotonic Furfural,Levulinic acid,5Hydroxy acid,Glutamic methyl furfural, acid,Xylonic acid, Lysine,Gluconic Xylitol/Arabitol acid,Glucaric acid, Sorbitol
Fig. 3-1 Biobased Product Flow-chart for Biomass Feedstocks. Elaborated from US DOE report /80/. Fig. 3-1 evidences also the concept that there is still not unique identification of the preferred routes for biomass to chemical transformation. It was necessary nearly a 70 years to establish current pathways in petrochemical production and there is still significant degree of development. It is thus obvious that it is still necessary a large R&D effort to establish preferential routes for bio-based chemical production. It should be also considered that there are still many technical barriers. This concept is illustrated in the case of the use of 3-Hydroxypropionic acid (3HPA) as building block. Fig. 3-2 illustrates the main routes of conversion of 3HPA. Table 3-3 reports some of the technical barriers to overcome to implement the pathways of transformation of 3HPA shown in Fig. 3-2.
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derivativesincommercialuseandproduced in commodityscalevolumetoday.
O O N OH O
acrylonitrile
acrylic acid methyl acrylate
HO
OH
1,3-propanediol
HO
OH
NH2
3 hydroxypropionic acid (3HPA)
acrylamide
O O
HO
OH
malonic acid
HO O
propiolactone
ethyl 3 hydroxypropionate
Fig. 3-2 Main routes of conversion of 3HPA. Adapted from ref. /80/
Table 3-3. Technical barriers and potential use of derivatives in the transformation of 3HPA. Adapted from ref. /80/. Building Block Pathway, Direct Uses of Building Block, Technical Barriers Derivative or Derivative Family Potential use of derivatives Sugar Transformation to 3-HPA Chemical Unknown or multistep, Costly process Being done by industry. Fermentation pathway not known General needs in fermentation Improving microbial biocatalyst to 1) reduce other Biotransformationacid coproducts, 2) increase Fermentation yields and productivities Lower costs of recovery process to reduce unwanted salts Scale-up and system integration issues Reductive Transformation 3HP to 1,3 PDO via catalytic dehydrogenation Direct reduction of carboxylic acid with high selectivity Reduction at mild Sorona fiber (new material) 1, 3-propanediol (1,3 PDO) conditions moderate hydrogen pressure, low T Tolerance to inhibitory elements or components of
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biomass based feedstocks Robust catalysts and catalyst lifetimes Dehydrative Transformation 3-HPA to acrylic acid via catalytic dehydration Selective dehydration without side reactions (high value need for biomass) New heterogeneous Contact lenses, diapers (Super Acrylate family catalysts (i.e. solid acid Absorbent Polymers SAPs) catalysts) to replace liquid catalysts and to improve existing catalyst based systems 3-Hydroxypropionic acid (3HPA) is a C3 building block and has the potential to be a key building block for deriving both commodity and specialty chemicals. The major technical hurdles for the development of 3HPA as a building block include the development of very low cost fermentation routes. Major technical considerations are the development of an organism with the appropriate pathways. In principle, the fermentation should be equivalent to lactic acid from a yield perspective. The major elements of improvement in the fermentation include the following considerations: /80/ - Productivity: Productivity improvements are required to reduce the capital and operating costs of the fermentation. A minimum productivity of 2.5 g/Lhr. needs to be achieved in order to economically competitive. Pathway Engineering: It will be necessary to engineer the appropriate pathway in an organism to produce 3-HPA. If successful the yield of the fermentation should be equivalent to lactic acid. Nutrient Requirements: It is essential for commercial fermentations to be run using minimal nutrients. Expensive nutrient components such as yeast extract and biotin must be eliminated. The nutrient requirements should be limited to the use of corn steep liquor or equivalent if at all possible. Final Titer: Final titer is also important when considering overall process costs. This is not a showstopper but a high final titer will reduce overall separation and concentrating costs. pH Considerations: In an ideal situation the fermentation could be run at low pH, most preferably without requiring any neutralization. The cost of neutralization is not necessarily cost prohibitive, the conversion of the salt to the free acid does add significant costs. If derivatives such as butanediol (BDO), tetrahydrofuran (THF) and gamma-butyrolactone (GBL) are going to be competitive from a cost perspective then low pH fermentation will be essential.
Similar considerations are found in the given reference /80/ for other building blocks. Regarding the primary derivatives obtained by reduction, e.g. 1,3 PDO: - The hydrogenation/reduction chemistry for the conversion of 3-HPA to 1,3-PDO will require the development of new catalyst systems that are capable of the direct reduction of carboxylic acid groups to alcohols. A second option is to esterify the acid to an ester and reduce the ester. This may be technically easier but will add costs to the process. Currently 1,3-propanediol is being produced by Dupont Tate & Lyle Bioproducts, a joint venture between DuPont and Tate & Lyle, in Loudon, Tennessee. Dubbed Bio-PDO, it's being produced with genetically modified strain of E. coli that's fed a refined corn syrup (http://duponttateandlyle.com). 1,3-PDO has been widely publicized as monomer for use in fibers for carpet. The new properties imparted by 1,3-PDO include better dye ability, and improved elasticity. Direct reduction of 3-HPA from a fermentation
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broth will require the development of robust catalysts that are not susceptible to fouling from impurities. Regarding the primary derivatives obtained by dehydration, e.g. Acrylates: - The dehydration of 3-HPA to the family of acrylates including acrylic acid and acrylamide will require the development of new acid catalyst systems that afford high selectivity. In addition, there is the potential for polymerization and this must be avoided during the dehydration. One advantage for the production of acrylamide is that the starting material could be ammonium 3HPA. Starting with ammonium 3-HPA would eliminate the need for low pH fermentation. In conclusion, there is a significant market opportunity for the development of biobased products from the C3 building block 3-HPA. The major challenges include the development of a low cost fermentation and a family of catalysts for the conversion of 3-HPA to desired products. In order to be competitive with petrochemical routes to acrylates both the fermentation and catalysis must afford high yields. In assessing the preferential platform molecules and building blocks for a bio-based chemical production it should be also identified the most viable biological and chemical transformation pathways. Table 3-4 reports currently known pathways to building blocks from sugars. /80/ Again it should be remarked that this table should be considered a guideline for current status, because research is quite active in discovering new options both for sugar transformation and to convert other components of biomass to possible building blocks (for example, lignin to aromatics). Aromatics comprise a very large commodity market for polymers and surfactants. Polysaccharides are a growing market segment because of their potentially valuable properties in various applications such as enhanced oil recovery and paper/metal finishing. Oils, although produced in an established industry, have a broad range of opportunities for diverse market applications (see next section). Lignin can afford the entire family of aromatic compounds that are difficult to produce via sugars or oils. It would be worthwhile to assess the potential value of products derived from both oils and lignin. In general terms, Table 3-4 evidences that a large number of sugar to building block transformations can be done by aerobic fermentation employing fungi, yeast or bacteria. Chemical and enzymatic transformations are also important process options. It should be noted however, that pathways with more challenges and barriers are less likely be considered as viable industrial processes. New knowledge and better technologies are needed in dealing with chemical transformations that involve milder oxidations, selective reductions and dehydrations, better control of bond cleavage, and improvements to direct polymerization of multifunctional monomers. For biological transformations, there is the need for better pathway engineering of industrial hosts, better understanding of metabolic pathways and cell biology, lower downstream recovery costs, increased utility of mixed sugar streams, improved molecular thermal stability; and better understanding of enzyme functionality. /82//82/ It should be also remarked that while it is possible to prepare a very large number of molecular structures from the top building blocks, there are very limited publicly available information about these molecules behavior, material performance or industrial processing properties. /83/ Table 3-4. Actual and Potential Pathways to Building Blocks from Sugars. x = under study; C = commercial. Adapted from ref. /80/. AEROBIC ANAEROBIC CHEM-Enzyme FERMENTATIONS FERMENTATIONS TRANSFORMATIONS Building Blocks Chem. & Biotransform Yeast or Yeast or Catal. Bacterial Bacterial ation Fungal Fungal Processes 3-Hydroxy x x
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propionic acid Glycerol Lactic acid Malonic acid Propionic acid Serine 3-Hydroxy butyrolactone Acetoin Aspartic Acid Fumaric Acid Malic acid Succinic acid Threonine Arabitol Furfural Glutamic Itaconic Acid Levulinic acid Xylitol 2,5 Furan dicarboxylic acid Aconitic acid Citric acid Glucaric acid Gluconic acid Levoglucosan Lysine Sorbitol
x x x x
x x
x C x
C x
C x
x x x x x x x x C x
x x x x x C x C
x x x x C C x x x x C x x
x C X C x x
x x C x
x x x C x
It should be remarked that other alternative strategies in chemical production from biomasses exist. In general terms, three different options exist /84/: - From Biomass to Products via Degraded Molecules - From Biomass to Products via Platform Molecules - From Biomass to Products via New Synthesis Routes Biomass can be converted into synthesis gas by adapting the well known gasification processes based on reforming conversions. An alternative approach is the fast pyrolysis of biomass at high temperatures in the absence of oxygen to produce a bio-oil. Some valuable compounds, particularly phenolic compounds derived from the degradation of lignin, can potentially be recovered. Furfural and furfuryl alcohol are present at up to 30 and 1230%, respectively, and may be used to produce phenolformaldehyde resins. However, the main motivation to produce bio-oils are is to facilitate transport (it is less costly to transport the bio-oil than the starting biomass) to a centralized facility for further conversion of bio-oil to syn gas. Syngas is then converted into methanol or hydrocarbons which are subsequently converted into chemicals via usual synthesis routes developed for petroleum feedstock. As commented before, the overall sustainability and economics of these high temperature processes has to be established. An alternative to conventional route via syn gas to produce bio-based chemicals consists of performing aqueous phase reforming of biomass yielding directly alkanes. Thus, a water solution of
58
ethylene glycol, glycerol and sugar-derived polyols was converted into hydrogen and alkanes at 550 K under 1550 bar pressure. /85//86/ The reaction chain leading to liquid alkanes up to C15 involves the acid-catalyzed dehydration of sorbitol, yielding intermediates that are subjected to aldol condensation over solid base catalysts, and the resulting oxygenates are hydrogenated to alkanes over metalsupported catalysts. However, the sustainability and economics of this processes has to be demonstrated and other routes are preferable especially to produce bio-based chemicals. /87//88//89//90/ However, if biomass gasification or liquid phase reforming should be conducted using organic wastes or cheap and abundant vegetative biomass rather than high priced molecules such as sugar polyols obtained from cereals, the process could become more attracting. Regarding the route via platform molecules, several of them were already identified, as commented above particularly in the case of carbohydrate. Some of them are already currently employed to produce specialties and fine chemicals. /91//92//93//94/ Monosaccharides such as glucose, and disaccharides such as sucrose, which are easily obtained with great purity from various carbohydratecontaining crops are well-known platform molecules in sugar chemistry. Lactose, with a production of over 6th million tons per year is also a useful platform molecule obtained from the cheese industry. Most other platform molecules are obtained via fermentation from glucose or other carbohydrates using continuously improved processes with new genetically modified bacteria or yeasts. /95//96/ In future, the challenge will be to produce fermentable sugars from cellulose and hemicelluloses, which are available in huge amounts from vegetative biomass. This involves progress in the chemical and enzymatic hydrolysis of cellulose. Vegetable oils or triglycerides obtained from the seeds of various plants are the source of a wide variety of fatty acid esters and derivatives (fatty acids and alcohols) with different molecular structure (chain length, number and position of C=C bonds) that can be used as platform molecules, as well as glycerol, which is a co-product of triglycerides transesterification. The three main platform molecules employed in terpene chemistry are -pinene and -pinene, which are extracted from turpentine oil (about 350 000 tons per year) which is a co-product of paper pulp industry, and limonene extracted from citrus oil (about 30 000 tons per year). A limit in developing bio-based technologies for the synthesis of chemicals is the process cost which, however, can be greatly reduced by developing new approaches /84//91/ which: 1. Decrease the number of reaction steps via a one-pot reaction associating two or more catalytic steps. This can be achieved by multistep reactions carried out by cascade catalysis without intermediate product recovery, thus decreasing the operating time and reducing considerably the amount of waste produced. 2. Integrate in a single reactor the synthesis step with the separation steps, for example performing the catalytic reaction in the presence of membrane which allow the continuous removal of the products or reactions. 3. Convert renewable feedstocks into a mixture of products that can be used as such in the synthesis or formulation of end-products. This approach is widely used in food and feed industries where there is no requirement to prepare specific molecules from bio-resources but rather mixtures of triglycerides, carbohydrates and proteins. Approach (1) is very similar to classical synthesis routes except that the number of steps is reduced. To be successful it is necessary to preferably integrate approach (1) with the approach (2). The alternative is the approach (3). Some examples of one-pot reaction with cascade catalysis are the following: - The use of a bifunctional Ru/HY catalyst for the hydrolysis in water solutions of corn starch (25 wt.%) (on the acidic sites of the Y-type zeolite) to glucose which is on-site hydrogenated on ruthenium to a mixture of sorbitol (96%), mannitol (1%), and xylitol (2%). /97/ Similarly a one-
59
pot process for the hydrolysis and hydrogenation of inulin to sorbitol and mannitol has been achieved with Ru/C catalysts where the carbon support was preoxidized to generate acidic sites. /98/ Fructose has been converted into furan-2,5-dicarboxylic acid with 99% selectivity at 72% conversion in a one-pot reaction. /99/ p-Cymene, a precursor of p-cresol and various flavors and fragrances, can be obtained by dehydrogenation of -pinene at 300C in a continuous fixed-bed flow reactor in the presence of 0.5-wt.% Pd/SiO2. /100/ The p-cymene has been produced under similar reaction conditions with nearly 100% yield from a mixture of di-pentene isomers (Sylvapine), showing that even unpurified raw materials can still be converted into the desired product in one step. /101/ Combined bio- and chemocatalytic reactions for a four-step conversion of glucoside into aminodeoxysugar without intermediate product recovery. /102/
Some examples of one-pot conversion into a mixture of products are the following: - Conversion of sugars into a mixture of polyols. In a first reactor starch can be hydrolysed to glucose and hydrogenated then to sorbitol on a bifunctional Ru/HY catalyst. The solution can be then send to a second reactor where, reactor, depending upon reaction conditions, sorbitol is catalytically converted either by dehydroxylation into C4-C6 products or by cyclodehydration into cyclic polyols. /84/ The mixture of polyols, obtained either by dehydroxylation or cyclodehydration, was effectively employed to synthesize alkyd resins and make decorative paints with performances comparable to commercial ones. Oxidation of Starch and Other Polysaccharides. It is possible, but difficult, to convert polysaccharide polymers such as starch or cellulose into valuable end-products via one-pot process. The problem arises from the fact that these natural polymers are insoluble and partially crystallized and heterogeneous catalysts cannot be employed with these solid substrates. Hydrophilic starch obtained by partial oxidation is used in paper and textile industries and can be potentially applied in various applications, e.g., for the preparation of paints, cosmetics, and superabsorbents. Oxidation occurs at the C6 primary hydroxyl group or at the vicinal diols on C2 and C3, involving a cleavage of the C2-C3 bond to give carbonyl and carboxyl functions. It is possible to catalyze the reaction The water-soluble iron tetrasulfophthalocyanine (FePcS) complex, which is cheap and available on an industrial scale. The oxidation of starch in aqueous suspension with H2O2 in the presence of FePcS gives both carboxylic and carbonyl groups. /84/ Even very low amounts of the catalyst are sufficient (an anhydroglucose unit (AGU)/catalyst ratio over 20.000). The hydrophilic starch so obtained can be used in the paper, paint and cosmetic industries /103/.
3.2
PLATFORM CHEMICALS
Previous section has already evidenced that the bio- and/or chemio-catalytic conversion of platform molecules produced by bioconversion of renewables into bioproducts is already the basis of many industrial processes, leading to important tonnages of chemicals and polymers from carbohydrates and triglycerides and fine chemicals from terpenes. Nevertheless, this approach needs to be extended and process efficiency should be strengthened by designing more active and selective catalysts. Below some selected examples of platform molecule conversion into bioproducts will be discussed in a more detail. 3.2.1 Carbohydrates
Sucrose (total production 130 million tons per year) and starch (40 million tons per year used in industry) are two major sources of glucose and fructose. Several information on the numerous
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catalytic reactions starting from glucose to derive valuable chemicals can be found in review articles by van Bekkum and Besemer /104/ and by Lichtenthaler and Peters. /105/ Hydrogenation of glucose to sorbitol /106/ and oxidation of glucose to gluconic acid /107/ are illustrative examples of very selective catalytic conversion (yield > 99%) where the catalysts are used many times with negligible loss of activity and selectivity. The production of sorbitol is practiced commercially by several companies and has a current production volume on the order of 100 million tons annually. All of the commercial processes are based on batch technology and the use of Raney nickel as the catalyst. The major reason for using batch technology is to ensure complete conversion of the glucose, but the need to develop a continuous process is clear. The complete conversion of glucose is associated to the predominant use of sorbitol in the food industry and the very strict requirements for the amount of reducing sugars in the sorbitol product. For chemical applications this requirement could be less stringent and there is thus space for new process technologies. Engelhard has demonstrated that the continuous production of sorbitol from glucose can be done continuously using a ruthenium on carbon catalyst. This would make sorbitol a very inexpensive feedstock for producing derivatives. Inexpensive sorbitol affords the potential for the production of isosorbide at low costs. Isosorbide has been demonstrated to be a very effective monomer for raising the glass transition temperature of polymers. The major applications are as a copolymer with PET for the use in bottle production. These applications include ridged bottles as well as the ability to use plastic to replace glass in hot fill applications. Figure 3-3 summarizes the sorbitol chemistry to derivatives /80/.
O H OH HO H HO OH O HO OH
propylene glycol
Isosorbide
O HO HO HO OH HO OH HO OH HO OH HO
(2R,3R,4S)-tetrahydro-2-((R)1,2-dihydroxyethyl)furan-2,3,4triol (1,4-sorbitan)
O HO OH
ethylene glycol
sorbitol
OH O HO OH HO OH
HO
OH
lactic acid
(3R,4R,5R)-tetrahydro-2,5bis(hydroxymethyl)furan-3,4-diol (2,5anhydro sugar)
glycerol
Fig. 3-3. Main routes of conversion of sorbitol. Adapted from ref. /80/. Anhydrosugar alcohols are produced by dehydration of the corresponding sugar alcohols by the action of various dehydration catalysts, typically strong acids. Anhydro sugar alcohols, in particular derivatives of sorbitol, are known for their therapeutic uses and uses in food. Isosorbide (1,4:3,6dianhydrosorbitol) is a monomer useful in the manufacture of polymers and copolymers, especially polyester polymers and copolymers. The challenge in producing isosorbide from sorbitol is the development of process conditions and dehydration catalysts that afford high yield of isosorbide. The best reported yields are around 76%. In
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order to increase the use of isosorbide, increased yields to 90% would be desirable. This not only reduces the production cost but also reduces the recovery and purification costs. The main technical barriers in the dehydration pathway of sorbitol (to isosorbide, anhydrosugars) are the following: /80/ - Selective dehydrations without side reactions - Dehydration steps to anhydrides or lactones - New heterogeneous catalyst systems (solid acid catalyst) to replace liquid catalyst systems Potential use of these derivatives is for PET like polymers such as Polyethylene isosorbide terephthalates (bottles, in use for hot-fill). The conversion of sorbitol to glycols, namely propylene glycol is based on the hydrogenolysis of sorbitol. The major difficulty is producing propylene glycol (PG) in high yields. New catalyst systems that afford high yield of PG are needed for commercial success. The main technical barriers in the bond cleavage (hydrogenolysis) pathway of sorbitol (propylene glycol, lactic acid) are the following: /80/ Specificity for C-C & C-O bonds - Increasing rates - Tolerance to catalyst poisons (biomass sugar streams) Potential use of these derivatives is for antifreeze and polylactic acid (PLA). Copolymerization with other glycols in the unsaturated polyester resin market would be a major opportunity. Other direct polymerizations would yield polyesters that would need to be evaluated for properties and compared with other polyesters. The main technical barriers in the direct polymerization of sorbitol (to Branched polysaccharides) are the following: /80/ - Selective esterifications to control branching - Control of molecular weight & properties Potential use of these derivatives is for water soluble polymers (water treatment,etc), and in new ecofriendly polymer applications. Glucose can be converted into arabitol by an oxidative decarboxylation of glucose to arabinonic acid followed by hydrogenation to arabitol (Scheme 3-1). The main pitfall is to avoid dehydroxylation reactions leading to deoxy-products not compatible with the purity specifications required for arabitol.
HO OH OH HO H OH O CH2OH
H+
* O HO OH O * HO HO
H2O2
OH
HO H H
H OH
H2
H H
OH
starch
glucose
arabinonic acid
CH2OH
arabinitol
CH2OH
Scheme 3-1. Synthesis of arabinonic acid and arabitol from starch. Adapted from ref. /84/. Aqueous solutions (20 wt.%) of arabinonic acid have been hydrogenated on Ru-catalysts in batch reactor. /108/The selectivity was enhanced by adding small amounts of anthraquinone-2-sulfonate (A2S), which decreased the formation of deoxy by-products. A2S acted as a permanent surface modifier since the catalyst was recycled with the same selectivity without further addition of A2S. The highest selectivity to arabitol was 98.9% at 98% conversion.
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Alternatively, arabinitol can be produced by hydrogenation from the corresponding sugars arabinose using supported nickel, ruthenium or rhodium as catalysts. In a similar way, xylitol can be produced by hydrogenation from the corresponding sugars xylose. Xylitol is used as a non-nutritive sweetener. C5 sugars such as xylose and arabinose have the potential to be an outstanding building block for commodity chemicals. One challenge will be getting a relatively clean feed stream of these sugars. The conversion of these sugars to the sugar alcohol and subsequent conversion to glycols has been demonstrated and could be a first generation process for the production of propylene glycol and ethylene glycol. Lactose is another interesting feedstock, being a co-product of the milk industry. The oxidation of lactose on PtBi/C catalyst at neutral pH produces lactobionate which is subsequently converted into 2keto-lactobionate with a final yield of about 80%. /109/ Starting from lactobionate without pH control, 2-ketolactobionate was obtained with 95% selectivity, but the oxidation reaction stopped at 50% conversion due to the poisoning of Pt-Bi/C catalysts. Lactic (2-hydroxypropionic) acid, obtained by fermentation of glucose and polysaccharides, is used by NatureWorks (Cargill/Dow LLC) (http://www.natureworksllc.com) to prepare polylactide (PLA) (Scheme 2.2), a biodegradable or recyclable polymer with a potential production of over 150.000 tons per year. This and other potential useful reactions from lactic acid have been reviewed by Datta and Henry. /110/ Lactic acid potential to become a major chemical feedstock derived from relatively broad range of applications to make plastics, fibers, solvents and oxygenated chemicals. Recently, new technologies have emerged that can overcome major barriers in separations and purification and processing. /110/ For the production of polymers, several advances in catalysts and process improvements have occurred in the technology to produce dilactide and its polymerization to produce plastics and fibers. Other advances in esterification technology with pervaporation and development of biosolvent blends also have a high potential for green solvents in many applications.
Scheme 3-2. Synthesis of polylactic acid (NatureWorks, LLC). Adapted from ref. /111/ 3-Hydroxypropionic (3-HP) acid obtained by fermentation from glucose is also a good candidate to produce various chemicals by catalytic routes, as commented in the previous section. /111/ An example of a possible integrated reactive separation process to convert 3-HP to acrylic acid is shown in Figure 3-4.
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Fig. 3-4. Example of integrated reactive separation:3-HP to acrylic acid. Adapted from ref. /111/. Levulinic acid (LA) is obtained by hydrolysis of cellulose-containing biomass. R&D is actively conducted at DuPont Co. to employ levulinic acid for the synthesis of pyrrolidones (solvents and surfactants), -methylene--valerolactone [monomer for the preparation of polymers similar to poly(methyl methacrylate)], and levulinic acid esters (fuel additives). /112/ LA is a product formed by treatment of 6-carbon sugar carbohydrates from starch or lignocellulosics with acid. Five carbon sugars derived from hemicelluloses (viz. xylose, arabinose) can also be converted to LA by addition of a reduction step subsequent to acid treatment. Thus, LA could serve as a valuable building block available from almost all sugars manufactured in the biorefinery. LA is one of the more recognized building blocks available from carbohydrates (and has attracted interest from a number of large chemical industry firms), and for that reason, has frequently been suggested as a starting material for a wide number of compounds. Figure 3-5 summarizes selected derivatives of LA, while Figure 3-6 summarizes the Biofine Process-Cellulose pathway to produce LA. /112/ The family of compounds available from LA is quite broad, and addresses a number of large volume chemical markets. Conversion of LA to methyltetrahydrofuran and various levulinate esters addresses fuel markets as gasoline and biodiesel additives, respectively. Deltaaminolevulinic acid is a herbicide, and targets a market of 100 200 million tons/yr. An intermediate in the production of aminolevulinic acid is -acetylacrylic acid. This material could be used in the production of new acrylate polymers, addressing a market of about 1 billion tons/yr. Diphenolic acid is of particular interest because it can serve as a replacement for bisphenol A in the production of polycarbonates. The polycarbonate resin market is almost 2 billion tons/yr. New technology also suggests that LA could be used for production of acrylic acid via oxidative processes. LA is also a potential starting material for production of succinic acid. Production of LA derived lactones offers the opportunity to enter a large solvent market, as these materials could be converted into analogs of N-methylpyrrolidinone. Complete reduction of LA leads to 1,4-pentanediol, which could be used for production of new polyesters. The technical barriers for this building block include improvement of the process for LA production itself. However, this conversion has been studied, and the LA yield is around 70%. Determination of the value of increasing this yield through more selective dehydration processes would be useful, and an effort in developing new catalysts is necessary. Of particular interest are processes to facilitate selective oxidation of LA to succinic and acrylic acid, focusing on the use of simple oxidants such as oxygen or peroxide. Selective reduction of LA to the corresponding lactones and methyltetrahydrofuran will improve access to large volume fuel markets. Finally, diphenolic acid as a bisphenol A replacement should be cited.
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CO2Me CN Nylon intermediates OH O levulinic acid * O O Biofuel Additives O * O O O R O O R N O R Solvents, Surfactants O
High Tg Polymers
Fig. 3-5. Selected Derivatives of Levulinic Acid. Adapted from ref. /112/.
Firststage Fixed Bed Reactor
FastReaction (seconds)
Cellulose
Sugars
IntermediateI
OHC O
CH2OH
HMF
SlowReaction IntermediateII (minutess) Levulinic Acid (50%wt.)

Second stage BackMixed Reactor Tars (30%wt.) Formic Acid (20%wt.)
Fig. 3-6. Biofine Process-Cellulose Pathway. Adapted from ref. /112/ . Furan derivatives catalytic processes used to obtain furan derivatives from carbohydrates and the al. /113/Some of the main reactions are summarized in Fig. 3-7. /84/ From fructose or carbohydrates based on fructose (sucrose, inulin), the first transformation step is dehydration to 5hydroxymethylfurfural (HMF). Fructose dehydration could be performed in the presence of dealuminated mordenite with a selectivity of 92% at 76% fructose conversion. Starting from raw inulin hydrolysates for better process economy, the selectivity to HMF was up to 97% at 54% conversion. /84/
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Fig. 3-7. Catalytic reactions on furan derivatives. Adapted from ref. /84/. The hydrogenation of HMF in the presence of metal catalysts (Raney nickel, supported platinum metals, copper chromite) leads to quantitative amounts of 2,5-bis(hydroxymethyl)furan used in the manufacture of polyurethanes, or 2,5-bis(hydroxymethyl)tetrahydrofuran that can be used in the preparation of polyesters. The oxidation of HMF is used to prepare 5-formylfuran-2-carboxylic acid, and furan-2,5-dicarboxylic acid (a potential substitute of terephthalic acid). Oxidation by air on platinum catalysts leads quantitatively to the diacid. Furfural is obtained industrially (200 000 tons per year) by dehydration of pentoses produced from hemicelluloses. Furfurylic alcohol is obtained by selective hydrogenation of the C=O bond of furfural, avoiding the hydrogenation of the furan ring. Liquid phase hydrogenation at 80C in ethanol on Raney nickel modified by heteropolyacid salts resulted in a 98% yield of furfuryl alcohol. Succinic acid, an similarly fumaric and malic acid (four carbon dicarboxylic acids), are another interesting building block. The market potential for succinic acid and its derivates is around 250 000 tons per year. The basic chemistry of succinic acid is similar to that of the petrochemically derived maleic acid/anhydride. Succinic acid is produced biochemically from glucose using an engineered form of the organism A. succiniciproducens and most recently via an engineered Eschericia coli strain. The chemistry of succinic acid to the primary families of derivatives is shown in Figure 3-8.
O O
HO OH
O H2N O NH2
-Butyrolactone
O
1,4-Butanediol
Succindiamide
Tetrahydrofuran
O HO OH O Succinic acid
H2 N
NH2
1,4-Diaminobutane
H N
NC
CN
2-Pyrrolidone
CH3 O N
Succinonitrile
O H 3C O O CH3
N-Methyl pyrrolidone 4,4-Bionolle

(polyester)
O Dimethylsuccinate
Fig. 3-8. Succinic Acid as a Platform Molecule. Adapted from ref. /80/.
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The major technical hurdles for the development of succinic acid as a building block include the development of very low cost fermentation routes. A primary technology for use of succinic acid is selective reduction to give the well-known butanediol (BDO), tetrahydrofuran (THF) and butyrolactone (GBL) family. The hydrogenation/reduction chemistry for the conversion of succinic acid to BDO, THF and BGL is well known and is similar to the conversion of maleic anhydride to the same family of compounds. The only real technical consideration here is the development of catalysts that would not be affected by impurities in the fermentation. This is a significant challenge but would not necessarily be a high priority research item until the costs of the fermentation are substantially reduced. Pyrrolidinones are materials that can be derived from GBL, and address a large solvent market. Reaction of GBL with various amines leads to the production of materials such as pyrrolidinone and N-methylpyrrolidinone. Succinic acid can also be converted more directly to pyrrolidinones through the fermentative production of diammonium succinate. One advantage with the fermentation derived succinic acid is that the conversion of diammonium succinate to the pyrrolidones directly could offer a significant cost advantage. This would eliminate the need for low a low pH fermentation for the direct production of succinic acid. Similar chemistry can be applied to transformations of malic and fumaric acid. Of particular interest is the ability to use selective reduction for the conversion of fumaric acid to succinic, and the use of malic acid in the production of substituted THF or NMP derivatives. 3.2.2 Fatty Acid Esters and Fatty Alcohols
The transesterification of triglycerides (vegetable oils) or the esterification of fatty acid with alcohol or polyols produces fatty acid esters which further catalytic hydrogenation form fatty alcohols (Fig. 3-9). Fatty acid esters and fatty alcohols are useful platform molecules to prepare surfactants, emulsifier, lubricants and polymers. The trends is to (i) replace nickel and copper chromite metal catalysts by platinum-metals catalysts and (ii) replace homogeneous catalysts by acidic and basic solids for esterification and transesterification reactions.
Fatty alcohols H2 Edible oils,fats H2

metal catalyst metal catalyst
+glycerol
triglycerides
H2O
CH3OH OH H+
Methyl esters
+glycerol H+ CH3OH
H2
metal catalyst
Fatty alcohols H2
Fatty acids
+glycerol
H2
metal catalyst
Saturated fatty acids
metal catalyst
Fig. 3-9. General scheme of transformation of triglycerides. Surfactants. The transesterification of triglycerides with glycerol (glycerolysis) or the esterification of fatty acids with glycerol are two important reactions to produce fatty acid ester of glycerol, a relevant class of efficient surfactants (Fig 3-10a). It is necessary to improve the selectivity to obtain glycerol monoesters that are non-ionic surfactants with a good hydrophilic/hydrophobic. Glycerolysis is catalyzed by basic oxides. Glycerolysis of rapeseed oil on MgO catalysts gave a 63% yield of monoglyceride. /114/ Glycerol monoester has been prepared by esterification of fatty acid with glycerol, using acidic solids instead of sulfuric acid. /115/
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The transesterification of methyl ester with sugar on basic catalysts (acetalization) or the esterification of fatty acids with sugar on acidic catalysts is another relevant class of reactions to produce fatty acid esters of sugars. Also these chemicals are important biodegradable and biocompatible surfactants. Liquid acids and bases have been replaced by enzymatic catalysis with lipase, giving a higher yield of monoester. /116/ In general, in both type of reactions the trend is to replace homogeneous catalysts by acid or base solid catalysts to reduce waste, improve catalyst recovery. Using mesoporous solid catalysts it is also observed an improved selectivity to monoesters.
O O
a)
HO OH OH OH
+
HO
12-16
HO OH
O
12-16
b)
HO HO
+
HO OH
12-16
H+ -H2O
Glucose
OH
Fatty alcohol
OH O O OH O O OH n
12-16
OH O O OH
HO HO
HO HO
12-16
HO HO
hydrophilic
hydrophobic
Fig. 3-10. Reaction of esterification (a - synthesis of fatty acid ester of glycerol) and of acetalization (b synthesis of fatty acid esters of sugars. Alkylglucosides are a class of valuable commercial surfactants, particularly for cosmetics applications because of their biocompatibility. They are obtained by acetalization of carbohydrates with fatty alcohols in the presence of acid catalysts (Fig. 3-10b). Zeolites and MCM-41 have been used as acidic catalysts to achieve the acetalization of glucose with alcohols of different chain lengths. Shape selectivity effects decrease the amount of oligomers formed and the activity and selectivity can be controlled with the Si/Al ratio. Lubricants. Fatty acid esters, when used directly as lubricants, show poor resistance to oxidation and tribological properties. However, the epoxidation of the fatty acids followed by alcoholysis of the epoxide (Fig. 3-11) produce valuable lubrificats. The epoxidation of fatty acid methyl esters (FAME) is traditionally conducted in strong acidic media, e.g., with peracetic acid in sulfuric acid solutions, but more recently cleaner processes using solid catalysts have been proposed. A mixture of FAME from sunflower oil has been epoxided with tert-butyl hydroperoxide (TBHP) at 363 K in the presence of TiMCM-41 catalysts to yield 98% conversion with 85% selectivity for mono-epoxy compounds /117/. Selectivities > 95% were obtained whatever the structure of the supporting material, provided titanium is well dispersed. Alcoholysis with different alcohols of epoxidized FAME has been studied on acidic resins of various structure and acid strength /118/. The addition of methanol on epoxidized methyl oleate at 60C in the presence of Nafion entrapped in silica (SAC13) or of Amberlyst15, a sulfonated styrene-divinylbenzene copolymer, resulted in complete conversion with selectivity higher than 98%.
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Polymers. The C=C double bond in fatty acid esters could be used to prepare useful monomers for polymer synthesis. Catalytic C=C coupling reactions of unsaturated fatty compounds have been reviewed by Metzger et al. /119//120/. Metathesis reactions involving unsaturated fatty compounds to prepare o-unsaturated fatty acid esters have been reviewed by Biermann /121/ together with other new syntheses to use oils and fats as renewable raw materials for the chemical industry. Ethenolysis of methyl oleate catalyzed by ruthenium carbenes developed by Grubb yields 1-decene and methyl 9decenoate (Fig. 3-11), which can be very useful to prepare monomers for polyolefins, polyesters, polyethers and polyamide such as Nylon 11.
vegetable oils
O R O m n H2C CH2 +MeOH -glycerol
transesterification
epoxidation
O R O m
H+
TBHP H2O2
10 bar, 50C Ru carbene
- -olefins
O
metathesis
O R n ROH O
alcoholysis
O R O HO
H+
polyolefins polyesters
m OH n
polyethers
Fig. 3-11. Reaction of epoxidation and alcoholysis to produce lubrificants and of methathesis to produce monomers for polymers starting from fattyacid esters .
3.2.3
Terpenes
Terpenes such as -pinene and b-pinene (obtained from turpentine, an essential oil deriving from oleoresins of conifer; turpentine itself is widely used as a solvent in paints and varnishes) and limonene (extracted from lemon oil) (Fig. 3-12) are interesting products in the synthesis of flavors and fragrances, but are also commercially useful chemical building-blocks and pharmaceutical stereo isomers. The application of terpenes depends on the absolute configuration of the compounds because enantiomers present different organoleptic properties. Biotransformations allow the production of regio- and stereoselective compounds under mild conditions /122/. Enzymes and extracts from bacteria, cyanobacteria, yeasts, microalgae, fungi, plants, and animal cells have been used for the production and/or bioconversion of terpenes. In addition, whole cell catalysis has also been used. A variety of media and reactors have been assessed for these biotransformations and have produced encouraging results /122/.
limonene p-Cymene -pinene -pinene
69
Fig. 3-12 Main terpenes used as building blocks for renewable raw materials . The monoterpene hydrocarbons (primarily -pinene) are used to prepare synthetic pine oil (the biggest single turpentine derivative), polyterpine resins, perfumes/fragrances and insecticides. Variation in extraction method, fractionation and blending produces oils with different properties. There is a growing demand for terpene solvents. Pine oil is (i) agood emulsifier, (ii) an excellent solvent, (iii) an effective germicide (of low non-target toxicity), (iv) an effective 'frothing agent' for floating-off impurities and (v) a penetrant and dispersing agent for use in textile fibre processing. A range of low molecular-weight polymers can be also produced from tree-derived monoterpenes and diterpines by cationic polymerisation. The characteristics of the polymer are influenced by the mix of polymer building blocks. These polymers are used to impart 'tack' in adhesive compounds. Polyterpene resins are used in the preparation of solvent-based pressure-sensitive adhesives and diterpene resins in the manufacture of hot-melt adhesives. Other applications for these tacky, thermoplastic properties include use in surface coatings and sealants. Flavours and fragrance represents a small, but growing fraction of terpentine utilisation (10-15%). In most cases, the terpentine components are converted to other chemicals. Amongst this family of compounds, -pinene is the most important feedstock. Menthol is produced from -pinene and is used for its 'cooling' effect (the L-isomer in particular) in cigarettes, cosmetics and flavourings (peppermint); a wide range of flavour and fragrance additives are derived from myrcene, produced by the pyrolysis of -pinene. -Pinene derivatives include (i) linalool and its esters -'lilac-like' fragrance, (ii) gerianiol, nerol & esters - 'rose-like' fragrance, (iii) citronellol - a precursor of rose oxide an important oil in perfumery, and (iv) hydroxycitronellal - 'Lilly-Of-The-Valley' fragrance. Citral is an intense lemon quality used in preparation of citrus flavours and fragrances. Further chemical processing of citral with acetone produces a mixture of ionones, of which the -isomer is widely used for its violet odour. Condensation of citral with 2-butanone gives methylionones, which are also valued as perfume agents. Other perfume ingredients can be derived from pyrolysis of pinene, such as tertiary alcohols with sweet floral odours that are used in soaps and cosmetics, and citrus-type colognes. Hydrogenation of -pinene produces camphene, which can be used to synthesise materials with a sandalwood odour, a costly process otherwise. Limonene (diterpine) is the starting material for synthesising carvone. Carvone has the flavour and odour of dill and has recently been developed as a sprout suppressant for use in potato stores. However, there are a number of other natural competitor feedstocks for this derivative, including caraway seed. A rich catalytic chemistry is also possible from these chemicals, as recently reviewed /123//124//125/. Monoterpenes are key ingredients in the flavor and fragrance industry, with - and -pinene being the most important. Transformations of terpenes involving isomerization, hydration, condensation, hydroformylation, hydrogenation, cyclization, oxidation, rearrangement, and ring contraction/enlargement are routes to produce a variety of compounds of interest to the pharmaceutical, agrochemical, and flavors and fragrances industries. p-Cymene, a precursor of p-cresol and various flavors and fragrances, was obtained by dehydrogenation of -pinene at 300C in a continuous fixed-bed flow reactor in the presence of 0.5wt.% Pd/SiO2 /126/. Under similar conditions, but starting from limonene, p-cymene was obtained in 97% yield and the catalytic activity was stable for 500 h on stream /127/. The liquid phase alkoxylation of limonene with C1aC4 alcohols to 1-methyl-4-[a-alkoxy-isopropyl]-1-cyclohexene was carried out both in batch and continuousfixed-bed reactor at 60C on various acidic catalysts /128/.
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The best yields were obtained in batch (85%) or continuous reactor (81%) using a b-type zeolite with SiO2/Al2O3 = 25. Catalysis offers several opportunities to develop cleaner processes of synthesis using renewable raw materials. An interesting example using terpenes derivatives as raw material was reported by Corma et al. /129/. They developed a new, alternative, halogen-free synthesis for the fragrance compound Melonal using zeolites and mesoporous materials as oxidation catalysts. At present Melonal (2,6dimethyl-5-hepten-l-al) fragrance is industrially produced by a Darzens reaction from 6-methyl-5hepten-2-one, with ethylchloroacetate as reagent. Corma et al. /129/ developed a novel halogen-free synthesis strategy that involves the chemoselective oxidation of Citral (3,7-dimethyl-6-octen-l-al), a common compound in the fragrance industry, with H2O2 and Sn-Beta or Sn-MCM-41 as catalysts. The performance of tin Lewis acid sites is compared with other potential catalytic sites, and it is found that aluminium Brnsted acid sites and zirconium or titanium Lewis acid sites are less efficient and selective than Sn. In the case of Ti, epoxidation by-products could be found. The Sn-Beta zeolite is reusable. 3.2.4 Glycerol
Glycerol is a co-product of triglyceride transesterification in the production of fatty acid esters employed as bio-diesel. Being fast increasing its production, glycerol represents an interesting platform molecule. As far as the production of chemicals is concerned, the main outlet of glycerol is the production of glycerol esters employed as emulsifiers, surfactants and lubricants. Fatty acid esters of glycerol are obtained either by transesterification of triglycerides with glycerol (glycerolysis) or by esterification of fatty acids with glycerol. The challenge in both cases is to obtain glycerol monoesters selectively.
Fig. 3-13. Possible paths of transformation of glycerol. Source /131/. Glycerol is a quite versatile chemical (Fig. 3-13) /130/. More than 3000 uses, mainly on OH substitution, oxidations and eliminations have been reported, but due to the large surplus of glycerol and consequent reduction of the costs, there is still an intense research efforts to find new applications of glycerol /131/. Fig 2-14 reports a general scheme of the chemicals from possible glycerol reactions /132/.
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Fig. 3-14. Scheme of the chemicals from possible glycerol reactions. Source /131/. The main glycerol derived products are summarized below: 1. Chemical: Reductive processes: 1,3-propandiol, ethylen glycol, methanol, allyl alcohol, propylene Oxidative processes: Glyceric acid, dihydroxyacetone, acrylonitrile, pyruvic acid, oxomalonic acids Acid-Base and elimination processes: Monoglycerides, other mono-, di- and triesters, alkyl ethers, acetol, acrolein Polymerization processes: Polyglycerols, other polyethers, polyesters, polyurethanes, .. 2. Biotransformation: 1,3-propandiol, -3 polyunsaturated fatty acids, carotenoids Fig. 3-15 reports schematically the technological new uses of glycerol derivatives.
Fig. 3-15 Technological new uses of glycerol derivatives. Source /131/. The selective oxidation of glycerol leads to various valuable oxygenates (glyceric, tartronic, mesoxalic, and hydroxypyruvic acids, dihydroxyacetone). Besson and Gallezot /133/ have shown that they can be obtained by oxidation with air of aqueous solutions of glycerol in the presence of carbon-
72
supported platinum and palladium catalysts. The selectivity can be tuned by promotion of the noble metals with bismuth or by operating under controlled pH. The same authors observed /134/ that the oxidation of glycerol at basic pH on palladium and platinum catalysts yielded 70% glycerate. Glyceric acid oxidation on 5%-Pt-1.9%-Bi/C catalyst yielded 74% hydroxypyruvic at 80% conversion at acidic pH (34), but on the same catalyst under basic conditions (pH 1011) a 83% yield of tartronate was obtained at 85% conversion. 93% selectivity for hydroxypyruvic acid at 95% conversion of glyceric acid could be obtained on 5%-Bi-5%-Pt/C catalyst without pH regulation /135/. More recently, the oxidation of glycerol was conducted in the presence of gold catalysts in basic medium. The selectivity was shown to depend critically upon the size of gold particles /136/. Acrolein has been obtained in 38% yield by glycerol dehydration at 360C, 25 MPa in the presence of zinc sulfate /137/. The usage of a homogeneous catalyst leads to an economical and ecological alternative to the established crude oil based process. Polyglycerols, obtained by the dehydration of glycerol (Fig. 3-16), are employed as surfactants, lubricants, cosmetic, food additives, etc. Their esterification with fatty acids leads also to valuable emulsifiers or metal-working fluids. Zeolites have been used to take advantage of their shape selectivity effect to minimize oligomer formation. A fair compromise between activity and selectivity has been obtained by Clacens et al. /138/ using cesium-impregnated mesoporous MCM-41.
OH
Diglycerol
OH OH HO O OH OH
HO
+ H2 O
+ glycerol Polyglycerols Triglyrecol
Fig. 3-16 Synthesis of polyglycerols by catalytic dehydration of glycerol derivatives. Source /84/. Catalytic dehydration by reactive distillation forms acetol as intermediate with high selectivity (>90%), opening then a series of interesting pathways of transformation, including the hydrogenation to form propylene glycol, an interesting alternative route for converting glycerol to 2-propanediol (1,2-PDO) (anti-freezing agent).
Fig. 3-16 Glycerol dehydration and acetol chemistry. Source /131/. Glycerol can be transformed selectively also to 1,3-propanediol (1,3-PDO), which when copolymerized with terephthalic acid gives polyesters with unique mechanical properties. 1,3-PDO is currently produced by catalytic routes from ethylene oxide (Shell route) or acrolein (Degussa-DuPont
73
route). The microbial production of 1,3-PDO was developed by DuPont-Genencor to produce 1,3PDO from glucose. Glycerol carbonate, obtained by reaction of glycerol with ROCOOR(CO2), is another interesting family of products (mon-, di- and tri-carbonate; linear and cyclic). Glycerol Carbonate (4hydroxymethyl-[1,3]dioxolan-2-one) is a benign solvent (co-formulant) and can be used in (i) medical and sanitary field, (ii) polymer bases for emulsions (polyglycerol carbonates, polyurethanes) and (iii) phenolic resins preparation. Further information on the catalytic transformation pathways for glycerol can be found in the review of Jacobs et al. /140/ 3.3 HIGH VALUE CHEMICALS
Bio-mass derived products constitute a highly attracting raw material for high-value chemicals, e.g. in the field of fine chemicals /141/. Sometimes natural fine chemicals are by-products in bulk products refining. Examples are: (a) lecithin and steroids in vegetable oil refining; (b) betaine, pectin and raffinose in sugar manufacture; (c) quinic acid in quinine extraction of the bark of Cinchona trees; (d) chitin and the red pigment asthaxanthin in lobster and shrimp processing; and (e) lanolin, lanosterol and cholesterol in sheep wool purification. However, typically, bio-mass derived products should be further chemically processed to obtain the necessary characteristics suitable to compete to traditional routes. We will describe here some examples additional to those discussed in the previous section. Vanillin. An important flavoring compound is vanillin with an estimated total production of about 14 000 t/h. Natural vanillin beans are expensive and the vanillin content is just 1.52 wt.%. Borregaard company produces vanillin by chemo-oxidation of cheap natural lignin. However, the process is complex and only 4 kg vanillin are obtained from one ton of wood. Rhodia has developed a new catalytic synthesis route. The process (Fig. 3-17) involves four catalytic steps starting from phenol: aromatic ring hydroxylation, O-methylation, hydroxymethylation, and oxidation. Catechol, the first oxidation product, can also be prepared starting from glucose. Vanillin is the starting point for several chemicals. Thus capsaicin, the pungent principle of red pepper (Capsicum annuum), used in pepper-spray and pain killing ointments, is made in two steps from vanillin.
Fig. 3-17. Rhodia vanillin process. Monoterpenes. Terpenes are classified according to their number of isoprene (C5) units as: monoterpenes (C10), sesquiterpenes (C15), diterpenes (C20), etc. -Carotene is a tetraterpene. Many oxygenated monoterpenes (alcohols, carbonyl compounds, esters) serve as fragrances. Natural starting compounds are -pinene, -pinene and limonene (Fig. 3-12), with production volumes of about 18 000, 12 000, and 30 000 t/y, respectively.
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Several examples could be indicated in addition to those cited in the section 3.1.2.3. Limonene can be alkoxylated with lower alcohols using zeolite H-Beta as the catalyst /142/ at room temperature already, with high selectivity and conversion (Fig. 3-18). The alkoxy compounds are applied as fragrances with, dependent on the length of R, characteristic odors.
HPW AcOH
ROF / H-Beta R = C1-C4
OH
OAc
OR
-terpineaol
-terpinyl acetate
Fig. 3-18. Alkoxylation and hydration of limonene. Source /141/. Heteropoly acids such as H3PW12O40 (HPW) are good catalysts for the hydration of limonene and other monoterpenes. HPWs can be used as homogeneous catalysts in solution or supported on, for example, silica or MCM-41 materials. In aqueous acetic acid limonene gives, in the presence of HPW, mainly -terpineol and -terpinyl acetate /143/. Dehydrogenation of limonene gives p-cymene with yields (>95%) using Pd-catalysts /141/. p-Cymene can be then oxidized to the hydroperoxide, which can be rearranged to p-cresol, a valuable chemical. - and -pinene are thus versatile renewable raw materials. The four-membered ring is strained; upon H+-catalysis an alkyl shift takes place and the bornyl cation is formed, which can enter various reactions. In contrast, the four-membered ring remains intact upon epoxidation or hydrogenation. Upon thermal treatment the four-membered ring transforms into a diene. Thus, -pinene is industrially converted into the noncyclic triene myrcene. This type of ring opening also plays a role in a semisynthetic route to linalool starting from -pinene (Fig. 3-19a). Linalool is an important fragrance and fragrance precursor (esters) with an annual production of over 15.000 t. Another large volume monoterpene is (-)-menthol. Only (-)-menthol (1R,2S,3R-configuration) possesses the characteristic peppermint odor. Most (-)-menthol is obtained by freezing peppermint or cornmint oil, followed by recrystallization. In 1983, Takasago company developed a new enantioselective catalytic method. Key steps are the enantioselective isomerization of diethylgeranylamine and the diastereoselective ring closure of (-)-citronellal to (-)-isopulegol (Fig. 319b). In the Takasago process ZnBr2 is used as the Lewis acid catalyst for the ring closure. Recently, zeolite Sn-Beta has been reported as a heterogeneous and recyclable catalyst /145/. Also the two final steps ring closure and hydrogenation can be combined by applying H-Betasupported iridium as the catalyst. It is thus possible to use multi-functional catalysts for a one pot cascade process.
75
OOH
OH
OH
H2
ROOH
H+
a) b)
NEt2 Et2NH Li Rh((S)-BINAP)2+
Linalool
NEt2
99% ee
Myrcene
H2O H+
H2 Ni raney OH OH
ZnBr2 CHO
(-)-Citronellal
(-)-Methol
(-)-Isopulegol
Fig. 3-19. Linalool synthesis from a-pinene (b) and Takasago enantioselective catalytic synthesis of (-)-menthol. Source /141/. Other example of one pot synthesis is the epoxidation of -pinene and the isomerization of the epoxide to campholenic aldehyde using Ti-Beta zeolite. Campholenic aldehyde is the starting material for several sandalwood fragrances. Alkaloids and Steroids. Another example of use of bio-mass based chemicals is that of alkaloids, nitrogen-containing compounds generally found as secondary metabolites in plants. Many pharmaceutically active alkaloids are directly applied as medicines, e.g., morphine, codeine, ephedrine, atropine, physostigmine, vinblastine, vincristine, quinine, colchicine, and galanthamine. However, bio-activity can often be improved by conversion into more effective derivatives with fewer unwanted side-effects. The synthetic production of morphine starting from renewable could be realized with an acidcatalyzed ring closure of a 1-(3,5-dihydroxy-4-methoxybenzyl) isoquinoline derivative that is prepared starting from (natural) gallic acid /141/. Morphine can be then converted to various pharmaceutically important derivatives via catalytic transformation. Steroids, compounds with a cyclopenta[a]phenanthrene skeleton, include a wide range of natural products such as sterols (e.g., cholesterol), sex hormones, adrenocorticoid hormones, cardiac glycosides and vitamin D. Sterols are steroids having a hydroxyl group at position 3 of the basic skeleton. Steroids can be found both in plants and in animals. Plant sterols such as sitosterol and camposterol, as by-products from vegetable oils at rather low prices, are an important starting materials for the production of steroid hormones /141/. A new application is the cholesterol lowering property of these sterols esterified with fatty acids (with a production of about 10.000 t/y). Proteins. A co-products of biofuel biorefinery are proteins which can be thus an interesting raw materials for chemical applications. Industrial uses of proteins include glues and adhesives, detergents, cosmetics, foils and packaging material, polyurethane and polyester, plastics for foams, and amino acid production. In fact, there are several functional properties of proteinic froducts from oilseeds which can be exploited: (1) water retention capacity: (a) water and oil absorption capacity and (b)
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protein solubility; (2) viscosity and thickening, (3) gelation: least gelation concentration; (4) foaming capacity; and (5) emulsifying activity and stability /146/. 3.4 BIOBASED OLEOCHEMICALS
The use of vegetable fats and oils in oleochemistry allows the development of competitive products that are both consumer- and environmentally-friendly /147//148//149//150/. In polymer applications derivatives of oils and fats, such as epoxides, polyols and dimerizations products based on unsaturated fatty acids, are used as plastic additives or components for composites or polymers like polyamides and polyurethanes. In the lubricant sector oleochemically-based fatty acid esters have proved to be powerful alternatives to conventional mineral oil products. For home and personal care applications a wide range of products, such as surfactants, emulsifiers, emollients and waxes, based on vegetable oil derivatives has provided excellent performance. 3.4.1 Life cycle assessment
When switching from fossil feedstocks and chemical production processes to renewable feedstocks processed with biotechnological methods the assessment of the environmental and economic benefits provided by the process should cover the entire life cycle (cradle-to-grave) of a product raw material production, manufacture, product use and fate /149/. The major elements of the environmental assessment include primary energy use, raw materials use, emissions to all media, toxicity, safety risk and land use. The method that is usually referred to as a life cycle assessment (LCA). There are limited examples of analysis of bio-based products from a life cycle perspective, but they provide good glimpse about the need to look in a more detail on LCA to assess the real impact of renewable raw materials. Bioplastics from corn. Biodegradable polymers based on renewable raw materials have attracted considerable attention for replacing at least some of the traditional plastics. Among these are polyhydroxyalkanoate (PHA) a microbially synthesized polyester manufactured by Metabolix /151/ and polylactic acid (PLA, NatureWorksTM), a product of Cargill Dow /152/ from lactic acid generated by fermentation. The LCA for the production of PHA using corn as a feedstock showed no environmental benefits because the amount of fossil fuel used to produce 1 kg of PHA exceeds that required to produce an equal amount of the polystyrene it would replace /153/. The main hot spots in the life cycle of bioplastics with respect to energy input were the raw material production and the fermentation process, particularly in the case of PHA. Corn is one of the more energy-intensive crops and accounts for substantial amounts of fertilizer, insecticide and herbicide use. The subsequent transport and processing of the corn, involving wet milling and fractionation to yield gluten meal, oil, starch and sugar, also expend energy. For such a feedstock, the fuel source used for energy generation could have a profound impact on the environmental credentials of the product. Oleochemical products for wood coatings. An assessment of the total energy consumption for wax ester production by lipase-catalysed esterification demonstrated that 34% less energy was consumed and less waste generated than by chemical esterification, where a strong acid is used as catalyst /154/. However, from a life-cycle perspective, comparison of the wax ester as a wood-coating ingredient with other coating products showed that UV-curable coatings based on fossil feedstock were the most favourable alternative in all environmental categories /155/. A similar observation was made using the eco-efficiency analysis method of BASF /156//157/. These two examples stress the importance of evaluating the environmental impact of bio-based products with respect to their entire life cycle, demonstrating that the choice of the raw material often turns out to be an important parameter influencing the life cycle performance. However, it should be
77
remarked that often products based on renewable resources are more ecologically compatible than petrochemical-based substances. Therefore, the general assumption of better ecological compatibility of bio-based products has to be proven for each new product. 3.4.2 Industrial uses of natural oils and fats
Apart few exceptions, such as castor oil (a glycerol triester of 12-hydroxyoleic acid - ricinoleic acid), oils and fats are triglycerides that typically consist of glycerine and saturated and unsaturated fatty acids. Triglycerides offer two reactive sites, the double bond in the unsaturated fatty acid chain and the acid group of the fatty acid chain. Most derivatization reactions are carried out at the carboxylic group (>90%) whereas oleochemical reactions involving the alkyl chain or double bond represent less than 10%.
Sebacic acid
NaOH
Natural Fats andOils Oleic Acid
Biooxidation
C18Dicarboxylic Acid
Ozonolysis
Azelaic Acid
Polyamides Nylon6.9 Nylon6.6.9 Polyurethanes Laminating adhesives
Dimerization
Dimer Fatty Acid
Oxid./Epoxid./RingOpening
Polyols
Polyamido amines Polyuethanes Epoxy curing Radiation Curing agents acrylates NonNylon polyamides Hotmelt adhesives Printing ink resins Modified Epoxy resins
Fig. 3-20
Industrial processing of natural oils and fats and selected product derivatives. Elaborated from /148/.
In terms of application, oils and fats must be converted into the so-called oleochemical base materials: fatty acid methyl esters, fatty acids, glycerol and, as hydrogenation products of the fatty acid methyl esters, fatty alcohols (Fig. 3-20). In terms of products, the main classes of applications are the following: polymers, esters lubricants, surfactants, emulsifiers and emollients for home and personal care applications. Industrial oleochemistry has concentrated predominantly on the carboxy functionality of fatty acids but, more recently, modern synthetic methods have been applied extensively to fatty compounds for the selective functionalization of the alkyl chain /122/. Radical, electrophilic, nucleophilic, and pericyclic as well as transition metal catalyzed additions to the C-C double bond of, for example, oleic acid as the prototype of a readily accessible, unsaturated fatty acid have led to a large number of novel fatty compounds from which interesting properties are expected. Functionalization of C-H bonds in the alkyl chain is also feasible with remarkable selectivity. Effective and highly versatile catalysts for the metathesis of esters of unsaturated fatty acids have been developed, which lead to new and interesting -unsaturated fatty acids. The epoxidation of unsaturated fatty acids has been developed extensively. Enzymatic reactions allow syntheses with high selectivity and yield of mono- and diglycerides and esters of carbohydrates with a variety of surfactant properties. Regio- and enantioselective microbial hydrations and hydroxylations widen the spectrum of selective reactions. Of considerable significance is that, with the use of gene technology, natural oils and fats have been improved significantly and will be improved still further, insofar as they show a more uniform and often unusual fatty acid spectrum. Numerous fatty acids are now available in a purity which makes them attractive for synthesis and as raw materials for the chemical industry.
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3.4.3
Oleochemicals for Polymer Applications
Selected examples of the use of oleochemicals in polymers are reported in Table 3-5. One can differentiate between the use as polymer materials linseed oil and soybean oil as drying oils), polymer stabilizers and additives ( epoxidized soybean oil as plasticizer), and building blocks for polymers (dicarboxylic acids for polyesters or polyamides. The share of oleochemical based products is still relatively small, but growing. Of increasing interest is the area of natural fiber reinforced plastics for various applications, among them the automotive and public transportation industries. Composite with natural fibers, such as flax, hemp, sisal, and yucca find application as in door pockets, covers, instrument panels, and sound insulation. Oleochemical based dicarboxylic acids azelaic, sebacic, and dimer acid (Fig. 3-21) amount to ca. 100.000 t/y as components for polymers. This is about 0.5% of the total dicarboxylic acid market for this application, where phthalic and terephthalic acids represent 87%. However, these oleochemical based dicarboxylic acids improve properties such as elasticity, flexibility, impact strength, hydrolytic stability, and flexibility. Table 3-5. Selected examples of the use of oleochemicals in polymers. Source /148/. Product/use Source Polymer materials Polymerized soybean oil, castor oil Polymerized linseed oil Polymer additives Epoxides Soaps (Ba/Cd, Ca/Zn) Fatty acid esters, amides, waxes Building blocks for polymers Dicarboxylic acids Ether-/ester polyols Drying oils Linoleum Soybean oil, castor oil Linseed oil
Stabilizers, plasticizers Stabilizers Lubricants Polyamides, polyesters alkyd resins, polyurethanes
Soybean oil Stearic acid Rapeseed oil Tall oil, soybean oil castor oil, sun-flower oil, linseed oil, oleic acid
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starch
fatty acid methyl ester
glucose
Alkyl polyglycosides derivatives Guerbet alcohols Alkyl chlorides Fatty Alcohol ethoxylates Fatty alcohol sulfates Technical esters Triacetin (poly)glycerol esters Fatty acidesters Conjugated fatty acids Alkyl epoxyesters Dimer acids Azelaic/pelargonic acids Acylated aminoacids
fatty alcohols
Oil& Fats
glycerine
fatty acids
protein
Protein hydrolyzate
Proteinfatty acid condensate
Fig. 3-21. Building blocks for polymers based on natural oils. Elaborated from /148/.
3.4.4
Dimer Diols Based on Dimer Acid
Dimerization of vegetable oleic acid or tall oil fatty acid (TOFA) yields dimer acids. The reaction is very complex, resulting in a mixture of aliphatic branched and cyclic C36-diacids (Dimer acid) as the main product besides trimer acids and higher condensed polymer acids on one hand, and a mixture of isostearic acid and unreacted oleic and stearic acid on the other hand. Hydrogenation of dimer acid methyl ester or dimerization of oleyl alcohol leads to dimer alcohols (dimer diols). Oligomers based on dimer diol are industrially manufactured by acid-catalyzed dehydration of dimer diol. Oligomers in the molecular weight range 10002000 Da are commercially produced by this route. Another method used to produce oligomers is the transesterification of dimer diol with dimethyl carbonate. The resulting dimer diol polycarbonate has an average molecular weight of 2000 Da. Both types of oligomers, ethers and carbonates, show improved chemical stability compared with dimer diol polyesters. Owing to their improved stability towards hydrolysis and oxidation, dimer diol polyethers (and dimer diol polycarbonates) are used as soft segments in the preparation of thermoplastic polyurethanes. Polyurethanes prepared from such oleochemical building blocks are very hydrophobic and show high stability. Soft segments based on dimer diol ethers are used to prepare saponification resistant TPUsealings, which allow the contact with aggressive aqueous media at elevated temperature. A typical field of application is in nutrition technology. 3.4.5 Polyols Based on Epoxides
The reaction of epoxidized oils with low molecular weight mono- or polyfunctional alcohols or acids gives rise to low molecular weight liquid epoxy polyol esters or ethers that can be employed as polyols for polyurethane. Depending on the reaction conditions, either polyols with high OHfunctionality (complete reaction) or epoxy polyol esters with remaining epoxy groups (partial conversion) are obtained. Although hydroxyl-functional triglyceride oils have found applications in casting resins and adhesives the carboxyl groups of the triglyceride backbone are not fully resistant against hydrolytic attack, particularly by alkali. To overcome this specific behavior fatty acids are
80
used as starting oleochemicals in the preparation of (epoxy) polyols. Three categories of products are obtained via this route: 1. fatty acid derivatives with reactive OH groups in the ester position only, e.g., glycerol monostearate, 2. fatty acid derivatives with reactive OH groups in the ester position and in the hydrocarbon chain, e.g., glycerol monoricinoleate, 3. fatty acid derivatives with reactive OH-groups in the hydrocarbon chain only. These new polyols are of low molecular weight and relatively low viscosity. They offer outstanding hydrolytic stability against both alkali and acids and very high chemical resistance towards corrosive solvents, such as super fuel. They also offer significantly improved mechanical properties compared with hydroxyl functional oils after reaction with aliphatic isocyanates. Oleochemical polyols have an average molecular weight of 2502500 Da. Owing to their relatively low viscosity and their compatibility with methylene di(phenylisocyanate) (MDI) they are particularly suitable for solvent-free, two pack, full solids polyurethane systems, to be applied as thin decorative or protective coating by brush, roller or spraying. They can also be applied in thick coatings, bearing even high filler loads. In industrial flooring applications, selfleveling polyurethane or epoxy/polyurethane multilayer systems offer good chemical and mechanical properties and benefits such as minimal shrinkage, high mechanical strength and durability, and favorable cost of installation. They are broadly used for wear and crack resistant floorings on parking decks, for concrete protection in assembly areas, as well as in large kitchens, slaughterhouses and groceries, due to the ease of cleaning. Oleochemical polyols can also be used to bind porous filler materials, like perlite, and rubber particles for applications of composites in construction, soil protection, sport tracks, and playing fields /148//149/. 3.4.6 Biodegradable Fatty Acid Esters for Lubricants
Fatty acid esters, which are obtained from fatty acids and alcohols, are becoming increasingly interesting as biodegradable replacements for mineral oils. In some application areas such as chainsaw oil, gearbox oils, hydraulic oils and lubricants for crude oil production these oleochemical products have already proved themselves. Esters for lubricant applications are divided into five groups: monocarboxylic acid esters (monoesters), dicarboxylic acid esters (diesters), glycerol esters, polyol esters, and complex esters. Monoesters are obtained by reacting carboxylic acids with alkyl chain lengths from C8 to C22 and branched or linear alcohols. The typical diesters are obtained, for example, from adipic, sebacic, azelaic, or dimer fatty acids by reaction with butanol, ethyl hexanol, isodecanol, isotridecanol or Guerbet alcohol. Complex esters are formed by esterification of polyols with mixtures of mono, di, and tricarboxylic acids and are oligomer mixtures, which from a technical application viewpoint are characterized by their high shear stability. Fatty acid esters that are used as replacements for mineral oil products not only have ecologically compatible properties but also a comparable or even better performance than that of conventional products. 3.4.7 Surfactants and Emulsifiers
Surfactants are also used in the food sector, in crop protection, in mining, and in the production of paints, coatings, inks, and adhesives. The basic manufacturing routes to important surfactants are schematically reported in Fig. 3-22. Most important surfactant is still petrochemical-based alkyl benzene sulfonate. However, in recent years a continuous increase in surfactants based on renewable resources was observed. The total worldwide market amounts to ca. 20 million tonnes.
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Petroleum /Natural Gas Alkanes Alkenes Alkyl benzene

Nonionic surfactants
Oils /Fats Methyl esters Fatty alcohols Alkyl polyglycoside Fatty alcohol ethoxylate Fatty alcohol sulfate
Ethene
Linearalkyl benzenesulfonate
anionic surfactants
Fig. 3-22. Simplified scheme of production of surfactants from fossil and renewable sources. Elaborated from /148/. Fatty alcohol sulfate (FAS) is produced directly from fatty alcohol by reaction with sulfur trioxide (SO3) gas (18% v/v in air or nitrogen) in a falling-film reactor. The crude product is then neutralized with aqueous sodium hydroxide. Fatty alcohol sulfates are readily biodegradable (no metabolites in the degradation) under both aerobic and anaerobic conditions. FAS can be produced either from vegetable oil based or petrochemical-based fatty alcohol. The comparison of the environmental impact of vegetable oil based fatty alcohol sulfate with that of the petrochemical based product indicates that the former shows: 70% less use of fossil resources, 50% less emissions to the atmosphere, 15% less waste, 50% more emission to water (low toxic waste water from small, decentralized oil plants).
Interesting surfactants (alkyl polyglycosides) can be derived also from carbohydrate The hydrophobic (or lipophilic) hydrocarbon chain is formed by a fatty alcohol (dodecanol/tetradecanol) obtained from palm kernel oil or coconut oil. The hydrophilic part of the molecule is based on glucose (dextrose) obtained from starch. The chemical challenge to process technology was to find reaction conditions that allowed fatty alcohol to react directly with glucose on a commercial scale and at an acceptable cost. Cognis was the first company to offer alkyl polyglycosides on an industrial scale at the required quality. Currently, Cognis has a capacity of ca. 50.000 t/y. The use of alkyl polyglycosides in lightduty detergent or shampoo formulation allows to reduce the total amount of surfactants. In other combinations a particularly stable and fine foam can be produced that protects sensitive textiles during the washing process. Alkyl polyglycosides have a good compatibility with the eyes, skin and mucus membranes and even reduce the irritant effects of surfactant combinations. In addition, they are completely biodegradable, both aerobically and anaerobically. Alkyl polyglucoside carboxylate (INCI-name Sodium Lauryl Glucose Carboxylate (and) Lauryl Glucoside, Plantapon2 LGC SORB) is a new anionic surfactant with excellent performance for personal care cleansing applications. In shampoo and shower bath formulations the anionic surfactant shows a good foaming behavior. In body wash applications it improves sensorial effects. A new industrial process based on the reaction of sodium monochloroacetate with aqueous alkyl polyglycoside (without additional solvents) enables the manufacturing of this product in an economically and ecologically favorable way.
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Emulsifiers based on glycerol or polyglycerol are a class of products well known in the market and used particularly in products for personal care and the food area. Emollients in another relevant area of application of oleochemical-based products. The latter include glycerides, esters, alcohols, ethers, and carbonates with tailor-made structures. One example of new class of compound in this area is dioctyl carbonate. The product is synthesized by the trans-esterification reaction of octanol and dimethyl carbonate in the presence of alkali catalyst. Dioctyl carbonate (Cetiol2 CC) is a dry emollient with excellent dermatological compatibility and a comprehensive and convincing performance profile for various applications in the personal care segment. Guerbet alcohols, derived from the self-condensation reaction of alcohols, which, via the aldehyde as an intermediate, lead to branched structures (2-alkylalcohols) is another class of efficient emollients. Starting with fatty alcohols from vegetable sources, such as octanol and decanol, the corresponding C16 and C20 alcohols are produced (2-hexyldecanol and 2-octyldecanol, respectively). The reaction is carried out under alkali catalysis and high temperatures (>200C). These chemicals find use also as plasticizers or components for lubricants. 3.5 CONCLUSIONS
Biomass feedstocks are already used in some processes, such as in oleochemistry. In addition, biopolymers are somewhat well established, although their use and production still needs to increase and new improved (catalytic) methods for their production are required. Fine chemicals from renewable is another area in which various examples already exist, demonstrating that natural products play an important role in chemical production. Catalytic methods, chemo- as well as bio-catalysis, are of vital in the conversion of natural products into derivatives (semi-synthesis). In chemo-catalysis conventional catalysts, such as mineral acids, are being replaced by recyclable solid catalysts. Further progress is also expected in cascade processes in which synthesis steps are combined to give one pot methods. A thorough analysis of value chains and the development of alternative value chains starting from biomass derived feedstocks, including assessment of the economic viability of the transformation of the chains, is required. This should be followed by the identification of easy entry points for the implementation of novel value chains. Major market opportunities and potential applications for renewable raw materials (fall into four main areas: chemicals, speciality chemicals, industrial fibers and industrial oils. chemicals: e.g., chemical intermediates and polymers; speciality chemicals: adhesives, solvents, surfactants (e.g., in personal care products and soaps & detergents), specialized organics and pharmaceutical and healthcare products (e.g., vitamins); industrial fibers: paper & board, composites, textile fibers and bulk fibers; industrial oils: lubricants, e.g., hydraulic oils, motor & gear oils, transmission fluids and metalworking fluids.
The main current products in the field of biopolymers are (a) composite materials for special and high quality performance applications, (b) fashion and comfort/hygiene where their silky feel, breath ability and anti-static characteristics create a value over and above the environmental aspects (e.g., sports wear and carpets made from poly-lactic acid (PLA), and the diaper liners and working overalls made from starch-based materials), (c) materials for agriculture, such as biodegradable mulch films, (d) plastic bags for the collection and composting of biodegradable waste, (e) food and industrial packaging materials, and (f ) catering products, i.e., plates, cutlery etc.
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In the lubricant sector, oleochemical based fatty acid esters have proved to be powerful alternatives to conventional mineral oil products. For home and personal care applications a wide range of products, such as surfactants, emulsifiers, emollients and waxes, based on vegetable oil derivatives have proved to provide excellent performance benefits to the end-customer. Selected products, such as the anionic surfactant fatty alcohol sulfate, have been investigated thoroughly with regard to their environmental impact compared with petrochemical based products by life-cycle-analysis. Other product examples include carbohydrate based surfactants as well as oleochemical based emulsifiers, waxes and emollients.
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TECHNICAL PROFILES OF BIOREFINERIES
Part 4:
4.1
THE CONCEPT
Although a number of new bioprocesses have been commercialized it is clear that economic and technical barriers still exist before the full potential of this bio-processing can be realized. One area gaining considerable momentum is the biorefinery concept. A Biorefinery is a facility that integrates biomass conversion processes and equipment to produce fuels, power, and chemicals from biomass. In other words, a biorefinery efficiently separates biomass raw material into individual components and converts these components into marketable products. A biorefinery (Scheme 4.1) is similar to todays petroleum refineries, which produce multiple fuels and products from petroleum.
Scheme 4.1: Overview of general integrated biorefinery process. Adapted from /157/. A biorefinery, by producing multiple products, can take advantage of the differences in biomass components and intermediates and maximize the value derived from the biomass feedstock. A biorefinery might, for example, produce one or several low-volume, but high-value, chemical products and a low-value, but high-volume liquid transportation fuel, while generating electricity and process heat for its own use and/or for sale /159/. The high-value products enhance profitability, the highvolume fuel helps meet energy needs, and the power production reduces costs and avoids greenhousegas emissions. The production of biofuels in the biorefinery complex will service existing high volume markets, providing economy-of-scale benefits and large volumes of by-product streams at minimal cost for upgrading to valuable chemicals. A pertinent example of this is the glycerol byproduct produced in biodiesel plants. Glycerol has high functionality and is a potential platform chemical for conversion into a range of higher value chemicals. The high volume product streams in a biorefinery need not necessarily be a fuel but could also be a large volume chemical intermediate such as ethylene or lactic acid. A key aspect of the biorefinery is the imbalance between commodity chemical needs and transportation fuels. Using the petroleum industry as an illustrative example, presently, about 85 percent by mass of the aggregated output of petroleum refining consists of transportation fuels and
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energy (gasoline, distillate fuel oil, jet fuel, residual fuel oil), with the remaining 15 percent consisting of over half a dozen product types that add considerably to the profitability of the overall operation while ensuring that all fractions of crude oil are used /160/. Products ratios from a biorefinery will be based on the biomass feedstock option and the technological routes through which the feedstock is processed. By analogy with crude oil, however, every element of the plant feedstock is expected to be utilized including the low value lignin components. The motivations for adopting the biorefinery can be economic, social or environmental as presented in Table 4.1. Table 4.1: Motivations for biomass refining Economic Feedstock cost: May provide a means to access markets for bioproducts whose Motivations volume is too high and/or price too low to be accessed using corn as a raw material. New markets: Provides potential to create new markets, such as polylactic acid and 1,3- propanediol. Tax incentives: Can benefit from tax incentives likely to be offered to promote such investment.
Societal Motivations:
Sustainable resource supply: Biomass refining has the potential to significantly reduce both greenhouse gas emissions and the extent of nonrenewable resource depletion Energy security: By reducing dependence on foreign oil, large-scale biomass refining would enhance a nations energy security. Rural economic development: By creating a large market for energy crops, could potentially balance demand for agricultural products with current production capacity.
Environmental Motivations: Source: /160/
Waste management: By utilising close to 100% of the entire biomass raw material, less waste is generated, which even reduces further, the cost of managing waste
Consistent with the interests outlined in Table 4.1, both the private and public sectors are active today in anticipating and enabling the emergence of a new biomass refining industry. 4.2 BIOREFINERY FEEDSTOCKS
The products from a biorefinery will be strongly influenced by the feedstock processed by the facility. Currently most feedstocks used for fermentation processes in the ethanol industry are based on sugar cane, corn and sugar beet. Sugars are a very abundant renewable resource and there are many ways of transforming sugars into bioproducts. In the United States, much attention has been paid to corn-based biorefinery, and the products have been mainly starch and carbohydrate derivatives from it, but also smaller amounts of oil, protein, and fibre. However biorefineries require a large and constant supply of biomass and other substrates would have to be used if costs are going to be reduced. Such biomass could include grains such as wheat and barley, oils, agricultural residues, waste fruits, straw, waste wood and forest trimmings and dedicated
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energy crops such as switchgrass or hybrid poplar /161/. The most significant impact of biorefineries on energy, greenhouse gases and climate change is likely to come from the conversion of lignocellulosic materials to ethanol /160/. Due to the huge volumes of corn grown across the globe, corn stover is and will continue to be the leading candidate of biomass source to support a lignocellulosic biorefinery. Vegetable oil-based products are also another excellent feedstock for biorefineries because of their versatility. They can be used for the production of several products, such as solvents, lubricants and hydraulic fluids, polymers, resins, printing inks, cosmetics, pharmaceuticals and numerous other applications /162/. It is expected that feedstock properties will influence design of thermochemical biorefineries in the future. Scheme 4.2 shows connections between different types of feedstocks and different approaches of product utilization.
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Feedstock: BIOMASS
Biomass components:
Starch, lignin, hemicellulose, cellulose, protein, oils
Platform intermediates:
Glucose, xylose, arabinose, fructose, lactose, sucrose, starch
Biobased syngas
Building blocks:
C3: glycerol, lactic acid, 3-hydroxy propionate, propionic acid, malonic acid, serine C4: succinic acid, fumaric acid, malic acid, aspartic acid, 3- hydroxy butyrolactone, acetoin, threonine C5: itaconic acid, furfural, levulinic acid, glutamic acid, xylonic acid, xylitol/arabitol C6: citric/ aconitic acid, 5hydroxymethyl-furfural, lysine, gluconic acid, glucaric acid, sorbital Aromatics: gallic acid, ferulic acid & direct polymers & gums
Hydrogen, methanol, mixed higher alcohols, oxo-synthesis products, iso- synthesis products, Fischer-Tropsch liquids, etc.
End products:
Polymers, fuels, lubricants, water chemicals, fertilizers, paints, resins, pesticides, pharmaceuticals, cosmetics, etc.
Scheme 4.2: Biorefinery: feedstocks to products evolution
4.3
BIOREFINERY TYPES ACCORDING TO FEEDSTOCK AND TECHNOLOGIES
Biorefineries can be classified based on the biomass feedstock to be processed or the technological platform. Based on the biomass feedstock, biorefineries can be classified as: Whole crop biorefineries Green biorefineries Lignocellulosic biorefineries
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4.3.1
Whole crop biorefinery.
The general concept of whole crop biorefinery is to take advantage of as much of the plant as possible and process it into products that deliver the highest possible value. This is a step forward from plants that make use of just the grains and leave the stalks as waste materials. The whole crop biorefinery aims to process about 100% of the biomass feedstock. As shown in Scheme 4.3 for whole crop cereals, the feedstock is transported from the field and milled (or pressed, in the case of oil seeds) to separate economically recoverable plant components, which might include sugar, starch, oil, protein, and fibre. Oil is recovered from the germ (in the case of wet milling) while the fibre remain mixed with the starch. The starch-rich mash is then fermented to produce ethanol. The unfermented constituents of the starch-mash from the grind operation known as distillers dried grains and solubles (DDGS) is also separated and dried. The DDGS is gasified to CO and H2 (syngas), which is cleaned and catalytically converted to alcohols or hydrocarbon-based fuels (Fischer Tropsch liquids) /163/. The straw can also be treated to produce fuels and other chemicals, or gasified to produce similar products as those realised from the DDGS. Depending on the feedstock and technology route, there can be different types of biorefineries in this category. The whole crop biorefinery concept is already being used to some extent in some industries such as the sugar industry, starch industry and food and feed industry, where fermentation of sugars is a key process. However, most of these plants make use of just the grains without deriving much value from the cellulosic parts of the crop. There are opportunities to derive higher values from some of the byproducts than occurs in the present plants and to make additional use of the whole crop biomass instead of just the grains.
Scheme 4.3: Whole crop biorefinery based on dry milling of cereals. Adapted from /164/. 4.3.2 Green Biorefinery
The Green Biorefinery is a based on the integrated processing of green biomass into multiple products. It uses fresh biomass crops, for example grass from cultivation of permanent grass land, closure fields,
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nature reserves; lucerne, clover, and immature cereals from extensive land cultivation. This biorefinery is especially suitable for places with excess grassland. The concept (see Scheme 4.4) is based on pressurisation of the wet biomass, resulting in a fibre-rich press cake and a nutrient-rich press juice /165/. Careful wet fractionation technology is used as a first step (primary refinery) to isolate the contents of the green crop (or humid organic waste goods) in their natural form /164/. The press cake contains cellulose, starch, dyes, pigments, crude drugs, etc. while the green juice contains proteins, enzymes, free amino acids and organic acids. The green juice is used for the production of such items as ethanol, lactic acid, proteins and amino acids. The cake is used for the production of feed pellets, other important components for the chemical industry and for conversion to syngas and synthetic biofuels. The press cake is the largest material stream encountered in a green biorefinery and as such the overall economic efficiency of a green biorefinery is strongly determined by the economic efficiency of converting this fibre fraction into marketable value added fibre products. The residues of substantial conversion are suitable for production of biogas combined with generation of heat and electricity. Products generated in a green biorefinery /166/ may be grouped as: 1. Bulk chemicals (e.g. organic acids like lactic acid, solvents like ethyl-lactate). 2. Fuels (e.g. ethanol, acetone, butanol, ester). 3. Food / feed (e.g. amino-acids, protein products, peptides). 4. Fibre products (e.g. fibreboards, biocomposites, insulation material). 5. Fine chemicals (e.g. flavours, chlorophyll, pigments). 6. Biogas (electricity + heat) The advantages of the Green Biorefinery are a high biomass profit per hectare and a good link with the agricultural production; whereas the price segment of the raw materials is still low. Green biorefineries can process from a few tonnes of green crops per hour (farm scale process) to more than 100 tonnes per hour (industrial scale commercial process).
Scheme 4.4: Green biorefinery system. Adapted from /164/.
4.3.3
Lignocellulosic feedstock biorefinery
Lignocellulosic feedstocks can include straw, switchgrass, hybrid poplar, cornstover, reed, wood, paper and municipal waste and consist of three primary chemical fractions or precursors: hemicellulose/polyoses, sugar polymers of, predominantly, pentoses;
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cellulose, a glucose polymer; and lignin, a polymer of phenols
The lignin, hemicellulose and cellulose components are first separated and then processed. As illustrated in Scheme 4.5, the plant material is first pretreated (some pretretments include dilute acid, hot water, steam explosion, and ammonia explosion) to increase the surface area of lignocellulose, making the polysaccharides more susceptible to hydrolysis. The product streams usually include cellulose, hexose and pentose from hydrolyzed hemicellulose, and lignin.
Cellulose
Sugar, raw material
Hemicellulose Lignocellulose
Fuels, chemicals, polymers, materials Cogeneration to produce heat and power
E-37
Lignin
Lignin raw material
Scheme 4.5: Lignocellulosic feedstock biorefinery. Adapted from /164/. The cellulose can be saccharified after which the sugars are fermented to ethanol or other fermentation products. The hemicellulose can be hydrolysed and the resulting sugars converted into alcohol and value added chemicals via fermentation and chemical catalysis. Lignin which is the noncarbohydrate constituent of fibre can be thermochemically converted to syngas followed by catalytic conversion to alcohols, fuels, chemicals and other materials. The choice of the technology applied in converting lignocellulosic feedstock determines what the final products would be. For any of the aforementioned biomass feedstocks and biorefinery types, one or a combination of technologies is usually possible. To generally describe the technological approach used to treat biomass or some of its components, a classification according to the technological pathway is usually adopted. Such general technological pathways include biochemical, thermochemical, and hybrid. In the former two the respective technologies (of biochemical or thermochemical nature) constitute the primary method of converting biomass components into intermediates and/or final products (in some cases certain intermediates can be converted to final products using a different nature of technology). In the case of hybrid technology, the primary treatment step is thermochemical followed by the biochemical treatment of intermediates. Listed below there are several examples of the technological routes appertaining to these pathways: Biochemical Fermentation of sugars to alcohols and other products Enzymatic hydrolysis of starch or cellulose to sugars (sugars can be then converted to alcohols/chemicals via either biotechnological or chemical catalytic approaches, and the residuals can be also treated via anaerobic digestion or gasification)
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Anaerobic digestion of humid biomass to biogas (can be successively converted to methane via chemical catalytic technology) Thermochemical Gasification of biomass to syn-gas and successive catalytic syntheses Fast pyrolysis of biomass to bio-oil and successive extraction of chemicals or chemical catalytic synthesis/upgrading based on bio-oil components Hybrid thermochemical/biochemical Production of syngas via gasification and its successive fermentation Production of bio-oil via pyrolysis and its successive fermentation Other chemical Acid hydrolysis of cellulose to sugars Transesterification of vegetable oils and esterification of fatty acids Fine organic synthesis of drugs and speciality chemicals based on various plant substances
One of the main technological challenges of modern biorefineries lies in the possibility to efficiently treat the lignocellulosic feedstock. Therefore, cellulose hydrolysis to sugars (biochemical) or its gasification to syn-gas (thermochemical) are usually referred to as the two basic biorefinery approaches called sugar platform and syngas platform. However, apart from the syn-gas and sugar platforms for cellulose conversion and other biochemical and hybrid pathways for biomass treatment (e.g. biogas and pyrolysis based) a biorefinery can be, in principle, built around other chemical technologies, like classical acid hydrolysis of cellulose, transesterification of oils, etc. 4.3.4 Biochemical pathway
A classical example of this pathway is the enzymatic hydrolysis of starch or cellulose with subsequent fermentation of sugars to produce ethanol and other products. As shown in Scheme 4.6, fibrous feedstock must first be pre-treated (usually with strong acid) to break down the hemi-cellulose fraction and make the remaining cellulose material more accessible for subsequent saccharification. Cellulose enzymes are then introduced to hydrolyze the carbohydrate material, providing a variety of sugars which are fermented to produce ethanol and other fermentable products. The lignin portion of the original biomass feedstock is generally unreacted throughout this process, and is recovered to be used as a fuel or feedstock for thermochemical conversion processes. Major technical challenges and barriers to the biochemical pathway include dealing with the variability of biomass feedstocks, general recalcitrance of lignocellulosic materials to biological degradation, and the need for improved effectiveness of cellulose enzymes and fermentation organisms /167/.
Lignin to thermochemical conversion
Saccharification Fibrous crop
C5 & C6 Sugars Fermentation
Pretreatment
Scheme 4.6: Biochemical biorefinery based on lignocellulosic feedstock. Adapted from /163/.
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Distillation
Cellulose enzymes
CO2
Ethanol & other products
Biogas technology is based on the biochemical process of anaerobic digestion of certain biomass components (e.g. proteins, sugars, oleochemicals, etc.) and can be an important component of certain biorefineries e.g. to process humid low value residuals coming from key product extraction processes (green and whole crop biorefineries). The biogas can be used on site for energy generation or be upgraded to bio-methane. In addition to the sugar platform biorefinery and energy generation via biogas, some other biochemical processes can be used in biorefinery for chemical production. For example, proteins contained in plants and in bio-waste can be treated by bacteria to obtain biodegradable plastics (polyhydroxyalkanoates). 4.3.5 Thermochemical pathway
Thermochemical pathways generally utilize either gasification or pyrolysis technologies as the primary processing step which yield sin-gas or bio-oil, respectively, as the intermediates for further syntheses. The gasification technology biorefinery is shown in Scheme 4.7. It involves high temperature thermal decomposition of the biomass, followed by partial oxidation to produce raw synthesis gas (consisting mainly of CO and H2). Following cleanup and conditioning, syn-gas can be reacted catalytically to produce mixed alcohols, FischerTropsch hydrocarbons and other products depending on the catalytic technology chosen. A range of syn-gas based technologies are well developed and applied in the petrochemical refineries. Pyrolysis also involves thermal decomposition of biomass, but it is done at somewhat lower temperatures, and in the absence of oxygen, to produce a bio-oil and gases. The bio-oil contains a range of valuable chemical components that can be extracted and used as speciality chemicals, or be converted into other valuable products, e.g. resins, fuels, etc. For example, bio-oil can undergo steam reforming to produce hydrogen or hydrogenation to hydrocarbon fuels. Another possibility is to convert bio-oil to syn-gas via its gasification to produce better quality syn-gas than that from the direct gasification of bio-mass. An example of the bio-oil based biorefinery is given in Scheme 4.8.
CO2
Gas cleaning syngas
Catalytic reactor
Chemicals
Heat Biomass Gasifier Air
Scheme 4.7: Thermochemical biorefinery using gasification and catalytic synthesis. Adapted from /163/.
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Green diesel
Cyclone
Char pyrolyzer
Bio-oil recovery
Steam reformer
Biomass
Phase separation
Carbohydrate derived aqueous phase
Scheme 4.8: Thermochemical biorefinery using pyrolysis and catalytic synthesis. Adapted from /163/. Gasification and pyrolysis processes do not require enzymes or microorganisms as do biochemical processes, they are applicable over a wide range of feedstocks, and they are generally compatible with conventional petroleum processing technologies /167/. However, the crude producer gas and bio-oil coming from the primary gasification or pyrolysis of biomass are low purity and cannot be fed into the known catalytic processes of classical petroleum refinery without prior purification or upgrade. The biochemical technology complementing the primary thermochemical treatment of biomass (hybrid pathway) can be, therefore, a promising opportunity to valorise the raw quality thermochemical treatment intermediates. 4.3.6 Hybrid thermochemical/biochemical
Syngas fermentation and bio-oil fermentation are the two major approaches of the hybrid pathway. In the syngas fermentation process (shown in Scheme 4.9), the intermediate products (CO, CO2 and H2) are fermented into metabolic products such as alcohols, carboxylic acids and esters using autotrophic organisms. In the bio-oil fermentation process, the anhydro-sugar is first separated from other bio-oil components and is then hydrolysed to produce glucose. The glucose is subsequently fermented to yield ethanol as shown in Scheme 4.10 /168/.
CO2 Syngas Biomass Gasifier Gas cleaning Bioreactor Fuels and chemicals
Scheme 4.9: Syngas fermentation. Adapted from /168/.
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Hydrocracker
Bio-oil vapour
Cyclone
Bio-oil vapour Ethanol Detoxification
Char
Bio-oil recovery
pyrolyzer
Biomass
Phase separation
Fermenter Anhydrosugar & other carbohydrate Lignin
Scheme 4.10: Bio-oil fermentation. Adapted from /168/.
4.4
CURRENT BIOREFINERIES AND OUTLOOK/DEVELOPMENT TRENDS
The development of biorefineries has begun in some countries across Europe and the United States. It has already proven successful in the U.S. agricultural and forest products industries, where such facilities now produce food, feed, fibre, or chemicals, as well as heat and electricity to run plant operations. Multi-product corn wet mills appeared in their current form in the 1970s, prompted by the development of commercial technology for production of high fructose corn syrup (HFCS), which today has largely replaced sugar produced from cane in the US. Sweeteners including HFCS, glucose, and dextrose today account for about 37 % of the output of the US corn wet milling industry, with gluten feed and gluten meal accounting for about an additional 32 %, and the balance consisting of starch, ethanol, carbon dioxide and corn oil /160/. These processes are similar to the whole crop technology except that the DDGS in most cases is used as feed instead of conversion into other high valued products. According to a report by Zwart /162/, Archer Daniels Midland (ADM) has a prototype expanded biorefinery in Decatur, US, where a large corn wet-milling plant produces industrial enzymes, lactic and citric acids, amino acids and ethanol. Enzymes are used to convert starch to maltodextrins and syrups, and the chemical products are used in foods, detergents and plastics. The ethanol is used as a solvent or for transportation fuels. Arkenol (an energy company) is marketing a biorefinery technology based on acid hydrolysis that can produce a variety of biobased chemicals and transportation fuels. The company is developing several biorefineries throughout the world, including a facility that will produce 90 million pounds/yr of citric acid along with 4 million gallons of fuel ethanol. Agrologistiek BV in the Netherlands has plans to install several biorefinery pilot plants for small-scale bioethanol production from arable crops. The idea is to realize multiple smaller plants close to the farms. This will lower the transport costs, and create a zero emissions system. The plant is being designed to be flexible in its use of feedstock so that several feedstock can be processed. Some of the feedstocks will include wheat, beet, leafs, fibres, maize and grass. By-products of the bioethanol will serve as feed for animals, biogas for energy generation and CO2. The capacity of the plants will vary between 5 and 50 million litres /165/. In 2000 a pilot plant was built in Foxhol (Groningen) by a consortium consisting of Avebe, Plant Research International, Nedalco, ABCTA, Agrifirm, NOM and Rabo; to study the technical and
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economic feasibility of the green biorefinery concept. The aim was to make use of grass surplus in the Netherlands. The main products were grass juice concentrate, grass protein and grass fibres. Other products that could be manufactured based on these grass fibres are potting soil, construction materials and filler materials for polymer extrusion products. The grass juice concentrate can be used as feed component for pigs or to produce biofuels. Finally, the grass protein can be used as feed component for pigs and poultry /165/. A demonstration Green Biorefinery plant in Brandenburg Germany will use 24,000 tonnes per annum fresh alfalfa, lucerne and wild grass. It will use mechanical separation (pressing) and fermentation technology. The main products are press cake for fodder and fuels, proteins for industry and cosmetics and heat and electricity. The primary biorefinery is combined with a green crop drying plant. Several other projects are being developed mainly in Europe and the United States and should be commercialised in the next few years. Most modern wet corn milling plants and pulp and paper mills claim to be biorefineries (and most US ethanol plants are referred to as biorefineries) because of the variety of products at the end of the production process. The food industry also try to add some value by supplying their by-products to other sectors, e.g. to the feed industry. However, in these industries, the main emphasis is still on producing their main products, and no large efforts are made yet to produce a broad spectrum of other added-value products, like bio-chemicals or biofuels. Over the coming decade, researchers anticipate a new category of refining processes based on cellulosic biomass. There are some challenges, however, that have to be dealt with for biorefining of cellulosic biomass to become fully sustainable. Major technical challenges and barriers to the biochemical pathway include dealing with the variability of biomass feedstocks, the difficulty of lignocellulosic materials to chemical and/or biological degradation, and the need for improved effectiveness of cellulose enzymes and fermentation organisms. Important technical challenges still remain with thermochemical approaches. Pre-treatment of the biomass and physical feeding into thermal processing units are challenging. For gasification, other challenges include minimization of tar formation, syngas cleanup, and development of effective catalysts. For pyrolysis, major challenges include cleanup of the bio-oil and sufficient stabilization of it for practical delivery and use in a petroleum refinery /167/. Future biorefineries needs intensive research in different areas such as agronomy of feedstocks, greener catalytic process, genetically modified crops and encouraging government policies on promotion of biofuels and co-product valorisation. Future biorefinery operations will aim to extract high-value chemicals already present in the biomass, such as fragrances, flavoring agents, food-related products, and high-value nutraceuticals that provide health and medical benefits /169/. The whole biorefinery concept requires more extensive research in the chemistry and technological applications and processes to reduce the cost of operations.
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Survey of Future Biofuels and Bio-Based Chemicals

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International Centre for Science and High Technology United Nations Industrial Development Organization

10% 15% 20% 10% 5%

1.3 BIOMASS AS A RESOURCE

Wood processing industry by-products Black liquor Used wood

Fibre crop processing by-products

Food processing industry by-products

End use materials

Used fibre products

Used products of fruits and seeds

Tab. 1-3. Properties of biogas substrates /7/.

Rye silageb 30 35 85 95 4.0 0.57 0.71 170 220 550 680 ~ 55

Biowaste 40 75 50 70 0.5 2.7 0.2 0.8 80 120 150 600 58 65

7 11 75 86 2.6 18 1 17 0.5 10 20 35 200 700 60 70

1.3.2 Technical biomass potentials

Former Soviet Union Middle East

Woody by-products Herbeaceous by-products Manure Energy crops

36% 40% Worldw ide (2000) approx. 104 EJ/a

Asia Latin America + Caribbean North America 0 5 10 15 20 25

Technical biomass potenial (base case 2000) [EJ/a]

Fig. 1-3. Technical biomass potential worldwide /10/.

1.3.3 Biomass provision

Technology availability - term

Fig. 1-6. Biomass demand of current and future biomass applications.

requirements on biomass site

provision on biomass site

provision on demand site

biomass conversion plant

requirements on demand site

Fig. 1-7. Overall biomass supply chain.

Fig. 1-8. Optional provision chains from biomass to plant site.

Tab. 1-5. General tradeability of different biomass sources /14/.

Other biomass Bioenergy

1.4 FUTURE BIOFUELS

Biomass energy sources

Electricity from biomass

Biogas Gas treatment / upgrading

Syngas / product gas (H2/CO)

Fuel synthesis from syngas

Current biofuel generation

Future biofuel generation

Without entitlement of completeness

TECHNICAL, ENVIRONMENTAL, AND ECONOMIC PROFILES OF FUTURE BIOFUELS

Part 2: TECHNICAL, ENVIRONMENTAL, AND ECONOMIC PROFILES OF FUTURE BIOFUELS

Pure Oil Fuel Gas Hydrotreating Biogasoline

Fig. 2-1. Principle of advanced biodiesel production.

TECHNICAL, ENVIRONMENTAL, AND ECONOMIC PROFILES OF FUTURE BIOFUELS

TECHNICAL, ENVIRONMENTAL, AND ECONOMIC PROFILES OF FUTURE BIOFUELS

Lignocellulosic Feed Stock

Electricity / Steam generation solid residues (ligning etc.)

mash Ethanol conditioning Destillation / Purification distillation Concentration residues

Fig. 2-2. Principle of bioethanol production based on lignocelluloses.

TECHNICAL, ENVIRONMENTAL, AND ECONOMIC PROFILES OF FUTURE BIOFUELS

2.1.3 Fischer-Tropsch fuels

TECHNICAL, ENVIRONMENTAL, AND ECONOMIC PROFILES OF FUTURE BIOFUELS

Fig. 2-3. Principle of FT fuel production.

TECHNICAL, ENVIRONMENTAL, AND ECONOMIC PROFILES OF FUTURE BIOFUELS

TECHNICAL, ENVIRONMENTAL, AND ECONOMIC PROFILES OF FUTURE BIOFUELS

TECHNICAL, ENVIRONMENTAL, AND ECONOMIC PROFILES OF FUTURE BIOFUELS

TECHNICAL, ENVIRONMENTAL, AND ECONOMIC PROFILES OF FUTURE BIOFUELS

TECHNICAL, ENVIRONMENTAL, AND ECONOMIC PROFILES OF FUTURE BIOFUELS

Fig. 2-4. Principle of methanol production.

H = -49 kJ/mol H = -91 kJ/mol

TECHNICAL, ENVIRONMENTAL, AND ECONOMIC PROFILES OF FUTURE BIOFUELS