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Resultaten en bevindingen van project High added value valorization of lignin for optimal biorefinery of lignocellulose to energy carriers and products (LignoValue)
Dit rapport is onderdeel van de projectencatalogus energie-innovatie. Tussen 2005 en 2011 kregen ruim 1000 innovatieve onderzoeks- en praktijkprojecten subsidie. Ze delen hun resultaten en bevindingen, ter inspiratie voor nieuwe onderzoeks- en productideeën. De subsidies werden verleend door de energie-innovatieprogramma's Energie Onderzoek Subsidie (EOS) en Innovatie Agenda Energie (IAE).
Datum September 2011 Status Definitief Agrotechnology and Food Innovations BV, e.a. in opdracht van Agentschap NL
Colofon
Projectnaam High added value valorization of lignin for optimal biorefinery of lignocellulose to energy carriers and products
Programma Energie Onderzoek Subsidie Regeling Lange Termijn Projectnummer EOSLT05011 Contactpersoon Agrotechnology and Food Innovations BV Hoewel dit rapport met de grootst mogelijke zorg is samengesteld kan Agentschap NL geen enkele aansprakelijkheid aanvaarden voor eventuele fouten.
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Final report LignoValue Energie Onderzoek Subsidie: Lange Termijn
High added value valorization of lignin for optimal biorefinery of lignocellulose to energy carriers and products
(acronym: LignoValue) Project No: EOS-LT05011 Project coordinator: Richard J.A. Gosselink, St. DLO – Food & Biobased Research (WUR-
FBR, Wageningen) Project partners: Energy Research Centre of The Netherlands (ECN), Petten
Aston University, Birmingham, UK, (third party of ECN) Groningen University (RUG) Wageningen UR, Valorisation of Plant Production Chains (WU-VPPC)
Period: January 2007 – December 2010 Date of publication: September 30, 2011
Public report
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Contents Chapter 1 Scientific final report ............................................................................................................... 3
Summary .......................................................................................................................................... 3 LignoValue introduction .................................................................................................................... 5 Industrial advisory board .................................................................................................................. 5 Technical approach .......................................................................................................................... 5 Task 1 Primary biorefinery ............................................................................................................... 7 Task 2 Secondary biorefinery .......................................................................................................... 9 Task 3 Modeling and system evaluation ........................................................................................ 14 Task 4 Conceptual design and economic evaluation ..................................................................... 15 Task 5 Techno-environmental chain evaluation ............................................................................ 19 Task 6 Socio-economic evaluation ................................................................................................ 22
Chapter 2 Bijdrage aan de EOS: Lange Termijn doelstellingen............................................................ 27 4.1 De bijdrage aan een duurzame energiehuishouding ............................................................... 27 4.2 De versterking van de kennispositie van Nederland ................................................................ 31
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Chapter 1 Scientific final report
Summary Durable and cost effective Lignocellulosic biorefinery for production of biofuels, materials and chemicals requires valorization of all fractions including lignin. The aim of a biorefinery is to fractionate biomass in components for further conversion into added value products and energy carriers, while minimizing the number of conversion steps and losses and maximizing the total added value. An essential element in this approach is the optimal utilization of existing functionalities in the biomass by development of an integral biorefinery technology for high added value valorization of all biomass fractions, including LIGNIN, as is the major aim of this LIGNOVALUE project. As a consequence of its poly-aromatic structure, lignin potentially serves as a source for aromatic chemicals. The developed biorefinery concept of the LignoValue project comprises two major steps: (1) Organosolv fractionation of wheat straw and willow into (hemi)cellulose and high purity lignin. (2) Further conversion of isolated lignin via either catalytic pyrolysis or supercritical depolymerization or partial hydrodeoxygenation (HDO) into low molecular phenolic compounds, wood adhesives and fuel additives. The cellulose fraction resulting after organosolv fractionation is effectively hydrolysed by enzymes into sugars for fermentative biofuel production by fermentation. Quality assessment of the liberated lignins shows interesting characteristics for follow-up chemistry such as high purity, relatively low molar mass and polydispersity. Catalytic pyrolysis in a fluidised bed at 400-500°C was found to convert organosolv lignin in 35-55% phenolic oil, 10% identified monomeric phenolic compounds, 10-20% water, 5-20% gas and 35-55% char. Effective solutions have been developed for the continuous feeding of lignin into the pyrolysis reactor. Supercritical depolymerisation of lignin in carbon dioxide based solvents resulted in a similar spectrum of products, however, at a lower temperature (300°C) but at higher pressures. In both thermochemical processes the use of promotors or catalysts (hydrogen donors) lead to an improved yield of the target monomeric aromatic products. Also the residual char fraction shows interesting properties for use in bio-char, bio-asphalt or activated carbon applications. Catalytic semi-continuous HDO of lignin or depolymerised lignin in hydrogen atmosphere can be manipulated to yield both light oils or heavy oils as potential additives to fuels. Suitable catalysts were found to convert depolymerised lignin to phenolic oils in high yields and a high amount of alkylphenols. Best results were obtained with Ru/C. In this process no or negligible char formation is observed. Prior fractionation of lignin result in phenolic oils with different properties and composition. The lignin oils were successfully tested on lab scale as partial substitution of phenol, up to 75%, in resins for gluing wood panels (plywood). This indicates high potential for further development of lignin derived wood adhesives. The compositional analysis of HDO treated lignin oils shows that these products can be used as fuel additives. Depending on the process conditions the composition can be manipulated to gasoline compatible or diesel compatible additives. Finally, the LignoValue concept is critically reviewed in a techno-economic analysis demonstrating the potential for further commercial development and adoptation of this innovative biorefinery process in Europe. The organosolv-based biorefinery of wheat straw will produce second generation bio-ethanol, furfural and lignin. The economic evaluation shows that such as a biorefinery might be economically profitable if lignin could be sold for €500/ton. Of course, lignin applications with a higher value drastically improve the economics. The total fixed capital is estimated to be 60 M€. With a net revenue of 10.3 M€/yr, the paid back time is about 6 years. For lignin conversion by pyrolysis, the system assessment has been performed on a 300,000 ton/year lignin pyrolysis scale which needs a biorefinery scale of 1.6 million ton/y biomass input. Economic analysis show that lignin cannot be used only for energy applications in an economic viable way. Therefore lignin pyrolysis products need to be upgraded to products which represent a value between € 800 to € 1000/ton. Potential applications are phenol resins, carbon fibers, activated carbon, and bio-bitumen. Total capital investment for the secondary biorefinery step, lignin pyrolysis plant, was estimated to be about 190 M€ and ROI's ranging from 20 to 120 % for the viable cases. Finally, the economic profitability of the biorefinery studied is highly dependent on the feedstock prices.
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The environmental performance of different options for lignin biorefineries have been evaluated and compared with electricity production from lignin by applying a screening Life Cycle Assessment (=LCA). The results of this assessment showed that using lignin to replace fossil fuel based products has advantages in most of the environmental categories considered. Depending on feedstock, wheat straw, the categories acidification, eutrophication and terrestrial ecotoxicity showed a negative impact. Therefore it is recommended to evaluate more lignocellulosic feedstocks (eg. woody biomass and agro-residues). Using lignin for the production of biofuels and biochemicals is environmentally favorable over using lignin for electricity. Comparison of the different biorefinery routes shows that routes producing bulk products perform better than routes where high-value specialty chemicals are extracted from the lignin pyrolysis oil. Comparison of using the biochar as carbon black and as substitute of a fertilizer shows that the former option is preferred from an environmental point-of-view. This biorefinery concept was evaluated by a socio-economic analysis to identify a potential “set-up” for the chain from raw material to products(s) and to identify chances and bottlenecks in the bio-refinery process. This analysis show that based on its energy content 6 mln tonnes of lignin are needed to replace 100PJ of fossil energy. However if lignin were used to replace phenol or other aromatic chemical or material, then each tonne of lignin could theoretically save ca. 60 GJ of fossil energy as opposed to 15-20 GJ if only used for its energy content. Enough quantities of lignin could be generating in Europe from different sources and industries like residues from biofuel production, paper & pulp production and forestry residues. This biomass could be processed decentralised close to the farming areas as for wheat straw. Other biomass sources could be brought in via large ports (such as Rotterdam, Antwerp and Hamburg) with integrated chemical complexes where processes such as the organosolv fractionation and pyrolysis could be established. Ports also offer good river access to important chemical producing regions further inland reducing the need for road freight. As The Netherlands and Germany are major producers and users of fossil based phenol establishment of new (lignin to) phenol production processes seems favourable in these countries. For The Netherlands and EU it is important to maintain interest in alternative phenol production technologies. With rising oil (and phenol) prices this will make new technologies even more attractive.
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LignoValue introduction Lignocellulosic biomass offers numerous opportunities as feedstock for energy, chemicals and materials due to its chemical composition and relatively low costs. The cellulose- and hemicellulose fractions (60-70 wt%) are a source of sugars for fermentative production of biofuels and for the industrial synthesis of e.g. surfactants and polymers. The third major component is lignin (20-30 wt%), a co-polymer consisting of phenylpropane units, that is rich in functionalized aromatic groups and is particularly suited as a source of chemicals and products. Thus far however these possibilities are hardly utilized. The aim of the biorefinery concept, studied in LignoValue, is to fractionate biomass in its main components for further conversion into added value products and energy carriers, while minimizing the number of conversion steps and losses and maximizing the total added value. An essential element in this approach is the optimal utilization of existing functionalities in the biomass by development of integral biorefinery technology for high added value valorization of all biomass fractions including lignin, as is the aim of this project. The objective of the project is the development of an innovative biorefinery concept for optimal valorization of all biomass fractions. The upgrading of the lignin stream (LignoValue) is the key in this approach for optimal technical and economic biorefinery of lignocellulose.
Project team WUR-FBR: Richard Gosselink, Jan van Dam, Wouter Teunissen, Jacinta van der Putten ao. ECN: Paul de Wild, Wouter Huijgen, Hans Reith, Herman den Uil, Claudia Daza Montano ao. Aston University: Daniel Nowakowski, Tony Bridgwater WU-VPPC: Elinor Scott, Johan Sanders RUG: Arjan Kloekhorst, Erik Heeres, Ton Broekhuis
Industrial advisory board In this project an industrial advisory board was formed by Bayer Material Science AG, Germany, prominent producer and developer of polymers, high-performance plastics, coatings and adhesives, BASF Catalysis, The Netherlands, producer of catalysts, and Avantium Chemicals, The Netherlands, high throughput screening system developer. These companies attended the progress meetings during the course of the project and took part in all discussions.
Technical approach The technical of approach comprises seven tasks: (1) Primary biorefinery, (2) Secondary biorefinery, (3) Modelling and system evaluation integral process configuration, (4) Conceptual design and economic evaluation, (5) Life cycle analysis, (6) Socio-economic evaluation, and (7) Knowledge mobilisation and dissemination. The technological research in Tasks 1 and 2 is depicted in the scheme below.
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On a task to task basis the overall project results are described hereafter.
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Task 1 Primary biorefinery Partners involved: ECN + WUR-FBR Introduction For optimal biorefinery of lignocellulosic biomass a sufficient fractionation technology needs to be developed to get the main biomass components (cellulose, hemicelluse AND lignin) in a high quality. So far, most pulping and biorefinery technologies are meant to produce high quality (hemi)cellulose and assume the lignin stream as a side stream for energy production. In LIGNOVALUE, the extracted lignin will be used for development of high value added applications. Goals Task 1 focuses on the investigation of the optimal process conditions for lignocellulose pretreatment and fractionation via modified organosolv processing. Research will especially be aimed at how to improve the lignin extraction efficiency and the quality of the different biomass fractions for further conversion. In this task two lignocellulosic model feedstocks are selected for pretreatment and fractionation. The fractions produced are characterized and passed through as feedstock for the secondary biorefinery research in Task 2. Methodology Via desk studies and in-house expertise (database Phyllis, database DLO), and detailed discussion with the project partners, a selection was made of two model lignocellulosic feedstocks based on composition (lignin and (hemi)cellulose content); type of lignin monomers) and the (potential) availability in respectively The Netherlands and the EU-25. To ensure the availability of sufficient experimental material for the secondary biorefinery task 2 and 3, organosolv(ethanol-water) Alcell lignin was used as a model lignin. Organosolv fractionation development was performed on labscale in 0.5L and 2L reactors for both feedstocks. Optimal conditions were applied to scale up the fractionation of wheat straw at 20L scale. The enzymatic digestibility of fresh and pretreated lignocellulose was measured with enzyme Accellerase 1500 (Genencor, Rochester, NY) at 50 °C at 35 FPU/gr dry substrate and incubation for 72 h. The enzymatic glucose yield was calculated on the basis of the mean glucose concentration in the hydrolysate after 72 h and the glucan content of the substrate. Lignin was precipitated from the organosolv liquor and the washing solution upon dilution with refrigerated water. After sedimentation of the particles by centrifugation, the supernatant was decanted and the lignin was dried and weighted. Main lignin characteristics were determined. Results and Discussion Selection of feedstocks and characteristics During the kick-off meeting two selected feedstocks that will be used throughout the project were identified and subsequently purchased: 1 m3 willow wood chips and 100 kg wheat straw (Tatarus = winter wheat). For starting the work in tasks 2 and 3 20 kg Alcell lignin (Organosolv lignin from mixed hardwoods, Repap. Technologies) was purchased and distributed to the project partners. Both feedstocks contain a substantial amount of lignin of respectively 20 wt% and 25 wt% for wheat straw and willow. On basis of the biochemical composition, these lignocelluloses are good candidates for this biorefinery process development. Alcell lignin is very pure (96-98%) and is a good model lignin for development of the thermal depolymerisation processes. Other lignins were used for comparative reasons. Organosolv pretreatment and fractionation of lignocellulose Willow and wheat straw can be effectively separated by organosolv fractionation in ethanol-water mixtures into its major compounds. Temperature and catalysts have a clear effect on this fractionation.
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The temperature should not exceed 200°C as cellulose hydrolysis starts. In Figure 1, an example of results obtained is given.
Figure 1 Effect of temperature on the organosolv fractionation of willow, EtOH:H2O 60:40 wt%, 60 min, no catalyst.
For willow and wheat straw maximum enzymatic cellulose hydrolysis was obtained with 0.02M HCl at the reaction conditions studied: liquid:solid : 9.6 kg/kg dry biomass, ethanol:water : 55-45% w/w, pretreatment severity: log R = 4.65. The obtained enzymatic glucose yield based on the glucan content of the feedstock was 86 and 99% for willow wood and wheat straw, respectively (Figure 2). These conditions lead to 73 and 83% hemicellulose hydrolysis, 51 and 68% delignification for these feedstocks. For acidic catalysts it was found that their effect was directly correlated to the pH, largely independent of the type of acid used.
Figure 2 Effect of catalyst type on enzymatic digestibility of organosolv treated willow wood
and wheat straw From the organosolv black liquors lignin could be recovered with up to 70% yield from the original lignin in biomass. Organosolv lignins obtained were relatively pure (see Table 1). Main impurity is oligomeric xylan. These lignins are sulphur- and ash-free and have a relatively low Mw of 2000-3500 and narrow distribution (Table 1).
Table 1 Characteristics straw and hardwood organosolv lignin
Straw Hardwood
Lignin (%) 99 97
Carbohydrates (%) 0.8 0.3
Ash (%) 0 0
Mw (D) 2650 3400
Polydispersity 4.5 4.6
S-OH (mmol/g) 0.6 1.3
G-OH (mmol/g) 1.0 0.8
H-OH (mmol/g) 0.5 0.2
COOH (mmol/g) 0.6 0.3
0
20
40
60
80
100
160 190 200
T [°C]
Fra
cti
on
ati
on
[%
]
Pulp yield
Glucan hydrolysis
Xylan hydrolysis
Delignification
0
20
40
60
80
100
Fresh No cat H2SO4 HCl MgCl2
Glu
cose
yie
ld (
%)
Willow
Straw
9
Conclusion and recommendations Organosolv fractionation of willow and wheat straw in ethanol-water is effective. The cellulose in pretreated biomass can almost completely be hydrolysed to glucose. High purity organosolv lignin can be recovered up to 70%. Upscaling from 2L to 20L was successfully performed. For future work a novel continuous operating organosolv fractionation process is recommended. It is anticipated that this will take approximately 1 – 2 years. Involved costs are estimated at 1.5 M€.
Task 2 Secondary biorefinery Task 2.1 Lignin pyrolysis (ECN, Aston) Introduction Lignin is a complex and recalcitrant biopolymer towards thermal depolymerisation, e.g. via pyrolysis (thermal degradation of organic matter in absence of air). The literature on the pyrolysis of lignin for the production of chemicals typically reports yields of mono-phenolic compounds that rarely exceed 5-6 %, based on lignin. The main practised option to date for lignin, is its use as a low-cost solid fuel for generating heat. This task started with a phase of knowledge transfer/exchange between Aston University and ECN on the state-of-the-art of fast pyrolysis, and specifically the catalytic pyrolysis of lignin. The exchange addressed experimental installations, infrastructure, procedures and analytical methods and included harmonization of protocols when required Goals The objective of this task was to investigate the process variables including the optimal catalyst to attain a high degree of lignin depolymerization combined with a high yield of substituted mono phenols through (catalytic) fluidized bed pyrolysis. Methodology Pyrolysis on lignin was conducted at 400 - 500°C in an 1 kg/h bubbling fluidized bed reactor with a cooled screw-feeder and integrated product recovery. Several organosolv lignins and soda lignin were used. To support the process development thermal properties of lignin were determined by DSC and TGA and analytical Py-GC/MS was carried out at 400 - 800°C. Pyrolysis products, lignin oil composition, gases and char were extensively characterized. Results and Discussion Fast pyrolysis of organosolv lignin in a bubbling fluid bed reactor was successfully conducted by feeding the lignin in a form of a paste using an alcohol or by co-feeding the lignin with a proprietary additive. These inventions were patented by respectively Aston and ECN.. Py-GC/MS showed that a maximum yield of phenolic compounds was obtained at 600°C of 17.2% for Alcell lignin and 15.5% for soda non-wood lignin (Granit). Most of the phenolic compounds had an individual yield of less than 1%; however, for Alcell lignin, 5-hydroxyvanillin had a yield of 4.29 wt %, and for soda lignin, 2-methoxy-4-vinylphenol had a yield of 4.15 wt % on dry ash-free lignin. At lower temperatures more monomeric phenolics were produced. Molar analyses support these results as a higher Mw was obtained at higher temperature maybe due to secondary condensation reactions. Bubbling fluidized bed pyrolysis at 500°C resulted in good mass balances for 3 lignins studied with the highest oil yield of 55% for ECN wheat straw lignin resulting from task 1 (Figure 3). Pyrolysis oils contain a substantial amount of oligomeric lignin fragments. Granit soda lignin from grass/straw pyrolysis resulted in the highest monomers yield. Main aromatic compounds obtained from wheat straw lignin (ECN) and non-wood lignin (Granit) are guaiacols, for hardwood lignin (Alcell) mainly syringols. The pyrolysis results reflect the compositional differences between the lignins.
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Figure 3 Products from lignin pyrolysis, 500°C, fluidised bed Conclusion and recommendations Catalytic pyrolysis of organosolv lignin lead to 55% phenolic oil, 40 char, 15-24% water and 15-20% gases. Closed mass balances were obtained. The phenolic oil consists of 8-11% monomers and 14-21% oligomers. Catalysts improve the overall conversion of lignin to monomeric phenolics. Task 2.2 Lignin depolymerisation in supercritical media (WUR-FBR, WU-VPPC) Introduction Lignin depolymerisation is studied in the presence of a supercritical solvent based on carbon dioxide and a hydrogen donor. Base solvent is supercritical CO2 (> 31 ˚C and 74 bar) in combination with co-solvents like ethanol and acetone/water. This process is performed at a lower temperature (300°C) than typical pyrolysis conditions, but need a high pressure. Important advantages of using CO2 are that it is non-toxic, abundantly available, already used in industrial processes and after expansion of the pressure will leave no residue in the product. Goals Development of a novel effective and environmentally process for the production of aromatic chemicals out of lignin. Methodology Lignin was converted in a mixture of carbon dioxide/acetone/water under supercritical conditions (SCC) in a 100 ml PARR reactor at 300-370°C, 100 bar. Products were captured after pressure release in acetone for further analyses by GC-MS. Phenolic oil and char were extensively characterized by using a variety of techniques such as SEC, FT-IR, elemental composition, NMR. Results and Discussion
Organosolv hardwood (Alcell) and organosolv wheat straw lignin (ECN, 20L scale) were converted to
a total yield of identified aromatic compounds of 10-12% based on dry lignin together with 40-50%
char, 10% gases and 30-45% phenolic oil with oligomers and monomers.
ECN GRANIT ALCELL
Gas 15.1 15.2 20.7
Oil 54.7 47.6 38.9
Char 35.6 39.0 43.0
Balance 105.3 101.8 102.6
Water 23.9 17.1 14.5
Light ends 1.8 1.4 1.9
Guaiacols
OH
O
2.0 3.0 1.5
Syringols
OH
O O
1.1 1.6 2.6
Alkylphenols
OH
0.6 1.1 0.3
Total catechols
OH
HO
0.6 1.2 0.5
Monomers 7.8 11.2 8.5
Oligomers 21.4 18.0 14.0
Phenolics 29.2 29.2 22.5
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In scCO2/acetone/water hardwood lignin (Alcell) is not only depolymerised into monomeric compounds
but also extensively in oligomeric fragments of about 1000-1400 Dalton relative to 3400 of the starting
lignin (Figure 4).
The yields of the individual monomeric compounds are different for straw and hardwood lignins
(Figure 5). Phenolics are separated from residual char by pressure expansion in this supercritical
process.
The overall mass balance of hardwood lignin (Alcell) in sc scCO2/acetone/water at 300°C and 100 bar pressure is almost complete (94+%). Formic acid act as a hydrogen donor and increases the yield of aromatics. During this process a strong competition occurs between depolymerisation of lignin and recondensation of fragments. This leads to a residual lignin char fraction consisting of a substantially reduced oxygen content, improved thermal stability and a high content of carbon.
Figure 4 Effect of SSC treatment on molar mass of phenolic oil derived from lignin
Conclusion and recommendations Supercritical depolymerisation of lignin lead to a yield of 10% aromatic monomers and a phenolic oil yield of 30-45%. As a substantial amount of char is formed further research is needed to prevent recondensation reactions. The phenolic oil mixture is an interesting product for use as a wood adhesive (resin) for wood panels (see task 3).
Figure 5 Identified phenolics produced during sc depolymerisation of lignin
in scCO2/acetone/water at 300°C, 100 bar
-0.2
0.0
0.2
0.4
0.6
0.8
1.0
1.2
10 15 20 25 30 35
Retention time (min)
UV
28
0 n
m r
esp
on
se
Untreated lignin
Phenolic oil uncat.300°C (1) Phenolic oil uncat.300°C (2) Phenol
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Task 2.3 Hydrodeoxygenation (HDO) of (depolymerised) lignin (RUG)
Introduction
For conversion of lignin into alkyl substituted phenols with one or more hydroxyl groups a part of the
oxygen content needs to be removed. This means that oxygen-lowering conversion technology has to
be applied. A promising option is hydro-deoxygenation (HDO) with which the oxygen content of a
feedstock is decreased via a treatment with molecular hydrogen and a solid catalyst under the
formation of water. The catalysts that are to be used have to be selective for the HDO process.
Hydrogenation of the aromatic rings of the depolymerised lignins and the formation of saturated
cyclohexane derivatives have to be suppressed. Also from the viewpoint of minimalisation of the use
of hydrogen for the HDO process, it is necessary to suppress these reactions as much as possible.
Certain Ru-based catalysts are capable to convert pyrolysis-oil into mixtures of substituted phenols in
reasonable yields. These catalysts will be used to study the conversion of (depolymerized) lignin into
mixtures of substituted phenols.
Goals
The objective of this task is a technological assessment of the catalytic hydrodeoxygenation of lignin
and depolymerisation of lignin to low molecular weight phenolics. Three subtasks have been defined:
1. Model studies using lignin model compounds to gain insights in catalytic reaction
pathways and to aid catalyst selection
2. Exploratory catalyst and solvent screening in batch set-ups
3. Process optimization studies using the preferred catalyst and lignin feed
Methodology
Lignin model compounds and organosolv lignin were converted by hydrodeoxygenation (HDO) in a
100 ml reactor at 350 – 400°C, 100 bar hydrogen pressure in the presence of a heterogeneous
catalyst, e.g. Ru/C, with the formation of water and low molecular weight phenolics. Products were
characterized by a variety of techniques including 2D-GC, GC-MS, Py-GC/MS, NMR, SEC.
Results and Discussion
The lignin model compound reactions show that Ru/C is able to deoxygenate and cleave the bonds in
lignin. Also ringhydrogenation can occur when the conditions are too harsh. This information forms the
basis for the lignin HDO processing.
Figure 6 showed that hardwood lignin (Alcell) was converted to a lignin HDO oil yield of about 70 %
depending on the choice of catalyst. The highest alkylphenolic amount was achieved by using Ru/C.
Under these conditions negligible char formation occurs.
Lower molecular weight fractions of lignin lead to oil products with a significantly lower O/C and higher
H/C ratio and higher amounts of hydrocarbons (Figure 7).
Figure 6 Effect of catalyst type on HDO of lignin to oil yield and composition
Ru/C Ru/Al2O
3Ru/TiO
2Pd/C Pd/Al
2O
3Cu/ZrO
2
0
2
4
6
8
10
12
14
60
70
Wt%
on
ligni
n
Catalyst
Oil
Alkylphenolics
Guaiacolics
Catechols
Aromatics
Cyclohexans
Cyclohexanols
Alkanes
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Figure 7 Van Krevelen plot of lignin, fractionated lignin and resulting HDO oils
Conclusion and recommendations
Catalytic hydrodeoxygenation of lignin resulted in high phenolic oil yields (70%) with substantial
amounts of alkylphenolics and hardly any char formation. HDO conversion of fractionated lignins lead
to oils with distinguished composition.
Task 2.4 Application of lignin derived phenols in performance products
Introduction
As lignin acts in nature as a glue, it seems the obvious candidate to use as a resin for gluing wood
panels or fibres together. Compared to phenol, lignin needs to be depolymerized and functionalized to
become a reactive component in a PF type of resin.
Goals
Goal of this research is an experimental study on the application of the substituted phenols derived
from lignin as substitute for phenol in phenol-formaldehyde wood adhesives.
Methodology
The lignin oil was obtained after catalytic hydrotreatment (HDO). Wood adhesive formulations with 50
wt% and 75 wt% lignin oil were compared with a standard resin made with phenol-formaldehyde resin
only. Wood veneers were glued with 150 g/m2 resin with a contact interface of 25x25 mm. The
specimens were hot pressed at 200°C under 3 MPa pressure for 5 min and tested according to
European standard EN-314.
Results and Discussion
Figure 8 showed that up to 75 wt% replacement of phenol in a PF-resin can be achieved with HDO
lignin oil to get sufficient glue strength of a plywood specimen. This result indicates the potential for
lignin oil as glue component in wood panels.
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Figure 8 Strength of wood adhesive partially substituted by lignin oil
Conclusion and recommendations
50wt% and 75 wt% phenol replacement by lignin oil in a phenol-formaldehyde type of wood adhesive
was successful. Phenol substitution levels as high as 75% while maintaining the norm are to the best
of our knowledge unprecedented. Future work will be targeted towards the complete replacement of
phenol in the formulations with lignin oil and further evaluation of basic properties.
The depolymerized and HDO treated lignin into low molecular weight phenols have potential as fuel
additive. Depending on the process conditions the composition of the resulting lignin oil seems to be
easily tailored to form a diesel or gasoline additive.
Task 2.5 Separation technology (FBR, ECN)
The activities of this task are integrated in the studied processes described in previous tasks for
biomass fractionation (task 1), products recovery in pyrolysis, supercritical media and HDO (task 2.1-
2.3). In all cases separation is achieved between gases, phenolic oil and char. In the case of HDO
only limited amounts of char are formed and separation was easily accomplished.
Task 2.7 Characterisation and conversion of residues (FBR, ECN)
Lignin chars were characterized for its composition, thermal stability and O/C ratio. In the lignin chars
the oxygen content can be substantially reduced from 27% to 12%. Potential uses of lignin residue
(char) are as bio-char, bio-bitumen, carbon fibres and active carbon. As char is a major product from
the pyrolysis or supercritical depolymerisation of lignin value added applications are needed as
discussed in detail in Task 4.
Task 3 Modeling and system evaluation
Partners involved: ECN + all.
Results of Task 3 related to the modeling and system evaluation of the organosolv fractionation are
used to create a conceptual design and economic evaluation as described in Task 4.
The lignin pyrolysis process was modeled and evaluated and detailed lab-scale results were described
in a patent called "Pyrolysis of lignin” submitted at 17 June 2010 by ECN. Further details can be found
in this patent.
Standard 50wt% 75wt%0,0
0,5
1,0
1,5
2,0
2,5
3,0
3,5
ShearS
trength
(MP
a)
15
Task 4 Conceptual design and economic evaluation
Partners involved: ECN + all.
Organosolv fractionation (primary biorefinery step)
Process description
Figure 9 shows the process flow sheet of the organosolv-based biorefinery modeled with ASPEN Plus. This work has been conducted as a joint effort with the EU-FP6 Integrated project BIOSYNERGY. The biorefinery converts wheat straw into bioethanol, furfural and lignin.
Organosolv
Filter
Cellulose
Primary recycle
Make up
(ethanol, water)
Ethanol / water
Cellulose
Cellulose
Recycle
Furfural /
Ethanol
Distillation
Recycle
Ethanol / Water Recycle
Filter
Wet
Lignin
C5 sugars
Furfural (aq)
Make up
(water)
Straw
Lignin
precipitation
Air DryerLignin
Air
Hot
Air
Ethanol
Waste water
CO2
Waste water
Furfural
Furfural
purification
Hydrolysis,
fermentation,
ethanol
distillation and
dehydration
Figure 9 Process flow sheet of the biorefinery
The process was divided into five sections.
The organosolv section contains the reactor for biomass delignification and hemicellulose hydrolysis.
The primary recycle returns a part of the organosolv liquor back to the organosolv reactor.
The following conversions were assumed for the organosolv reactor:
Delignification: 80% wt
Xylan hydrolysis: 80% wt
Cellulose hydrolysis: 5% wt
Other hemicellulose components hydrolysis: 50% wt
Xylose to furfural: 37.5% of the xylose present after hydrolysis
The organosolv reactor was assumed to be operated at 200 °C using aqueous ethanol (60 wt%) as
solvent.
16
In the cellulose section, the cellulose coming from the filter in the organosolv section is separated from
all other valuable liquid and soluble components with a washer and a stripper. The lignin stream is
purified by first recovering the ethanol in the stripper, where the lignin also precipitates. The majority of
the liquid is then removed from the solid lignin in a filter.
The remaining moisture is removed in an air dryer. A dedicated series of separations purifies the
furfural. The cellulose is hydrolyzed and the resulting glucose is fermented to ethanol together with the
C5 sugars.
Mass and energy balances
The mass flows of the biorefinery are shown in Table 2.
Table 2 Mass flows biorefinery
kton/yr
In
Straw (10% moisture) 1561
Ethanol 0.58
Water 337
Toluene 0.026
Out
Ethanol (95%) 33.8
Furfural 9.19
Lignin (20% moisture) 28.9
Waste water 362
CO2 29.8
The unit operations are designed such that heat integration reduces the total heating and cooling
requirements by more than 50%. Resulting heat duties are given in Table 3.
1 Arbitrary scale chosen. Optimum scale including logistics has not been determined.
17
Table 3 Heat requirements
Heat requirements Total process
MJ/kg straw (GJ/yr)
Heating 3.300 513,000
Cooling 2.879 448,000
In comparison, the energy value of the straw is 2,410,000 GJ/yr, based on the LHV of straw and 10%
moisture.
Equipment cost estimate
The purchase costs of each unit operation was determined.
The physical plant costs are estimated to be 43 M€. The total fixed capital is estimated to be 60 M€.
To realise such an organosolv plant, research and technology development is needed to scale up the
batch process that was studied in Lignovalue to a pilot scale continuous process. In addition, to
thermochemically valorise the organosolv lignin it is needed to scale-up the pyrolysis technology to
pilot scale as well, especially to be able to produce lignin pyrolysis oil samples that can be researched
further for downstream processing (DSP) to establish the (im)possibilities of product purification and
separation. Additionally, representative lignin and product samples can be produced which can be
tested and evaluated by the interested industrial parties.
Economic evaluation
The economic evaluation is based on 8000 hrs of operation per year. The raw materials, excluding
utilities, are estimated to be 13 M€/yr. The main factor of the raw materials is the straw (a total of 9.3
M€ assuming a price of 60 €/ton dw).
The utilities are estimated to cost 4.7 M€/yr. Steam for heating is the main cost factor at 4.0 M€/yr.
Based on the total fixed capital, the raw material costs and the utilities, the operating costs are
estimated at 34.0 M€/yr.
The income of the biorefinery comes from its three products: ethanol, lignin and furfural: 24.1 M€/yr
(based on a value of 712.5 €/ton calculated from 750 €/ton for fuel-grade ethanol), 14.5 M€/yr (500
€/ton) and 5.7 M€/yr (625 €/ton), respectively. The total income is 44.3 M€/yr. The ethanol production
accounts for a little more than half the income.
Lignin accounts for about one third, and furfural for a little more than one eighth. The total fixed capital
is estimated to be 60 M€, and the total operating cost are 34.0 M€/yr. The income is 44.3 M€/yr. The
net revenue is 10.3 M€/yr, which means that the investment costs of 60 M€ can be paid back in 5.8
years.
The organosolv reactor is the largest factor in the total fixed capital costs and accounts for nearly a
third of the total investment. It is noted that the costs of the reactor are very uncertain. The lignin dryer
and the hydrolysis and fermentation section are also relatively expensive. Finally, the economic
profitability of the biorefinery studied is highly dependent on the wheat straw price.
18
Conclusion
This economic evaluation of an organosolv-based wheat straw biorefinery shows that such as a
biorefinery might be economically profitable if lignin could be sold for €500/ton. Of course, lignin
applications with a higher value drastically improve the economics.
System assessment lignin pyrolysis (secondary biorefinery step) It was decided to perform only the system assessment for lignin pyrolysis. This pyrolysis technology is the most advanced and already in an upscaled phase (bench/pilot scale) compared to supercritical processing and HDO processing. Pyrolysis data is therefore more realistic to be used for a system assessment and economic analysis. The system assessment has been performed on a 300,000 ton/year lignin pyrolysis scale using a biorefinery scale of 1.6 million ton/y biomass input. Detailed analysis has been described in a confidential report written by ECN and was disclosed to the project partners. We have estimated the capital and operational expenses for a 300,000 ton/year lignin biorefinery using pyrolysis of lignin for conversion into a gas, pyrolytic lignin oil and a char fraction. The pyrolytic lignin oil of this biorefinery comprises of a monomeric and oligomeric phenolics fraction. We have evaluated three different cases for upgrading the oil and char fraction to marketable outlets, and one case which simply uses the three fractions as energy carriers. However, this energy carrier case is not economically feasible at any lignin feedstock price. In the other three cases, we estimated that the pyrolytic oil and char fraction need to be upgraded to products which represent a value between € 800 to € 1000/ton of the oil and char respectively. We have identified carbon black, carbon fibers and activated carbons as potential high value high volume marketable outlets for the char fraction which meet this price requirement. We have identified bitumen additive and carbon fibers as marketable outlet for the pyrolytic lignin oil. The monomeric phenol fraction could be marketed as phenolic resins at or above this price range. The oligomeric phenol fraction was evaluated as bitumen additive and appears to be able to command this market price. Finally, the monomeric phenolic could be separated to some or all of the individual very high value compounds and individually marketed. The most complex case isolates some or all of the monomeric phenols from the pyrolytic oil, and evaluates several char upgrading cases. This is the most profitable case, but we expect that the market for the individual phenols is likely to be difficult to penetrate and can at most adsorb two biorefineries. ROI's range from 20 to 300 % for the viable cases, with a total capital investment of around 200 M€. The next option is to separate the pyrolytic lignin oil monomeric and oligomeric phenols and upgrade the char to the three carbon forms. We estimate the total capital investment to be around 190 M€ and ROI's ranging from 20 to 120 % for the viable cases. In the last upgrading case, the pyrolytic lignin oil is upgraded to carbon fiber and the char fraction is upgraded to the three forms of carbon. Total capital investment is estimated to be around 190 M€ with ROI's ranging from 30 to 100 % for the viable cases. The profitability is strongly dependent on yield and raw material price. For a lignin price of € 500/ton, as is the case for a organosolv based biorefinery, the raw materials represent 75 % of the total production cost.
19
We therefore recommend to:
• Initiate or expand application, separation and conversion research for the product outlets identified to be profitable and marketable
• Carbon black, carbon fiber and activated carbon for char • Bitumen additive and carbon fiber for the whole pyrolytic lignin oil fraction • Phenolic resin replacement for the whole monomeric phenol fraction • Bitumen additive and carbon fiber for the whole oligomeric phenol fraction • Validate our market model by identifying and contacting potential producers and users of the
products. Preliminary contacts with several industrial parties have shown a keen interest from the (chemical) industry. Especially, the use of the primary products lignin, lignin pyrolysis oil and biochar were deemed to be interesting to evaluate the potential for these products. This effort will be continued.
• Evaluate to use the sale of monomeric phenols to finance the development of the first of its kind of this technology. Although it seems difficult and costly to separate the monomeric phenols as individual components, it seems that the mixture has a significant value in itself for the chemical industry.
• To expand the development of this technology to include lower cost existing large sources of lignin to expand the market for this technology as well as reducing the risk of implementing this technology by reducing the number of unknown processes.
• To focus the pyrolysis research on maximizing the yield of the fractions to convertible products.
Task 5 Techno-environmental chain evaluation
Partners involved: ECN + all.
Introduction In the Lignovalue project biorefinery processes have been developed to produce a high purity lignin from lignocellulosic biomass and to convert this lignin into biofuels and biochemicals that replace fossil fuel based counterparts. The environmental benefits of lignin biorefineries have not been quantified up till now and been compared with the use of lignin for electricity production. Furthermore, it is not known which route for the production of biofuels and biochemicals from lignin has the highest environmental impact. Based on the results of the modeling and system evaluation (task 3) and conceptual design and economic evaluation (task 4), the environmental performance of different options for lignin biorefineries have been evaluated and compared with electricity production from lignin. Goals The goals of this task are: - To determine the environmental benefits of using lignin for the production of biofuels and
biochemicals.
- To determine whether from an environmental point-of-view biofuels and biochemicals production
from lignin is preferred over electricity production from lignin.
- To determine which lignin biorefinery concept has the highest environmental benefits.
Methodology The environmental performance of the different options considered has been determined by a screening Life Cycle Assessment (=LCA). The LCA was performed using the software package SimaPro (version 7.2.4) developed by Pré Consultants. The method used for the assessment is the CML 2 baseline 2000 V2.05 developed by the Centre of Environmental Science from Leiden University. The method evaluates the impact in 10 different environmental categories. Data used for the inventory analysis are all based on the Ecoinvent database that’s part of the SimaPro software. The functional unit for the analysis is 1 kg of lignin. The LCA is based on data generated in the system assessment of lignin pyrolysis (see task 3). For the products of lignin pyrolysis the fossil based counterparts have been selected where possible. Where fossil based counterparts were not available, similar products have been selected. The cases analyzed, yields of products and fossil counterparts are given in table 5.
20
Table 5 Products, product yields and fossil counterparts for the different cases analyzed.
Case Material Unit
(kg/kg lignin) Fossil-based counterpart
Case 1a Gases 0.125 50% natural gas Oligomeric phenols 0.220 Bitumen additive
Separated monomers 0.110 Pthalic anhydride2
Char as carbon black 0.275 Carbon black
Case 1b Gases 0.125 50% natural gas Oligomeric phenols 0.220 Bitumen additive/asphalt
Separated monomers 0.110 Pthalic anhydride
Char as soil amendment 0.375 Fertilizer
Case 2 Gases 0.125 50% natural gas
Monomeric phenols mixture 0.110 Phenol
Oligomeric phenols mixture 0.220 Bitumen additive
Char as carbon black 0.275 Carbon black
Case 3 Gases 0.125 50% natural gas
Pyrolytic Lignin oil 0.250 Bitumen additive
Carbon black 0.275 Carbon black
Case 4 Gases 0.125 50% natural gas
Pyrolytic Lignin oil 0.500 Crude oil
Char as energy carrier 0.375 Coal
MJ/kg lignin
Electricity Electricity 9.45 Electricity by Natural Gas
First for each case the environmental impacts have been determined when the product spectrum is produced from fossil sources, giving the gross environmental impact of substitution of the fossil based products. Subsequently the environmental impact of lignin production from wheat straw was determined. From the gross environmental impact of substitution of fossil based products and the environmental impact of lignin production from wheat straw the net environmental impact of lignin biorefineries was determined and compared with the net environmental impact of using lignin for bioelectricity production. Results and discussion The relative environmental impact of the different lignin biorefinery cases and electricity production from lignin are given in figure 10. In figure 10 the change in emissions compared to fossil based routes is given. A positive number means that emissions are higher than for the fossil route and a negative score means that emissions are lower than for the fossil based route. Furthermore, the emissions are scaled to the largest absolute value. The results in figure 10 show that in most of the impact categories lignin biorefineries result in emission reduction. Only for the categories acidification, eutrophication and terrestrial ecotoxicity the emissions are significantly higher than the fossil fuel based route. These negative impacts are due to the feedstock being used: wheat straw. The emissions related to wheat straw production are mainly due to the production of seeds, application of fertilizers, polyethylene synthesis (for baling), production and transport of diesel fuel, production of agricultural machinery, agricultural services (tillage, ploughing, harvesting, baling, loading bales).
2 We have used pthalic anhydride to replace the individual monomeric phenols due to their similar
molecular structure.
21
Figure 10 Relative environmental impact of lignin biorefineries and electricity production from lignin. With only a few exceptions, the environmental scores of the biorefinery routes are better than for electricity production from lignin (Figure 10). This means that environmentally it is better to use the lignin for the production of biofuels and biochemicals. The results of intercomparison of the biorefinery routes strongly depend on the weight that is given to different environmental categories, or in other words on which environmental category is considered to be the most important one. When all categories are given the same weight, the cases 2, 3 and 4 give the best scores. In case 1a and 1b high-value specialty chemicals, as modeled by using phatalic anhydride, are recovered from the lignin pyrolysis oil. From an environmental point of view the impact of these cases is lower than for the bulk products in case 2, 3 and 4. Comparing case 1a, using the char fraction as carbon black, with case 1b, using the char as fertilizer, shows that case 1a scores better in almost all environmental categories. The implies that using that using the lignin char in materials has environmentally more value than using the lignin char as fertilizer. Conclusions and recommendations - Using lignin to replace fossil fuel based products has advantages in most of the environmental
categories considered. Only in the categories acidification, eutrophication and terrestrial
ecotoxicity the fossil fuel based products perform better. The negative impacts in the 3 categories
mentioned are due to the feedstock used, wheat straw. Improvements in the agriculture related
activities and the used of bio-based fuels and materials in the feedstock cultivation and production
would improve the environmental impact of lignin use for the biorefineries.
- It is recommend to evaluate the use of other feedstocks (eg. woody biomass) and alternative agro-
residues as well. Alternative feedstock with high content of lignin which don’t require the
production of seeds, use of plastics for baling, and require low (or none) fertilizers application (eg.
bamboo), should be also explored.
- Using lignin for the production of biofuels and biochemicals is environmentally favorable over
using lignin for electricity.
- Comparison of the different biorefinery routes shows that routes producing bulk products perform
better than routes where high-value specialty chemicals are extracted from the lignin pyrolysis oil.
- Comparison of using the biochar as carbon black and as substitute of a fertilizer shows that the
former option is preferred from environmental point-of-view.
-100
-80
-60
-40
-20
0
20
40
60
80
100
%
Lignin to electricity Lignin to case 1 Lignin to case 1b Lignin to case 2 Lignin to case 3 Lignin to case 4
Lignin to electricity -19 100 100 -33 1 5 24 3 100 0
Lignin to case 1 -92 44 96 -83 -77 -16 7 -10 99 -37
Lignin to case 1b -47 71 98 -26 -26 -3 8 -10 99 -29
Lignin to case 2 -100 41 90 -98 -78 -100 -7 -19 99 -100
Lignin to case 3 -95 46 100 -100 -100 -21 17 -2 99 -24
Lignin to case 4 -65 86 60 6 -3 -13 -100 -100 100 -10
Abiotic
depletion
Acidificatio
n
Eutrophicati
on
Global
warming
(GWP100)
Ozone layer
depletion
(ODP)
Human
toxicity
Fresh water
aquatic
ecotox.
Marine
aquatic
ecotoxicity
Terrestrial
ecotoxicity
Photochemi
cal
oxidation
22
Task 6 Socio-economic evaluation
Partners involved: WU-VPPC + all partners + industrial advisory board.
Goals:
Identify potential “set-up” for the chain
Identify chances and bottlenecks in the bio-refinery process This study was performed via a desktop study and discussion groups. Project approach and aims The major focus of the project is the use and conversion of lignin in order to reduce/replace 100PJ of fossil energy. Lignin could be used directly to produce energy but in this case a lower value application is produced. By processing lignin, higher value products and applications may be achieved. It is proposed that lignin could be used to substitute phenol, or used where applications of phenol is required. Given the volumes of these materials, and the energy costs to produce them by traditional petrochemical routes, this could represent substantial savings in energy. In the case of phenol, current production of phenol requires 60-70 GJ/tonne product representing the fossil costs for the molecule and the process costs in the process. Use of lignin would eliminate the fossil contribution to the molecule and potentially (partial) process energy. The char generated in the process may potentially be used for added value applications as well as energy and fill applications. The approach is represented in Figure 1.
Figure 11 The use of lignin processing to add value3
Biomass sustainability. availability and supply Sustainable use of biomass With governmental initiatives to stimulate the use of biomass for the application in the areas of energy, fuels and chemicals it was realized that large scale production and use may incur certain environmental risks. For these means it is important to establish sustainability criteria for responsible use of biomass obtained from various origins and obtained from either within the Netherlands or EU and also originating outside the EU.
3 6mln tonnes lignin input represents 100PJ. Due to energy required to obtain this, the figure will possibly be
higher *Calorific value of 15-20 GJ/tonne # coal price
Lignin
100PJ, ca. 6mln tonnes*
Process
Oil
CHP
Soil
€1100 / tonne
(3 mln tonnes)
€>500 / tonne
(10’s mln tonnes)
€60 / tonne#
€50 / tonne
Phenol
Resin
Value (market)
Bitumen, CactChar
€1500 / tonne
(0.6 mln tonnes)
Lignin
100PJ, ca. 6mln tonnes*
Process
Oil
CHP
Soil
€1100 / tonne
(3 mln tonnes)
€>500 / tonne
(10’s mln tonnes)
€60 / tonne#
€50 / tonne
Phenol
Resin
Value (market)
Bitumen, CactChar
€1500 / tonne
(0.6 mln tonnes)
23
These principles, together with the criteria that should be met and the indicators to assess the framework are described further in the report “Testing framework for sustainable biomass” from the project group Sustainable Production of Biomass, Creative Energy. Feedstock and compliance within the framework The use of lignocellulose biomass for the process described may be obtained via various strategies.
Residues from crop (grain and seed) production. Here one can think of straw from the likes of wheat and rape.
Forestry residues. The EU 27 production of wheat (grain) and rapeseed amounts to 120 mln tonnes and 18.1 mln tonnes respectively. In Germany and France alone the production of wheat and rapeseed is 55 mln tonnes and 10 mln tonnes respectively. Other grains such as barley (20 mln tonnes), grain maize (17.5 mln tonnes) and rye (3 mln tonnes) are also produced and also generate significant amounts of straw.
4
Based on these figures, straw production from a variety of sources amounts to more than 100 mln tonnes. With an average straw composition of cellulose (33%), hemicellulose (25%), lignin (15%), rest (26% - water, ash etc.) this could generate in excess of 15 mln tonnes of lignin at an EU level. Currently the use of straws from the cultivation of the grain and seed, as described above, fall into several categories.
The straws during/after harvesting are left on the field o In some instances all straw materials are left on, or ploughed back into the field
after harvesting as a means to retain soil quality. However, some studies have described that not all the straw is required and that 30wt% is sufficient to retain quality.
5
Roughage (of low energy and digestibility) for cattle and horses o Due to the low nutritional quality and risk of impaction, the use of straw in the diet
should be kept to a minimum.
Straws are used for bedding of livestock and horticulture mulch/coverage o Here it is unclear how much of the total is utilized in this area and requires further
elucidation.
Pelletisation and used in co-firing6
o Several examples have been demonstrated but low energy density and presence of certain metals, results in higher requirement
o demands for co-firing with coal. The exact price of straw remains unclear, some report figures as low as ca. €30-50 per tonne
7 in areas
of high straw production but a more realistic European price is anticipated to be in the area of ca. €75 per tonne (based on UK figures).
8
Forestry residues are generated during the production of wood for paper and building materials. Forestry residues represent an amount of approximately 1/5
th of the wood produced/used.
9 Residues
in this area are mainly used as energy sources. Based on wood use for pulp production (ca. 40 mln tonnes), residues of ca. 8 mln tonnes may be expected, which could supply 4 mln tonnes of lignin.
1011
Based on;
the production of straws is a consequence of current agricultural practices,
there is no need to use all of the straws generated to maintain soil quality,
it (straw) is not used as food and only limited need for feed purposes,
current demonstration of residues for energy,
4http://epp.eurostat.ec.europa.eu/statistics_explained/index.php/Crop_production_statistics_at_regional_level
5 Processing lignocellulosic by-product streams using organic acids. PhD Thesis A.M.J. Kootstra (2010)
6 http://ie.jrc.ec.europa.eu/publications/scientific_publications/2006/EUR22461EN.pdf
7 http://www1.agric.gov.ab.ca/$department/deptdocs.nsf/all/faq7514
8 www.farming.co.uk and www.telegraph.co.uk/earth/earthnews/8585140/Price-of-hay-and-straw-to-
rocket.html 9 Discussion W. Elbersen, WUR
10 carbohydrates:lignin is approximately 2:1
11 20 mln tonnes of lignin liquor from pulp production, ca. 10% of this may be made available.
24
coupled with large volume production (of diverse origin) and low costs of feedstock would indicate conformity to the sustainability criteria of the design developed in the project. New and alternative use of these residues for value added products would lead to new factories (conversion sites) and employment in areas that supply these residues and also increase economic and ecological prospects of existing practices. Alternative process feedstocks Residues from biofuel production. During the production of bio-ethanol from first generation feedstocks, such as wheat (grain) or corn, residues remain after the distillation process. The undried residues, wet distillers grains (WDG) and the resultant dried distillers grains and solubles (DDGS), contain a mixture of protein (ca. 30-40 dw%), carbohydrates (ca. 40-50 dwt%) and lignin (ca. 5-10 dwt%). Currently these materials are used as inexpensive feed materials with a value of ca. € 200/tonne.
12 The use of biorefinery could add
additional value to these (rest) streams. Protein materials could be used for feed and other applications while the rest could be used as a source of carbohydrates (for fermentation products) and lignin. If one considers the production of bio-ethanol by Abengoa (Europort, Rotterdam)
13 ca. 400 k
tonnes of ethanol is produced together with a comparable amount of DDGS, the potential for lignin generation form this stream could be 20-40 ktonnes. In general, large bio-ethanol producing areas particularly those in France, Germany and Spain (producing ca. 1, 0.6 and 0.4 mln ton bio-ethanol respectively) could also act as potential sources.
14 In conclusion, a total of ca. 80-160 ktonnes could
be an anticipated amount of lignin from these sources in the Netherlands, France, Germany and Spain. This may increase with anticipated increase in bioethanol production. A similar situation could be envisaged for the production of bio-diesel where a residual press cake obtained from rape.is obtained. Again biorefinery (at sites close to biodiesel production) could lead to substantial quantities of lignin available for further application.
15
Residues from pulp and paper production. During the various pulping process lignin products are generated in the form of a (black) liquor. Pulping processes in CEPI
16 countries generates ca. 40 mln tonnes of pulp. Based on the composition
of the (woody) materials used (cellulose pulp:lignin is approximately 2:1) ca. 20 mln tonnes of lignin (liquor) is generated. A consideration here is that other chemicals and reagents need to be isolated or removed from the black liquor lignin source.In the case of sulphite pulping lignosulphonates are produced. However due to the sulphonate groups this lignin is rendered unsuitable for the current conversion techniques and applications described within the context of this project. Particularly the use of soda and organosolv pulping (studied in this project) could generate high purity lignin with a low carbohydrate (and sulphur) content which could make it suitable for further transformation. The question of course arises how available is such a lignin? In the pulping mills the black liquor/lignin generated is generally used as (partial) fuel source for the process.
17 In other studies it has been
suggested that the kraft pulp and paper industry (Södra) are open to the idea of making a percentage (ca. 10%) of the lignin generated available for other applications to generate extra revenue.
18
12
www.extension.iastate.edu/agdm/.../agmrcethanolplantprices.xls 13
http://www.abengoabioenergy.com/corp/web/en/acerca_de/oficinas_e_instalaciones/mapa_global/europa/index.html 14
http://www.biofuels-platform.ch/en/infos/eu-bioethanol.php 15
EU production: Wheat - 120 mln tonnes, rapeseed – 18.1 mln tonnesGerman and French production: wheat – 55 mln tonnes, barley - 20 mln tonnes, grain maize - 17.5 mln tonnes, rye - 3 mln tonnes, rapeseed – 10 mln tonnes 16
CEPI: Confederation of European Paper Industries http://www.cepi.org/Content/Default.asp?PageID=2 17
It is suggested from CEPI that ca. 10% of the fuel used is from biomass origin. This is not exclusively lignin but also from bark and other woody residues. 18
Discussions with R. Gosselink
Case regarding increasing biofuel production: 20% replacement of EU fuel = 3 EJ
Assume 50% can be substituted by bioethanol = 1.5 EJ = 60 mln tonnes ethanol
» 3 – 6 mln tonnes potential lignin
25
In conclusion, an anticipated amount of kraft lignin from these sources in CEPI countries could amount to ca. 2 mln tonnes.
19
When considering these alternative feedstock the framework for sustainability should also be considered. Based on this DDGS, rape & soya cake have current applications in animal feed but added value could be gained by biorefinery and still satisfy feed market where the protein fraction could still be applied for feed and other applications. It is also considered that this could improve feed as minerals would be removed and the (protein) digestibility would increase. Products, market and economic growth The chemical industry in the Netherlands has a significant input into the gross domestic product (GDP).
20 Other European countries (e.g. Germany) also have large and significant chemical
industries. The Netherlands would like to increase its contribution to the GDP by the chemical industry. In order to achieve this many factors are required and this is further complicated by the fact that CEFIC describes a decrease in the share of a growing global market by the European chemical industry.
21 Innovation plays a key role as new technologies lead to new products and markets. As well
as this, innovation contributes to an increase in material and energy efficiency and improvement in the sustainability of processes and resources. Innovations described in this project could contribute to this. Specifically Germany and The Netherlands are major producers and users of fossil based phenol for a variety of chemicals and materials
22, therefore innovations could be very advantageous. If innovations
in the area of using lignin to produce materials where phenol is used were developed abroad this could lead to loss of existing production, products and markets. This would also mean more reliance on others for raw materials and products in this area. In general fluctuating oil prices and the security of supply make the use of biobased raw materials for chemical products more attractive. The logistical chain The production and conversion of biomass, biomass residues to fertilizers/soil improvers, energy (heat and fuel), bitumen products, fermentation products and products potentially derived from lignin involves various steps/process and stakeholders to form a logistical (value) chain. A number of potential stakeholders were identified. Attitude to developments described in this project were assessed together with their interests, influence and the potential impacts were considered. Notably within the context of this project there is an absence of interaction with biomass suppliers (farmers, co-operatives land owners / councils), those who are involved in the trade of biomass commodities (feed industry) and agro-based industries (biofuels, paper etc..). (Inter)action will be required in developments of a potential process with respect to realistic biomass supplies and impacts on soil quality, land erosion and biodiversity. Rural and regional development The use of residual streams generated from the agro-based industry (e.g. biofuels) and biomass processing industries (e.g. pulp and paper,) as a means to develop biobased fuels, chemicals and materials is gaining momentum.
23 Where (pre)processing occurs close to field, minerals may be
returned more readily to the land thereby allowing the farmer to maintain soil fertility without the need for additional fossil based fertilizers and prevents transport of large volumes of biomass. Developments and other studies show that processing biomass volumes of ca. 150,000 tonnes per annum for straw is achievable. For plantation woody biomass, as in Canada, volumes up to 1.6 mln tonnes per annum can be achieved (large Kraft pulping mill).
24 Larger processing volumes are
prohibitive mainly due to the needs for greater transportation over a larger area to supply the feedstock volume to the processing site. In areas where more intensive biomass production takes place this is likely to be less of an issue. Integrated biorefinery concepts to maximize the technological and economic potential of all biomass components are seen as an effective way of utilizing existing infrastructure and logistical chains. Synergy between companies is already taking place as companies are already exchanging and using
19
Global production based on global pulp production is approximately x5 20
http://www.regiegroepchemie.nl/pdf/Businessplan_ENGLISH.pdf 21
Source: Hubert Mandery, Cefic 22
Rotterdam – a port in a biobased economy. JPM Sanders, EL Scott, J vHaveren 23
Sanders J, Scott E, Weusthuis R, Mooibroek H. Bio-refinery as the bio-inspired process to bulk chemicals.
Macromolecular Bioscience 7 (2007) 105-117 24
Karin Lindgren Potential lignin products from the wood biorefinery NWBC 2011 Tom Browne, 3rd NWBC, Stockholm, March 23, 2011
26
residues as new feedstocks and energy.
25 Additional isolation and conversion of DDGS, rape cake
and black liquor to produce higher value products integrated into existing bio-ethanol, bio-diesel and pulp production respectively, could be an opportunity to improve economic and ecological factors in these existing production routes. Specifically biorefinery and transformation at large ports offer excellent perspective for example in Rotterdam and Antwerp as well as Gent, Groningen Seaports – Delfzijl as they:
allow access to large amounts of raw materials
are affiliated to large integrated chemical complexes
have on site bio-fuel and bio-refinery expertise
have good river access to important chemical producing regions o Reduction on road transport o Allow ease of export of products on a global scale
While not explored here, it is expected that biorefineries and new conversion technologies will lead to new and alternative use residues for value added products resulting in new factories (conversion sites) and employment in areas that supply these residues and also increase economic and ecological prospects of existing practices.
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Conclusions and challenges to be overcome Opportunities and bottlenecks in the process
Strengths
A lot of different sources of lignin have been identified which accumulate in sufficient quantities divers locations.
The use of phenolic oils show good technical performance
Low cost of feed stock as long as molecular functionality can be valorized
Ample technological potential available in Europe
Weaknesses
Current technology is still at an early stage.
Initial biorefinery results in lignin with a high price for the applications that can be currently proven.
Lignin price (highly) dependent on feedstock cost. Here relatively low feedstock costs were used.
For mass market potential – and maximum potential – yields on phenol are too low.
Downstream processing complex and unknown to access well defined products.
Complex mixtures of lignin derived chemicals are difficult to separate
Opportunities
Initial studies show most feedstocks have conformity with sustainability and solutions to overcome uncertainty look positive.
Use of lignin as a feedstock could make significant energy reductions in areas where phenols are traditionally used.
Integration into existing processes could improve economic and ecological perspectives of these processes.
Potential for (more) optimum use of European agro-residues and sidestreams
Potential for (more) optimum use of non-European agro-residues and sidestreams
Integration into existing processes could improve economic and ecological perspectives of these processes.
NL, Belgium, France and Germany are well placed to receive and convert biomass and export products.
Innovation could lead to strengthening of European chemical industry at a time of change in the sector.
Positive effect on rural and regional developments and employment.
Threats
Use of lignin might negatively be influenced because of price volatility
Public opinion could not agree with application for chemicals instead of soil fertility
(Subsidies for) application for electricity production will decrease availablity of lignin
Application as transportation fuels can be obtained with better economy
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Biopol project EU 44336
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Chapter 2 Bijdrage aan de EOS: Lange Termijn doelstellingen
4.1 De bijdrage aan een duurzame energiehuishouding
a. De bijdrage van dit project aan de doelstellingen van het desbetreffende onderzoeks-
programma (speerpunt/kennisimportthema).
EOS-LT doelstelling is besparing van 100PJ aan (fossiele) energiereductie door vervanging van een
chemisch productieproces door een bioraffinage proces.
Voor besparing van 100PJ is circa 6 miljoen ton lignine nodig als alleen de energie inhoud wordt
gerekend (base case). Als lignine wordt gebruikt om fenol of andere aromatische chemicaliën te
vervangen, dan bespaart iedere ton lignine circa 60 GJ en dat is aanzienlijk meer dan de energie
inhoud van 15-20 GJ/ton.
Deze 6 miljoen ton lignine kan jaarlijks in Europa worden verkregen uit 80 miljoen ton lignocellulose
biomassa, zoals agro-residuen (tarwe stro, raapzaad stro/cake, soja schroot, maisstengel, DDGS) en
houtige biomassa (crops en residuen). Beschikbaarheid van de biomassa is echter sterk afhankelijk
van huidige applicaties en er is veel competitie gaande. De verwachting is dat vanwege de
biobrandstoffen regelingen voldoende lignine zal worden geproduceerd om aan deze vraag te
voldoen.
Aanvoer en verwerking van biomassa kan decentraal gebeuren in kleinere (primaire) bioraffinage
units, waarin de lignine wordt geproduceerd (zie taak 5) en verschillende units kunnen lignine leveren
voor een meer centrale pyrolyse unit (secundaire bioraffinage) van 300.000 ton/jaar.
Uiteraard kan ook gebruik gemaakt worden van het havengebied (zoals Rotterdam, Antwerpen,
Hamburg en Le Havre) waar biomassa kan worden aangevoerd en in een grotere biomassa
bioraffinage (1.6 miljoen ton/j) kan worden verwerkt.
Omdat Nederland en Duitsland belangrijke producenten en gebruiker van fossiele fenol zijn, ligt het
voor de hand om de biobased productie van groene fenol uit lignine in Nederland te laten
plaatsvinden. Producten kunnen eenvoudig via de bestaande infrastructuur naar het achterland
(Nederland/Duitsland) worden vervoerd voor verdere verwerking.
Hiermee voldoet de ontwikkeling ruimschoots aan EOS Target 1.
b. De bijdrage aan een technologische doorbraak of innovatie in een internationaal
perspectief.
Resultaten van dit onderzoek hebben aangetoond dat middels organosolv fractionering zowel houtige
biomassa als agro-residuen (tarwe stro) effectief kunnen worden ontsloten. Dit levert kwalitatief
hoogwaardige stromen op die verder kunnen worden ingezet voor de productie van biobrandstoffen,
zoals bio-ethanol of bio-butanol, en fenolische chemicaliën vanuit de lignine fractie. Toepassing van
ethanol-water gebaseerde fractionering voor agro-residuen is een technologische doorbraak te
noemen, omdat elders in de wereld met name aan houtige biomassa wordt gewerkt (loofhout en
naaldhout, zie daarvoor Lignol activiteiten www.lignol.ca).
Daarnaast is de processing van lignine middels een continue pyrolyseproces een belangrijke
technologische doorbraak en daarvoor is een tweetal patenten aangevraagd door ECN en Aston
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University. Tot nu toe bleek het technisch niet mogelijk om een hoge kwaliteit lignine continue te
voeden in een pyrolyse bed reactor, vanwege propvorming en discontinue voeding.
Ook de toepassing van een supercritisch medium, bestaande uit kooldioxide, aceton en water voor
lignine conversie in toegevoegde waarde producten is niet eerder gepubliceerd en wordt momenteel
geëvalueerd op de mogelijkheid voor het aanvragen van een patent. In dit proces worden de target
producten continue verwijderd van de lignine voeding en vindt simultane fractionering plaats.
Partiële verwijdering van zuurstof in lignine door HDO is op zich niet nieuw, maar in dit project is veel
meer inzicht verkregen in de effecten van de lignine molmassa en heterogene katalytisatoren op de
lignine conversie. Hieruit kunnen strategieën worden opgezet om in de toekomst te komen tot een
continue HDO proces als integraal onderdeel van een lignine valorizatie proces. Gezien de
wereldwijde ontwikkelingen op dit gebied, zal RUG een belangrijke kennisdrager op dit gebied blijven.
De resultaten van de diverse onderzoeksgebieden zijn internationaal verspreid op congressen,
symposia en via wetenschappelijke publicaties (zie 4.2b).
c. De strategische visie op het implementatietraject van de onderzoeksresultaten en de
verwachtingen over toekomstige voortzetting van de ingezette onderzoekslijn.
Gedurende het project is reeds begonnen met het interesseren van industriële partijen om de
ingezette onderzoekslijn voort te zetten. De interesse van industriële partijen om dit te vervolgen is
aanwezig, echter de financiering ontbreekt vooralsnog. Een mogelijk vervolg is hierna weergegeven in
overleg met Energy Valley te Groningen:
Potentieel vervolg De experimenten in het project Lignovalue hebben op bench/labschaal plaatsgevonden. Voor een verdere ontwikkeling richting economische activiteiten is het nuttig aan te tonen dat deze processen ook op grote schaal hun waarde hebben. Dit geeft ook een duidelijker beeld omtrent de economische haalbaarheid. De stap van een labopstelling naar een commerciële installatie is erg groot. Daarom wordt in eerste instantie gedacht aan opschaling naar een pilot-scale installatie in een container. Dit levert wel de ervaring met opschaling en relatief grote productie-eenheden maar heeft nog niet de investeringsbenodigdheden die een commerciële installatie wel zou hebben. De Eemsdeltaregio is een logische landingsplaats voor een dergelijk initiatief. Hiervoor is een aantal redenen aan te voeren:
(1) De combinatie van landbouw in de regio en chemie op het bedrijventerrein is uniek. Reststromen uit de landbouw kunnen de basis voor het LignoValue proces vormen.
(2) Er vindt zowel in- als uitvoer van biomassa plaats. Groningen Seaport wil zich ontwikkelen tot bioport met een belangrijke rol in opslag en transport van biomassa.
(3) Combinaties met de energiecentrales zijn mogelijk, zowel wat betreft de levering van warmte vanuit de centrales als het leveren van biochar aan de centrales.
De in de verschillende routes geproduceerde biochar is ook interessant voor de regio omdat Kiemkracht/Productschap Akkerbouw in de Veenkoloniën een grootschalige biochar productie-eenheid wil realiseren ter stimulering van biochartoepassing in de landbouw. Potentiële partners in het vervolgproject zijn:
WUR/ECN/RUG
Kenniscentrum Papier en Karton
Dynea/Trespa: hars
IKEA
Kiemkracht
Productschap Akkerbouw
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Potentiële lignocellulose bioraffinage
Lignocellulose grondstoffen, bijvoorbeeld snoei- en afvalhout en stro dat verzameld wordt door staatsbosbeheer, gemeenten en boeren (cooperaties), kunnen als input dienen voor een organosolv ontsluitingsfabriek. Deze reststromen kunnen middels effectieve en kostenefficiënte omzettingen worden gebruikt voor hoogwaardige toepassingen, zoals in figuur 12 schematisch is aangegeven. De cellulose stroom kan worden gebruikt voor productie van bio-ethanol en papierpulp. Furfural kan worden verwerkt tot een biofuel component of dienen als start materiaal voor synthese van polymeren of als onderdeel van een biobased lijm (resin). De organosolv lignine kan via thermochemische conversie naar een lignine olie worden gebruikt als houtlijm voor de ontwikkeling van biobased en emissie-vrije lijmen voor vezelplaten. Het doel hiervan is zowel vervanging van fossiele fenol als van vervanging van het carcinogene formaldehyde dat wordt gebruikt voor het uitharden van de lijm. Een deel van de char en gas kan worden gebruikt voor interne energievoorziening. Voor de char zijn verschillende mogelijkheden voor hoogwaardige toepassingen zoals in bitumen, aktieve kool of als (laagwaardige) bodemverbeteraar.
Het merendeel van de producten die uit lignocellulose grondstoffen worden geproduceerd zullen ter vervanging van huidige fossiele producten worden ingezet. Dit levert naast een forse besparing van fossiele grondstoffen ook een forse besparing van CO2 emissie op. Daarnaast kan het gebruik van lignine in houtlijmen leiden tot een aanzienlijke reductie van formaldehyde-houdende lijmen.
Voor het opzetten van deze lignocellulose bioraffinage keten zijn diverse industriële partijen geïdentificeerd, die in potentie dit concept zouden kunnen realiseren in 2020. Hiervoor zijn allianties noodzakelijk waarin grondstoffenleveranciers, verwerkers en toepassers deelnemen.
Figuur 12 Lignocellulose bioraffinage concept en betrokken industriën
Om tot de realisatie van een lignocellulose bioraffinage fabriek te komen, zullen de resultaten van het Lignovalue project moeten worden geëvalueerd op pilotschaal. Een dergelijk traject wordt hierna beschreven.
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Idee-fase
Implementatie-fase
Uitrol-fase
Demo/pilot-fase
R&D-fase
LignoValue Fase 2
Traject naar realisatie van het project “Lignovalue Fase 2” Dit position paper richt zich op de realisatie van een demonstratie-installatie. Het echte R&D werk is in het voorgaande project uitgevoerd en de demonstratie-installatie zal de weg naar een commerciële fabriek vrij moeten maken. De demonstratie-installatie produceert waardevolle chemische bouwstenen vanuit ligninehoudende biomassa. De activiteiten richten zich ook op de mogelijkheden die reststromen uit het proces bieden. Een voorbeeld hiervan is de toepassing van biochar in de landbouw. In eerste instantie is gekozen voor een installatie die in een container past. Hiermee worden technolo-gische en financiële risico’s tot aanvaardbare proporties teruggebracht. De realisatie van de installatie zal xx m€ aan investering kosten. Inclusief projectmanagement, benodigd onderzoek en andere projectactiviteiten is de begroting van de projectuitvoering in de buurt van xx m€. Financieringsstrategie De benodigde middelen kunnen uit regionale, nationale en Europese fondsen verkregen worden.
Vervolg onderzoek
Een deel van het onderzoek wordt vervolgd in een recent gestart EU FP7 project “Biocore:
Biocommodity Biorefinery” met partners WUR-FBR en ECN en in diverse Catchbio projecten, waarin
ECN, WUR en RUG participeren.
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4.2 De versterking van de kennispositie van Nederland
a. De bijgedragen aan de versterking van kennis, kunde of onderzoeksfaciliteiten in
Nederland.
Dit LignoValue project heeft veel kennis op het gebied van lignocellulose bioraffinage opgeleverd, in
het bijzonder:
1. Organosolv ontsluiting van stro en houtige biomassa tot hoogwaardige cellulose,
hemicellulose en lignine stromen
2. De cellulose stroom is efficiënt om te zetten in monomere suikers, waaruit een biobrandstof
via een fermentatieve route kan worden geproduceerd
3. De lignine stroom heeft een hoge zuiverheid en is bij uitstek geschikt voor verder
thermochemische conversie naar een fenolische olie, gassen en char.
4. Pyrolyse van lignine in een continue proces, waarvoor een bench/pilot installatie bij ECN
aanwezig is
5. Veel kennis over de depolymerisatie processen van lignine (kinetiek, chemie) onder pyrolyse,
supercritische en hydrodeoxygenatie condities
6. Applicatie mogelijkheden voor lignine als vervanger van fenol in fenolformaldehyde harsen
voor het lijmen van multiplex houtplaten
7. Applicatie mogelijkheden voor brandstof additieven op basis van lignine chemicaliën
8. Economische randvoorwaarden voor de integrale bioraffinage van lignocellulose biomassa
naar biobrandstoffen, chemicaliën en producten
9. Een dergelijke bioraffinage fabriek zou in Nederland of elders in Europa kunnen worden
gebouwd, waarbij de biomass input in de regio of via de havens wordt aangevoerd.
Recent is het Wageningen UR Lignin Platform opgericht waarin Wageningen UR leerstoelen en
instituten zijn vertegenwoordigd te samen met bedrijven en kennisinstellingen, waaronder LignoValue
partners ECN, WU-VPPC en RUG. Dit platform wordt gecoördineerd door WUR-FBR. Voor meer
informatie: www.ligninplatform.wur.nl
b. De verspreiding en benutting van de in het project opgedane kennis, kunde en de
voorwaarden waaronder dit is gebeurd.
A promotion film was prepared on Lignin valorization “Lignine van reststof tot grondstof” by the
coordinator in collaboration with MugMedia, Wageningen and can be found on YouTube
http://www.youtube.com/watch?v=agpg8kbhXHw. This film has been presented to different policy
makers and bodies from the Ministry of Agriculture, Nature and Food Quality (LNV) and Wageningen
University & Research centre. This film was also shown at the official LignoValue dissemination
workshop for industrial parties and other interested parties.
The “LignoValue Dissemination” workshop was held at 14 September 2010 as part of the International
Biomass Valorisation Congress during 13-15 September 2010, Amsterdam, NL (www.biomass-
valorisation.com). In this workshop all partners presented their results and achievements. More than
80 International delegates were attending the conference with 54 participants in the LignoValue
workshop. From these about 40% were representatives of industrial parties, others from
institutes/academia and governmental organizations. This workshop was successful with an
interesting discussions on the topics presented and several leads for further continuation of this
lignocellulosic biorefinery concept.
General dissemination takes place through the project website www.lignovalue.nl.
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Conference contributions and Publications are given hereafter:
Wild de P J et al. (2007) IEA-Thermalnet / Pyne magazine, June 2007, Preliminary Results of Lignin Pyrolysis at ECN Wild de P J et al. (2007) PyNe (Pyrolysis Network) workshop at the Success and Visions for Bioenergy conference in Salzburg on 21-23 March 2007, IEA-PyNe Round Robin Test On Lignin Fast Pyrolysis R.J.A. Gosselink, E. de Jong, E. Scott and J. Sanders (2008) Lignin depolymerization under supercritical process conditions, poster at Nordic Wood Biorefinery Conference, March 10-13, 2008, Stockholm R.J.A. Gosselink, J.E.G. van Dam, E. Scott and J. Sanders (2008) Valorization of lignin resulting from biorefineries, 4th International Conference on Renewable Resources & Biorefineries (RRB4), Rotterdam, The Netherlands W.J.J. Huijgen, R.R. van der Laan, J.H. Reith (2008) Modified organosolv as a fractionation process of lignocellulosic biomass for co-production of fuels and chemicals, 4th International Conference on Renewable Resources & Biorefineries (RRB4), Rotterdam, The Netherlands W.J.J. Huijgen, R.R. van der Laan, J.H. Reith (2008) Modified organosolv as a fractionation process of lignocellulosic biomass for co-production of fuels and chemicals 16th European Biomass Conference, Valencia, June 2008, Spain W.J.J. Huijgen, R.R. van der Laan, J.H. Reith (2009) Biomass Fractionation by an Organosolv Process for Co-Production of Fuels and Chemicals, Biorefinica Conference, Osnabrueck, Germany, Jan 2009. W.J.J. Huijgen, R.R. van der Laan, J.H. Reith (2009) Organosolv-based Fractionation of Lignocellulosic Biomass for Co-Production of Fuels and Chemicals within a Biorefinery, RRB5, Gent, Belgium. A. Kloekhorst, J. Arentz, J. Wildschut and H.J. Heeres (2009) Hydrodeoxygenation of lignin model compounds with Ru/C catalysts, Xth Netherlands Catalysis and Chemistry Conference, Noordwijkerhout, 02-04 Mar 2009 Paul J. de Wild, R. van der Laan, A. Kloekhorst, E. Heeres (2009) Lignin valorisation for chemicals and (transportation) fuels via (catalytic) pyrolysis and hydrodeoxygenation, GTI organised Thermal Biomass Conference in September 2009. Wild de P J, Van der Laan R, Kloekhorst A, Heeres E (2009): Lignin Valorisation for Chemicals and (Transportation) Fuels via (Catalytic) Pyrolysis and Hydrodeoxygenation, Environm. Progress Sust. Energy, 28(3), pp. 461 – 469 Jiang G, Nowakowski D J, Bridgwater A V (2010): Effect of the Temperature on the Composition of Lignin Pyrolysis Products, Energy Fuels, 24 (8), pp. 4470–4475 Huijgen, W. J. J.; Reith, J. H. & den Uil, H. (2010) The organosolv process for pretreatment and fractionation of lignocellulosic biomass for fermentation and lignin valorization, 6th European Bioethanol Technology Meeting, Detmold, Germany. Reith, J. H.; Huijgen, W. J. J.; Wild de, P.J. & Den Uil, H. (2010) Fractionation of lignocellulosic biomass by an organosolv process for co-production of fuels and chemicals within a biorefinery, 18th European Biomass Conference & Exhibition, Lyon, France. P.J. de Wild et al. (2010) Lignin pyrolysis, XV International Humic Substances Society, Tenerife Richard J.A. Gosselink, J.E.G. van Dam, E. de Jong, G. Gellerstedt, E.L. Scott, J.P.M. Sanders (2010) Lignin depolymerisation in supercritical solvent, RRB6, Düsseldorf, June 2010. A. Kloekhorst and H.J. Heeres (2010) Hydrodeoxygenation of lignin with Cupper catalysts, Netherlands Catalysis and Chemistry Conference (NCCC XI), Noordwijkerhout, March 2010 Richard J.A. Gosselink, J.E.G. van Dam, E. de Jong, G. Gellerstedt, E.L. Scott, J.P.M. Sanders (2010) LIGNIN DEPOLYMERISATION UNDER SUPERCRITICAL PROCESS CONDITIONS FOR AROMATIC CHEMICALS PRODUCTION, EWLP11, August 2010, Hamburg P. de Wild (2010) Lignin pyrolysis, CHEMREACTOR-19, 2010, Vienna Paul de Wild, Ron van der Laan, Ruud Wilberink, Wouter Huijgen (2010) LIBRA; Lignin Biorefinery Approach; pyrolysis of lignin for value-added products, TCS-2010 September 2010, Iowa State A.Kloekhorst, J. Wildschut, J. Arentz, B. Huisman, H.J. Heeres (2010) Catalytic hydrotreatment of fast-pyrolysis oil using Ru/C catalysts. Insights in the reactivity of the pyrolytic lignin fraction, TCS-2010 September 2010, Iowa State Richard Gosselink, Jan van Dam, Paul de Wild, Wouter Huijgen, Tony Bridgwater, Daniel Nowakowski, Erik Heeres, Arjan Kloekhorst, Elinor Scott, Johan Sanders Valorisation of lignin for optimal lignocellulosic biorefinery – achievements of the LignoValue project, International Lignin Chemicals conference, 17-18 November 2010, Toronto & NWBC3/ILI9 Conference, 22-24 March 2011, Stockholm W .J.J. Huijgen , A.T. Smit, P.J. de Wild, J.H. Reith, H. den Uil (2011) Effects of Catalysts on Organosolv Fractionation of Willow Wood and Wheat Straw, poster presentation, NWBC3/ILI9 Conference, 22-24 March 2011, Stockholm P.J. de Wild et al. LIBRA, A novel pyrolysis-based lignin biorefinery approach for the production of phenolic chemicals and biochar, poster presentation, NWBC3/ILI9 Conference, 22-24 March 2011, Stockholm Huijgen W J J, Smit A T, Reith J H, den Uil H (2011): Catalytic Organosolv Fractionation of Willow Wood and Wheat Straw as Pretreatment for Enzymatic Cellulose Hydrolysis, Journal of Chemical Technology and Biotechnology (in press, DOI: 10.1002/jctb.2654) Gosselink R J A, van Dam J E G, de Jong E, Gellerstedt G, Scott E L, Sanders J P M (2011): Lignin depolymerisation under supercritical process conditions for aromatic chemicals production (submitted) Wild de P J, Huijgen W J J, Habets, S., Van Eck, E.R.H., Heeres, H.J. (2011) Pyrolysis of wheat straw-derived organosolv lignin (submitted) Paul de Wild, Hans Reith, Erik Heeres (2011) Biomass pyrolysis for chemicals. In: Biofuels, Vol. 2, No. 2, Pages 185-208
Patent submission: Paul J. de Wild et al. (2010) Pyrolysis of lignin, patent application, June 2010 A.V. Bridgwater et al. (2010) Feeding of lignin for pyrolysis, patent application Results of the LignoValue project will lead to 3 PhD thesis: Paul de Wild, Biomass pyrolysis for chemicals, ECN, thesis defence 15 July 2011 Groningen University (promotor Prof. Erik Heeres) Richard Gosselink, WUR-FBR, thesis defence December 2011 Wageningen University (promotor Prof. Johan Sanders) Arjan Kloekhorst, RUG, thesis defence 2012 Groningen University (promotor Prof. Erik Heeres).