XXI Encontro Nacional da TECNICELPA / VI CIADICYP 2010 12-15 Outubro 2010 - Lisboa, Portugal

BIOREFINERY DEVELOPMENT PATHWAYS: A SURVEY FOR THE PULP AND PAPER INDUSTRY
Gabriel D. A. Sousa1
1

RAIZ, Research Institute of Forestry and Paper, Quinta de S. Francisco, Apart. 15, 3801-501 Eixo, Portugal * gabriel.sousa@portucelsoporcel.com, phone: +351 234 920 146, fax: +351 234 931 359

SUMMARY Biomass, especially lignocellulosic material, represents an abundant renewable carbon source. This is potentially convertible in energy, fuels and products. The integrated production of bioenergy, biofuels and biochemicals, through advanced technological processes of separation and conversion that minimizes carbon cycle impact, defines the biorefinery concept. The pulp and paper industry is at the forefront of this concept, since it is already a biorefinery 1st Generation Biorefinery enabling the sustainable production of pulp/paper enhanced by the coproduction of bioenergy, biofuels and bioproducts, through mature technological processes that maximizes the value chain of pulpwood. However, the decreasing profitability of standard pulp and paper mills and the Worlds demand for a non-fossil Carbon Economy resulted in a new biorefinery platform based upon complex technology concepts with higher revenue potential. Biorefinery development pathways are multiple. These are dependant on raw-material, conversion processes, intermediate chemical components, chemical building blocks and end-product application. Due to biomass complex and resilient nature, conversion processes are the critical step towards a successful Biorefinery concept. They can be generically classified according to two conversion technological platforms: Biochemical and Thermochemical. This paper intends to discuss different biorefinery concepts and summarize the most relevant biomass conversion processes in both technological platforms, assessing its potential for the pulp and paper industry. KEYWORDS: Biochemical, Biofuels, Bioproducts, Biorefinery, Thermochemical.

BIOREFINERY CONCEPT Introduction Presently, world faces several challenges regarding socio-economic environment. One of the main challenges is to cope with the increasing demand for energy. Primary energy consumption has risen and will continue to rise in the future, at least as according to world population pressure growth (Fig. 1). This energy pool is mostly fossil carbon based and is mostly used for transportation and energy production purposes. About 50% of this energy demand is for transportation purposes only [1]. As a result, or a part of it, oil price has increased, that also influenced other primary energy sources prices [2]. This situation, along with the need of reducing foreign oil dependency and the environmental awareness of worlds population has lead to a search on alternative primary energy and carbon sources based upon renewable sources. Biomass, especially lignocellulosic material, represents an abundant renewable carbon source. This is potentially convertible in energy, fuels and products. The integrated production of bioenergy, biofuels and biochemicals, through advanced technological processes of separation and conversion that minimizes carbon cycle impact, defines the biorefinery concept.

Figure 1. Left: Primary energy consumption until 2005 and estimates until 2030 [1]; Right: World population growth profile (Source: World Bank, 2004).

There is no singular concept of a biorefinery. In fact, there is an infinite amount of concepts depending on the combination of production pathways from the raw material towards the finished products. Table 1 reveals some of the possible biorefinery production platforms that can be adopted in a biorefinery.
Table 1. Biorefinerys main production platforms. Biorefinery Production Platforms Conversion Intermediates

Raw Materials

Food Crops Energetic Cultures Agriculture Residues Biomass Residues Wood MSW ...

Biochemical Thermochemical Chemical Mechanical

C5 Sugars C6 Sugars Lignin Extractives Oils Fibre Syngas Bio-oil Bio-gas ...

Base Products Bioenergy Bioproducts - Lactic Acid - Succinic acid - Furans - PHA - Lisin - Hydroxipropionic acid - Biocomposites - ... Biofuels - Hydrogen - Methanol - DME - Ethanol - Butanol - FT fuels - ...

Of all the platforms considered, the conversion platforms is the one that presents more challenges. To answer these new challenges several new processes are being developed. The main processes are associated to two different technology basis: Biochemical and Thermochemical Platforms. Biochemical platform can be defined as an application of several extraction, separation and biological conversion processes of biomass elemental components in order to produce biofuels and biochemicals. The sugar-to-ethanol processes, lignin valorisation, vegetable sterols extraction are examples of different technological routes within this platform. Thermochemical platform can be defined as group of biomass thermal treatment processes that envisages the production of syngas or bio-oil as a building brick to their conversion in bioenergy, biofuels and biochemicals. Biomass gasification, black liquor gasification, biomass pirolysis or liquefaction and carbonisation, oils aqueous phase reforming are examples of different technological routes within this platform. The combinations of raw materials, conversion process/technology and final products portfolio, associated to any of these platforms, are virtually unlimited. Moreover, there is no defined border

between these two technology concepts, since there could be plenty of synergetic interactions that can maximize environmental and economical product value. The final decision about biofuels, biochemicals and bionergy production pathway will depend upon raw material availability, technological know-how, regional policies, market regulations and dynamics, etc.

Biorefinery on the Pulp and Paper Industry The pulp and paper industry is at the forefront of this concept, since it is already a biorefinery 1st Generation Biorefinery enabling the sustainable production of pulp/paper enhanced by the coproduction of bioenergy, biofuels and bioproducts, through mature technological processes that maximizes the value chain of pulpwood. However, the decreasing profitability of standard pulp and paper mills and the Worlds demand for a non-fossil Carbon Economy resulted in a new biorefinery platform based upon complex technology concepts with higher revenue potential Rather than having to start a Greenfield manufacturing operation, the pulp mill can become the nexus of a 2nd Generation forest biorefinery (Fig 2). It is possible to integrate wood management platform for both pulpwood and forest residues for energy generation. Already existing equipments as CHP plants that convert residues and by-products from pulp and paper processes and other woodbased fuels to energy can be used. Optimisation of both energy generation and consumption (steam and power) is also a plus and some conversion processes produce a large amount by-product energy, which can be integrated with any energy demanding industrial facility (i.e. Paper Mill). Finally, exhaust-cooking liquor (i.e. black liquor), a liquid biomass stream, is only attainable in pulp mills. These aspects represent an obvious competitive advantage for this industry.

Bioproducts Biofuels

Biochemical/Thermochemical Platform

Forest

Bark Solid Biomass

Biomass Boiler

Energy

Roundwood

Debarking and Chipping

Woodchips

Thermochemical Platform (BL Gasification)

Biochemical Platform (Hemicellulose extraction and fermentation)

extracted woodchips

Recovery Boiler

Kraft Cooking

BL

Energy

Bioproducts Biofuels

unbleached pulp Biofuels (Bioethanol) bleached pulp Primary Sludges Paper Residues Paper Machine Bleaching
Biochemical Platform (BL extraction)

Biochemical Platform (Hemicellulose extraction and fermentation)

Paper

Figure 2. Biorefinery concept on pulp and paper mills. Dashed lines represent process alternatives.

Biofuels or Bioproducts Biofuels production is presently being promoted worldwide. Several policy measures are in action in order to achieve this. EU and US are at the forefront of this movement. The search for energy security supply and fulfilment of environmental directives are the main driving forces justifying technological development in this area. Recent oil price increase thrived this concern even further. At present days, biofuels production is sustained by first generation technologies, i.e., biofuels that are synthesized using food crops (corn, wheat, sugarcane, etc.) as raw material. Although, these technologies can promote local agriculture dynamics, theres an increasingly controversial vision associated with competition for food supply. Second generation biofuels are a more consensual solution for biofuels future, even though technological development limits its commercial application. This generation of biofuels are based upon lignocellulosic material, which doesnt collide with human food supply.

World economy is highly dependant on fossil raw materials, not only for energy and fuel purposes but also for products and materials production. A petroleum refinery is able to deliver a full range of products, including fuels and chemicals. Each of those adjusted to its volume markets. It is expected that a biorefinery industry should accomplish the same purpose. Lignocellulosic biomass is highly heterogeneous, containing different natural components, thus resulting in a high potential for dedicated or integrated biochemicals production. Bioproducts or biochemicals can be obtained through the upgrade/downgrade of the intermediates components produced from biomass (Fig. 3). Due to its high volume low price markets, biofuels production should prevail in a biorefinery environment. Low volume high price chemicals should boost biofuels process economy. Scale economy and market volume/prices should determine the viability of a full dedicated biochemical plant. However, the potential for different biochemicals production is insurmountable, which can create new market opportunities. Different research pathways are being pursued to deliver biochemicals in a cost-effective way. These chemicals can represent end products their selves or building bricks of a more broad chemical industry.

Syngas starch

Figure 3. Upgrade/Downgrade of biomass primary components and syngas towards chemicals production (adapted [3]).
Extractives/Oils

CONVERSION PLATFORMS Biochemical Platform Wood and woody residues are mainly constituted by sugars, which can ultimately be biologically converted to biofuels (bioethanol, biobuthanol, etc.) or bioproducts (lactic acid, succinic acid, etc). However, sugars are involved in a complex lignocellulosic matrix, which hampers their extraction and consequently their conversion. In addition, one of the main sugars present on biomass is a C5 sugar, like xylan, which is harder to ferment than the C6 sugars, like glucose. Thus, there are several challenges to overcome in order to deploy this technology, namely: Biomass pre-treatment stage, sugar hydrolysis and C5 sugar fermentation. Pre-Treatment stage can be adjusted according to the specific objective: a) Full conversion of biomass; b) Pre-extraction of wood sugars prior to kraft cooking. Full conversion of biomass implies that pretreatment stage is directed to increasing the accessibility of all carbohydrates within the crystalline structure of cellulose. In the second case, a mild pre-treatment is required in order to extract selectively hemicelluloses from wood. These sugars are degraded inevitably in kraft cooking and are used as a low calorific value fuel in black liquor. Thus, wood hemicelluloses pre-extraction and its conversion to ethanol, or other products, should add more value to the kraft process. The main biomass pre-treatment processes include auto-hydrolysis, dilute acid hydrolysis and steam explosion. After biomass pre-treatment, the solid fraction has to be hydrolyzed and fermented. There are several process alternatives, with increasing integration and cost reduction potential but also with increasing complexity: 1) SHF Separated Hydrolysis and Fermentation; 2) SSF Simultaneous Sacharification and Fermentation; 3) SSCF - Simultaneous Sacharification and CoFermentation; 4) DMC Direct Microbial Conversion. Each one of these alternatives differs on the integration of the sugar hydrolysis, pentose fermentation and hexose fermentation stages (Fig. 4). These principles can be applied not only for ethanol production but other biofuels (butanol, etc.) or bioproducts (lactic acid, etc.) that involve biological conversion stages. Table 2 reveals the developing projects for 2nd generation ethanol production. Most of these projects are being developed under a partnership of two or more companies.

Enzyme Production (Cel) Biomass Ethanol (C+H - L) Solid (C+L) Fraction PreTreatment Cellulose Hydrolysis SSF (G+L) Hexose Fermentation (EtOH+L) Conventional Destillation Pentose Fermentation SSCF DMC (P+I) Destoxification (P) Effluent treatment (EtOH) (L) Ethanol Dehydration

Liquid Fraction

Steam, Power

Figure 4. Possible routes for ethanol production process integration.

Thermochemical Platform Biomass, either solid, as in the case of wood residues, or liquid, as in the case of black liquor, can be converted, through a thermal process, to a synthetic gas comprised manly of CO and H2 with low amounts of methane, CO2 and H2O. There are different system configuration depending on type of reactor (upflow, downflow, CFB, BFB, etc), pressure level (atmospheric, pressurized), gasification agent (air, O2, H2, H2O), and type of heating (direct, indirect). The tar elimination and/or cleaning specifications of syngas are the main technological barriers to overcome. After solid biomass and the residual pulping liquors have been gasified, there is a choice of turning the synthesis gas into power or into liquid fuels and/or chemicals (Fig. 5). The gasification system can be coupled with a Combined Cycle Power Production Unit. Higher power production efficiencies (30-40%) are expected with this system along with lower atmospheric emissions. High capital costs and large-scale operation inexperience hinder its commercial application. Technical and economical viability should be assessed within this option. Internal Combustion Engines (ICE) is another option for a small-scale application (<5MW). Normally, diesel and gas are used within this technology. Landfill gases or methane biologically generated have also been used. The main problem concerns the gas cleaning solution. The power production efficiency of these systems can reach up to 20-30%. Finally, burning syngas in dedicated boilers or co-firing it in coal, fuel and recovery boilers is the simplest application of biomass gasification product. In pulp and paper industry it also can be employed in limekiln operation, replacing fossil fuels. Syngas can also be upgraded to produce synthetic natural gas improving thermal gas applications.

Figure 5. Possible routes for syngas conversion [4].

Alternately, conventional chemical processes can be used to convert the syngas to conventional motor fuels (Fischer-Tropsch fuels), DME, methanol or hydrogen. Fischer-Tropsch fuels, namely diesel fuel, are pointed out as a strategic biofuels target, since these fuels have the same characteristics as fossil fuels, which enables them to be incorporated in the already existing supply chain structure and in the same low and hard duty engines. Because of its overall efficiency, DME is also being pointed out as an important biofuel for the future. Several demonstration projects are under way for Diesel FT and DME, as shown in the Table 3. Syngas can also be converted in ethanol through chemical processes, but also through the biological conversion of syngas. Ethanol from syngas is being assessed mostly in US, since its used as gasoline replacement. Replacing recovery boilers for gasifiers can improve significantly pulp and paper process profitability. However, thermal and power balances have to be adjusted in order to compensate black liquor energy stream migration to biofuels production.
Table 2. Summary of main worldwide cellulosic ethanol projects and facilities [5, 6, 7, Companies Websites]. Start Hydrolysis Output Status Company Location Country Raw-Material up Process (Ml/y) (May 2010) year Salamanca Spain Wheat Straw Enzymatic 5 2009 Operational Nebraska US Corn Stover Enzymatic 0.08 2007 Operational Abengoa Corn Starch Kansas US Enzymatic 60 2010 Estimated and Stover ADM Illinois US Corn Stover --0.1 ----Butalco Stuttgart Germany Agr. Residues Enzymatic --2010 Estimated American E. E. Connecticut US Wood waste Enzymatic 56-378 2011 Estimated American Wood Michigan US Chemical 3.4 2011 Estimated Process Residues Bioethanol Osaka Japan Wood scraps Chemical 1.4-4.0 2007 Operational Japan Copenhagen Denmark Agr. Residues Enzymatic 0.016 2006 Operational Biogasol Bornholm Denmark Agr. Residues Enzymatic 5.2 2011 Estimated Izumi Japan Wood chips Chemical 2.1 2002 --Blue Fire Cellulosic California US Chemical 15 2010 Estimated Ethanol wastes Mississipi US Wood wastes Chemical 72 2012 Estimated Colusa Biomass California US Rice hull Chemical 47 >2010 Estimated Zhao Dong China Corn Stover Enzymatic --2006 --CRAC Zhao Dong China Corn Stover Enzymatic 6 ----CTBE Campinas Brasil Bagasse Enzymatic --2010 Estimated Dedini So Paulo Brasil Bagasse Chemical 1.8 2002 --Dong Energy Kalundborg Denmark Wheat Straw Enzymatic 5.4 2009 Operational Dupont Danisco Tennessee US Corn Cobs Enzymatic 0.95 2010 Operational Ecofin Kentucky US Corn Cobs Enzymatic 4.9 2011 Estimated EdeniQ/Logos California US Corn Stover Enzymatic 0.19 2011 Estimated Wood Ethtec Harwood Australia Chemical --2011 Estimated Residues Agr. Residues, Ottawa Canada Enzymatic 2.1 2004 Operational Iogen Hardwood Saskatchewan Canada Cereal Straw Enzymatic 87 2012 Estimated KL Energy Wyoming US Wood chips --5.7 2008 Operational Lignol Energy Vancouver Canada Wood chips Enzymatic 0.1 2009 Operational Marubeni Saraburi Thailand Bagasse Chemical 3 2008 --New York US Wood chips Enzymatic 0.7 2009 Operational Mascoma Michigan US Wood waste Enzymatic 151 2012 Estimated Mission New --India Agr. Residues Enzymatic 0.07 ----Energy Old Town FF Maine US Wood Chips Chemical 8.4 2012 Estimated

Cont. Table 2. Pacific Ethanol POET Qteros SEKAB SunOpta TMO Tsukishima Kikai Verenium Verenium + BP Oregon South Dakota Iowa Massachusetts rnskldsvik rnskldsvik Toronto Surrey Chiba Louisiana Florida US US US US Sweden Sweden Canada UK Japan US US Agr. Residues, wood Corn cobs Corn cobs Corn Stover Wood chips Wood chips Wood chips Agr. Residues Bagasse, Wood Wastes Bagasse, energy crops Grasses Enzymatic Enzymatic Enzymatic Micorbial Chemical Chemical Enzymatic Bacteria Chemical Enzymatic Enzymatic 10.2 0.08 95 --0.15 6.4 2 0.4 0.100 5.3 136 2010 2009 2012 2011 2004 2013 2010 2008 2003 2008 2012 Estimated Operational Estimated Estimated Operational Estimated Estimated Operational --Operational Estimated

Table 3. Summary of main worldwide 2nd generation biofuel projects and facilities, based upon the Thermochemical Platform (Gasification G; Pyrolysis - P; H Hybrid). Product Conversion Technology (Catalytic C; B Biofermentation; Fischer-Tropsch FT). facilities - [5, 6, 7, Companies Websites]. Start Technology Output Status Company Location Country Raw-Material up /Product (Ml/y) (May 2010) year Chemrec Pitea Sweden Black liquor G-C/DME 2.1 2010 Estimated Freiberg Germany Biomass waste G-FT/FT Diesel 18 2008 Operational Choren Bure-Saudron France Wood residue G-FT/FT Diesel 18 2014 Estimated Schwedt Germany Various G-FT/FT Diesel 270 2014 Estimated Wood Waste, Clear Fuels + Colorado US G-FT/FT liquids 0.56 2011 Estimated bagasse Rentech Tennessee US Wood Waste G-FT/FT liquids 75.7 2014 Estimated Woody Coskata Pennsylvania US G-B/Ethanol 0.16 2009 Operational biomass Quebec Canada Sorted MSW G-C/Ethanol 5 2010 Estimated Enerkem Mississipi US MSW G-C/Ethanol 37.9 ----Flambeau River Wisconsin US Wood Chips G-FT/FT fuels 22.7 2013 Estimated Fulcrum Nevada US MSW G-C/Ethanol 39.7 2010 Estimated Bioenergy Gulf Coast Tennessee US Wood Waste G-C/Ethanol 0.76 2008 Operational Energy INEOS Bio Florida US MSW G-B/Ethanol 30.3 2011 Estimated New Page Wisconsin US Forest Wastes G-FT/FT fuels 20.8 2012 Estimated Colorado US Wood Wastes G-C/EtOH-MeOH --2008 Operational Range Fuels Georgia US Wood Wastes G-C/EtOH-MeOH 38-380 2010 Estimated REII Ohio US Agr. Wastes G-FT/FT diesel --2011 Estimated UOP Hawaii US Agr. Wastes P/liquid fuels 0.22 2014 Estimated Woodland Ontario Canada Wood Wastes G-C/Ethanol 0.76 2011 Estimated Biofuels ZeaChem Boardman US Forest Waste H - Ethanol 0.95 2010 Estimated

At this stage pulp and paper companies are positioning themselves towards this new business concept. However, many of them are undertaking this task in partnerships or even in joint ventures. Table 4 reveals the biorefinery actions of some of the worlds largest pulp paper companies. The rising of the biorefinery concept has also boosted the retrieval of alternative pulping technologies, which are considered, by some, to be more suited for the biorefinery implementation than the conventional pulping technologies. Organic solvent pulping was developed on the 70s but it was never considered a mainstream pulping technology. Presently, the use of formic acid, acetic acid or ethanol, at low

temperatures and low pressure, is being considered for the separation of the three big natural polymers from biomass (cellulose, hemicelluloses and lignin), without promoting its degradation. The development of a pulping technology designed specifically to refine lignocellulosic material into its main components can be the basis for a new generation biorefinery concept 3rd Generation Biorefinery. Several companies are developing this technology including: a) Compagnie Industrielle de la Matire Vegetale, CIMV (FRA); b) Chempolis (FIN); c) Lignol (CAN).
Table 4. Summary of main pulp and paper companys actions towards 2nd generation biorefineries. Pulp and Paper Partner Technology Company (JV Company) Neste Oil - FIN 12MW biomass gasification and FT diesel demonstration plant in (NSE Biofuels Oy) Varkaus mill (FIN). Collaboration with VTT and Foster Wheeler Stora Enso (FIN) Biomass gasification and FT diesel demonstration plant in Wisconsin TRI USA Rapids mill (USA) Carbona's gasification technology at the Gas Technology Institutes Andritz AUT pilot plant located close to Chicago (USA) for BTL UPM Kymmene Biomass-based bio-oil test to replace fossil fuels in heating and Metso - SWE (FIN) power generation. Metso's test plant in Tampere (FIN) Lassila & Tikanoja New ethanol and energy production concept that utilises commercial FIN and industrial waste. Collaboration with VTT. 2nd generation biofuel prototype-plant to be established in Several Feedstock Norske Skog connection with Norske Skogs paper mill at Hnefoss (2010-2011). suppliers (NOR) Plan & construct 1-2 full-scale BTL plants in Norway (2014). (Xynergo) Collaboration with Hydro (NOR), an energy company. Weyerhaeuser Chevron USA Develop technology for converting cellulose-based biomass into (USA) (Catchlight Energy) economical, low-carbon biofuels

CONCLUSIONS Implementation of a 2nd generation biorefinery is inevitable due to decreasing profitability of commodity orientated pulp and paper mills and to the World non-fossil carbon economy demand. Presently, there are few 2nd generation biorefinery technology options that are commercial available and/or risk-free. Further developments and validations are still necessary. In the first stage of a 2nd generation biorefinery, biofuels should be the main product target based on its process and energy integration potential, supply chain complexity and market perspectives. By its intrinsic nature, pulp and paper industry should be the starting point of a new biorefinery industry. However, partnerships are essential to secure competitive advantages, reduce costs, control product value chain and mitigate risks. Potential partners include Research Institutions, Feedstock Suppliers, Technology Providers, Transformation/Commercial Companies, End-User Industries, and Venture Capitalists.

REFERENCES
1. IEA, World Energy Outlook 2007: China and India Insights, IEA Publications (2007); 2. BP, BP Statistical Review of World Energy, June (2009); 3. Balensiefer, T., Chemicals from biomass: An industrial Perspective, Biorefining for the Pulp & Paper Industry Conference, Helsinki, Dec. 3rd 2008, 18-19 September (2008); 4. Spath, P. L., Dayton, D. C., Preliminary Screening Technical and Economic Assessment of Synthesis Gas to Fuels and Chemicals with Emphasis on the Potential for Biomass-Derived Syngas, Technical Report NREL/TP-510-34929, National Renewable Energy Laboratory (2003); 5. Johnson, B., Johnson, T., Scott-Kerr, C., Reed, J., The Future is Bright, Pulp and Paper International, October, pp: 19-22 (2009); 6. http://www1.eere.energy.gov/biomass/factsheets.html 7. http://www.thecesite.com/index.html