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chemical engineering research and design 8 7 ( 2 0 0 9 ) 1328–1339

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Chemical Engineering Research and Design
journal homepage: www.elsevier.com/locate/cherd

Thermally integrated bio-syngas-production for biorefineries
T. Bludowsky ∗ , D.W. Agar
Technical University Dortmund, Department of Biochemical and Chemical Engineering, Laboratory of Technical Chemistry B, Emil-Figge-Str. 66, 44227 Dortmund, Germany

a b s t r a c t
Maximising the thermal efficiency of a biorefinery is a major challenge in the production of economically competitive biomass-based chemicals. This paper compares different bio-syngas to methanol routes with respect to their energy demands and proposes a novel heat integration concept. Previous studies on biorefineries have tended to focus on the chemical transformations involved. The defunctionalisation of biofeedstocks required to eliminate the excess oxygen they contain is also a very energy-consuming process, which exerts a considerable influence on the overall yields which can be achieved. In this article we deal with the less appreciated issue of thermal integration by analysing two principle routes for the generation of ‘bio’synthesis gas for methanol synthesis: a conventional high temperature biomass gasification process and a scheme based on aqueous-phase reforming (APR). Low temperature gasification processes below 250 ◦ C, such as APR, permit one to use the heat liberated in the methanol synthesis for the endothermic synthesis gas production step. The composition of the resultant synthesis gas must be modified slightly to meet the demands of the methanol synthesis reaction using a low temperature retro-water-gas shift reaction in a special adsorptive reactor. The results indicate that the low temperature arrangement has an edge in terms of the net energy consumption for a given methanol production and the analysis reveals topics of interest for future research in this area. © 2009 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved. Keywords: Biorefinery; Thermal integration; Synthesis gas; Aqueous-phase reforming; Methanol synthesis

1.

Introduction

The depletion of fossil fuel reserves makes it necessary to find alternatives for both energy generation and the production of organic chemicals. The use of biomass has been proposed as a promising, environmentally compatible and sustainable solution to both problems. Whilst there are a variety of other options available for energy generation, e.g. atomic, solar and wind power, biomass alone can serve as a carbon source for the production of chemicals once fossil fuels are exhausted. It is thus necessary to develop new industrial manufacturing processes for chemicals based on renewable resources. The amounts of biomass required provide a further argument for its use in chemical production rather than for energy generation. Fig. 1 illustrates that the overwhelming proportion of fossil fuels is used for the generation of electrical and thermal energy or in the transport sector, whilst a relatively

small fraction is employed for chemical production. Since the amount of agricultural or other suitable land available for biomass harvesting is limited and must also serve the needs of food production, it can be easily calculated that it is unfeasible to meet even the present demands for energy production using biomass-based fuels, even using second generation lignocellulosic biofuels. On the other hand the use of renewable biomass resources for the chemical industry is a much more viable proposition, offering little competition to other land use needs. Of the 11,050 m2 of usable land available pro capita in 2050, woefully inadequate for energy requirements, it has been estimated that around 400 m2 would suffice to cover the needs of chemical production (Pfennig, 2007). The National Renewable Energy Laboratory (NREL, 2008) has designated the biorefinery concept, analogous to today’s petrochemical refineries, as the most promising approach for the production of biomass-based chemicals. Biorefineries use

Corresponding author. Tel.: +49 (0) 231 755 5332; fax: +49 (0) 231 755 2698. E-mail address: thomas.bludowsky@bci.tu-dortmund.de (T. Bludowsky). Received 13 October 2008; Received in revised form 24 February 2009; Accepted 5 March 2009 0263-8762/$ – see front matter © 2009 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved. doi:10.1016/j.cherd.2009.03.012

Fig. the constituent monomer of cellulose. Werty and Petersen (2004) have identified 12 attractive building blocks for the further synthesis of highvalue biobased chemicals. Cortright et al. making it especially suitable for the gasification of moist biomass. a concept which has the advantage of exploiting the natural synthesis potential available. This represents a considerable sacrifice in terms of yields and efficiencies and requires costly heat-integrated reactor systems. Depending on the raw material. Since the reaction takes place in the liquid phase. There are two major strategies for defunctionalising biomolecules. in contrast to high temperature gasification. gasification and steam reforming lie well above those of the typical chemical processes for converting synthesis gas to chemical. sis. A direct thermal coupling between the exothermic MS or FTS and the endothermic synthesis gas generation is thus not possible. can be used as catalysts (Davda et al. 2006). the energy-intensive evaporation of any water present can be dispensed with in APR.. The heat of reaction needed for pyrolysis or gasification therefore has to be supplied externally by combustion as in the conventional petrochemical plants described above.. 2 it can be seen that the only gasification process enabling an expedient thermal integration of this kind is that of aqueous-phase reforming (APR). 2007). A low temperature process would be more suitable for thermal integration with downstream exothermic processing steps. (2002) have demonstrated. that the operating temperatures for pyroly- Fig. 2 – Temperature levels of various syngas generation processes. 1 – Consumption of fossil fuels in 2006 (IEA. It can be recognised. it cannot process the substantial lignin fraction of the biomass. chemical. 2005. pyrolysis. either as a major pathway in its own right or as an essential component of defunctionalisation strategies (Kamm and Kamm. On the other hand this technique represents a relatively straightforward front-end substitution yielding a feedstock that can be used for conventional thermochemical syntheses in existing plants to produce a wide variety of commodity chemicals. Even so. 30 bar) in the presence of a catalysts into carbon dioxide and hydrogen by means of APR. can be considered as a benchmark: C6 H12 O6 + 6H2 O → 6CO2 + 12H2 0 HR = +627 kJ/mol (1) Methanation occurs as an unwanted consecutive sidereaction: CO2 + 4H2 CH4 + 2H2 O 0 HR = −165 kJ/mol (2) In order to be able to use the synthesis gas produced in the methanol or Fischer–Tropsch syntheses. all these processes have the elimination of unwanted functional groups as a common objective. 2 depicts the temperature levels required for various processes generating synthesis gas from biomass. gasification or steam reforming are commonly used to manufacture biosyngas. 2006).chemical engineering research and design 8 7 ( 2 0 0 9 ) 1328–1339 1329 Fig. thus saving the compression energy that would otherwise be need for most downstream processing. By way of an example. physical. which can only be provided through the combustion of by-products or some of the fossil fuel feedstock itself. The problem with such endothermic processes is the high temperature level required for conversion using conventional technologies. the APR of glucose. From Fig. As a consequence of these advantages many biorefinery concepts incorporate syngas generation. The major disadvantage of APR is that it is only able to convert the carbohydrate monomers derived from cellulose and hemicellulose and. Moreover synthesis gas or syngas generation is perhaps more appropriate for decentralised biomass processing and can be easily transported over pipelines to larger plants for further conversion. hydrolysis and fractionation of the biomass would thus be necessary before APR could be applied (Huber and Dumesic. The second strategy is to transform the biomass completely into the C1 feedstock synthesis gas. 2008). Ideally. A further advantage is that the gas is generated at higher pressure. Today’s petrochemical plants face a similar predicament: the initial functionalisation of alkanes to carbon monoxide or alkenes in steam reformers or steam crackers necessitate temperatures of around 900–1000 ◦ C. it is necessary to . which suppress the chemically undesirable methanation reaction. such as methanol synthesis (MS) or Fischer–Tropsch-synthesis (FTS). biological and thermal treatments and processes to fractionate and transform the biomass into platform chemicals that can be used for biobased commodity chemical production (Kamm et al. that carbohydrate monomers can be converted under relatively mild conditions (225 ◦ C. 2004).. the resulting molecules still often have to be defunctionalised further prior to their use for commodity chemical production and their integration into established chemical manufacturing network structures is a daunting challenge. providing the heat required for synthesis gas generation directly from the heat of reaction liberated by the MS or FTS could permit drastic improvements in the overall efficiency of biomass utilisation. On one hand this concept has the disadvantage that a lot of energy is needed to rupture carbon chains. The first is to breakdown the biomass partially into its underlying building blocks. which must then be reconstructed with considerable effort in the subsequent synthesis and processing steps. A pre-treatment. Supported Pt/Al2 O3 or Raney NiSn. Shabaker et al. Due to the high functional nature of the molecules present in the biomass.

which takes place on a CuO/ZnO/Al2 O3 catalyst. provide selective water adsorption characteristics (Richrath. CO + 2H2 CO2 + 3H2 CH3 OH 0 HR = −90 kJ/mol 0 HR = −49 kJ/mol (4) (5) CH3 OH + H2 O Fig.. CO2 + H2 CO + H2 O 0 HR = +41. the well-defined pore networks of which.. In order to permit a reaction temperature for the RWGS which is as low as possible whilst still permitting a reasonable conversion. an in situ adsorption of the water vapor formed takes place simultaneously with the catalytic reaction. 3 – Cycle phases of sorption enhanced RWGS adapted from Carvill et al. The first industrial methanol synthesis was implemented by BASF in 1923 on a Zn/Cr2 O3 -Katalysator at temperatures between 300 and 450 ◦ C and pressures of 250–350 bar. 1996. In the concept presented by Carvill et al.2 kJ/mol (3) The maximal conversion in the RWGS is dictated by the chemical equilibrium of reaction (3). Methanol is one of the most important basic chemicals manufactured globally in terms of sheer volume (41 × 106 t/a in 2007) (PCI . The main shortcoming of this process is naturally the cyclic operation. conversion of 50% or more can only be attained at temperatures in excess of 800 ◦ C in conventional reactors. Carvill proposed a “Sorption-Enhanced Reaction Process” (Carvill et al. The modified synthesis gas obtained from RWGS can then be fed to the methanol and Fischer–Tropsch syntheses. 2008). Apart from this. since the high reaction temperature would render thermal coupling with the MS or FTS impossible. as it provides an acceptable reaction rate for the reverse reaction at the temperature envisaged (Amadeo and Laborde. . for example. the non-linear adsorption isotherms of the pertinent zeolites exhibit high adsorption capacities even at low water vapor partial pressures. thus negating the advantage of the aqueous-phase reforming in this respect. for example in the NaX und 3A forms. 2007). for the regeneration of the adsorbent (Fig.Ockerbloom & Co. This can be done using the retro-water-gas shift reaction (RWGS). Normal operation of an RWGS reactor is thus unsuitable for an energy-efficient. The removal of the water vapor from the reaction mixture shifts the position of the chemical equilibrium toward the increased production of carbon monoxide.1330 chemical engineering research and design 8 7 ( 2 0 0 9 ) 1328–1339 raise the concentration of carbon monoxide in the gas. In this manner. The primary reactions occurring in the methanol synthesis reactor are the parallel hydrogenation of carbon monoxide (4) and carbon dioxide (5) to methanol and the reverse water-gas shift reaction (3). which means that at least two reactors must be operated in parallel to ensure continuous operation of the plant. (1996). A standard low temperature water-gas shift catalyst of CuO/ZnO/Al2 O3 can be used for this purpose. The adsorptive reactor for RWGS comprises a mixed fixed-bed of catalyst and adsorbent pellets. 1995). (1996) there are four further phases in addition to the reaction/adsorption period. take up water vapor selectively and be stable under cyclic operation under the prevailing conditions. 1996). The adsorbent must possess a high adsorption capacity at the reaction temperature of around 250 ◦ C. 3). 2000).. thermally integrated carbon monoxide production. if desired. one can achieve almost complete carbon dioxide conversion at temperatures as low as 250 ◦ C. Nararaj et al. Today the process is mostly carried out on a Cu/ZnO-based catalyst at lower pressures (50–100 bar) and temperatures (230–300 ◦ C) (Fiedler et al. Due to the endothermic nature of the reaction. These specifications are best met by zeolites. The reactor is then flushed with the product gas (Step 4) and the pressure raised back up to the operating level for the reaction phase (Step 5). The first stage in desorption is the depressurisation of the reactor (Step 2) and subsequent stripping of the fixed-bed with an inert gas (Step 3).

Hydrocarbon fuels may also be generated from methanol with the help of the methanol to gasoline (MTG) technology (Tabak and Yurchak. cobalt or ruthenium can be used as catalysts (Huber et Fig. 1994). which was discovered in the first half of the twentieth century and developed for large-scale production during the Second World War. Methanol is itself a feedstock for a whole series of further chemicals. By means of the methanol to olefin (MTO) process developed by Mobil (Stöcker. 1990). since the staged adiabatic reactor does not permit such an effective removal of the heat of reaction. adapted from Kamm and Kamm (2007). For optimal conversion the synthesis gas ratio (H2 –CO2 )/(CO + CO2 ) should be slightly above 2 in the methanol synthesis feed (Cheng. 1999) or the methanol to propylene (MTP) process recently presented by Lurgi (2008) methanol can also serve as a basic chemical for polymer production.chemical engineering research and design 8 7 ( 2 0 0 9 ) 1328–1339 1331 Fig. MTBE (9%) and acetic acid (9%) (Spath and Dayton. For this reason methanol represents a critical link in synthesis gas based product network structures. 2003). The direct synthesis for fuels from synthesis gas can be carried out directly using the Fischer–Tropsch process. The most widespread production processes for methanol are the quasi-isothermal Lurgi process and the adiabatic ICI process (Cheng. 4 – Two-platform concept of a conventional LCF biorefinery. Iron. The largest amounts are used in the manufacture of formaldehyde (35%). 5 – Process concept for a heat-integrated biorefinery. only the quasi-isothermal multitubular reactor need be considered further. 1994). . For the thermal coupling sought here.

2. (1992) corresponds to typical results for the steam gasification of biomass and is given in Table 1. will be developed as will a corresponding system comprising a conventional high temperature gasification with a downstream methanol synthesis. 250 ◦ C for the gasification in the APR reactor at 225 ◦ C. RWGS and MS arrangement . In order to attain a high level of hydrogen in the product gas. For the purposes of the balance equations an indirect gasification process was selected. but their combination in this way permits one to utilise the heat of reaction liberated in the methanol reactor at c. alternatively. only processes yielding a very low level of inert gases need be considered (Bridgwater. thus rendering further adjustment through the water-gas shift reaction superfluous. which is operated at around 800 ◦ C. Balance equations Mol% 51 24 19 6 In this section the process concept for synthesis gas production from biomass proposed in the previous section will be compared with a conventional gasification scheme. The lignin arising in this process can either be directly converted to chemicals or used to meet other energy demands within the biorefinery. The thermodynamic data required were calculated with the help of the Predictive Soave–Redlich–Kwong model (Holderbaum and Gmehling. since it provided the most appropriate comparison with the APR. Both processes involving synthesis gas generation and methanol synthesis are designed to produce one tonne of methanol per hour as a benchmark. in which waxes and long chain hydrocarbons predominate. In the indirect gasification.. so that complex product mixtures are always obtained.2 kJ/mol 0 HR = −206 kJ/mol (7) (8) (9) The product gas composition given by Herguido et al. watergas shift (8) and the methanation (9) reactions were taken into account. Component H2 CO CO2 CH4 2.. The sugars thus produced can either serve as substrates for further chemical or biological transformations to chemical intermediates or. 4). 2007). cellulose and hemicellulose. must be burnt to heat the gasification reactor. 5. 2006). All the mass and energy balances were implemented in ASPEN PLUSTM software. Attempts to overcome the intrinsic ASF-distribution have so far proved fruitless (Huber et al. 2006) and FTS can be practised in one of two basic variants: the high temperature FTS (330–350 ◦ C) producing mostly short chain hydrocarbons (gasoline) and light olefins in a fluidisedbed reactor usually based on the design of SASOL (Kaneko et al. 1992). from which further platform chemicals are then recovered as described earlier. Of course it can nevertheless be used elsewhere within the biorefinery. In this process a portion of the biomass. In accordance with the data provided by Herguido et al. Thus only either indirectly heated or oxygen-blown gasifications remain as options. C6 H12 O6 → 6CO + 6H2 CO + H2 CO + 2H2 CO2 + H2 O CH4 + H2 O 0 HR = +610 kJ/mol 0 HR = −41. The gasification (7). All thermal and electrical inputs and outputs given thus refer to this production rate. since the temperature level is too low. usually the chemically less accessible lignin. To fulfil the mass balance requirements with this composition the following overall reac- Table 1 – Product composition for steam-gasification (Herguido et al.1332 chemical engineering research and design 8 7 ( 2 0 0 9 ) 1328–1339 al. hemicellulose and lignin. e. In this concept some of the biomass is broken down into the basic component fractions of cellulose. (1992) in which the gasification product gas was reported to exhibit a H2 /CO ratio of 2. The synthesis gas composition required is adjusted by means of the adsorptive RWGS reactor. which must then be fractionated prior to subsequent processing for chemical production. To simplify matters. for thermohydrolysis. Gasification processes For the high temperature gasification of biomass to generate synthesis gas. The modification of the standard LCF biorefinery concept proposed here is illustrated in Fig. the pressure losses in the individual unit operations have been neglected. a steam gasification was chosen.1. To help visualise the concept being proposed for thermal integration the dual platform concept (sugar and syngas) for a lignocellulosic feedstock biorefinery) (LCF) as described by Kamm and Kamm (2007) will be considered (Fig.. so that the synthesis gas is uncontaminated by the flue gas from the air-blown combustion and thus contains no nitrogen. Air-blown gasification can thus be rejected because of the high nitrogen concentrations in the resulting synthesis gases. The heat of reaction from the MS or the FTS cannot be used for the purpose. the synthesis gas generation and the combustion take place in spatially segregated reactors. CO + 2H2 (1/n)Cn H2n + H2 O 0 HR < 0 (6) A drawback of FTS is the inherent chain growth mechanism according to Anderson–Schulz–Flory-probability distribution (ASF) (Güttel et al. The operating conditions were selected to reflect the measurements of Herguido et al. For this purpose a flowsheet for the APR. 1991). None of the processes involved are actually new. The last two components are then broken down into their monomeric carbohydrate constituents using biological and/or chemical processes. 1984). be converted into synthesis gas with the help of the APR process.. since it is the underlying building block of cellulose and its properties are well known. The FTS (6) is strongly exothermic and thus eminently suitable as a heat source for the APR process. The biomass is first fractionated into lignin.g.. which is then either used in chemical production or for the associated generation of energy to cover the biorefinery requirements. This ratio can be manipulated easily by varying the amount of steam fed. Glucose was used as a model component for biomass.. The methanol formed in the following synthesis step can either be used directly or further converted to whatever products are desired in the manner described earlier. 2001) or the low temperature (220–250 ◦ C) slurry bubble column reactor technology (Güttel et al. (1992) the gasification was considered to be carried out at 800 ◦ C and atmospheric pressure. 2007). The remaining biomass feedstock is converted to synthesis gas by gasification processes.

For balancing purposes only the formation of methanol via CO (4) was considered. tion equation was derived (10). since the gasification process under consideration is operated with external heating and the amount of biomass to be burnt to meet the heat demand is calculated retrospectively.7H2 O → 6.32H2 + 2. 2005). Since only minimal deviations were observed from the gasification process selected. tar and oil was neglected.. The process flowsheet is depicted in Fig. the gasification process itself.. can be used. The compression of the synthesis gas up to the methanol synthesis pressure of 50 bar was assumed to be carried out in two stages with intermediate cooling. Austria (Hofbauer et al. the cooling of the gaseous products. In the literature. The pressure selected was somewhat higher than that given in the literature cited to save on subsequent compression of the gas for the methanol synthesis. In practice one can use a simple nonregenerative water scrubber for removing carbon dioxide from pressurised gas streams. (2002). Component H2 CO2 CH4 Mol% 57 36 7 . 2008) with a water-gas shift conversion was also used for one set of balance calculations.85:0. 2000). 6. Wiese. In the actual indirectly heated gasification. The formation of coke. The methanol synthesis was carried out at 250 ◦ C and 50 bar. APR process The flowsheet proposed for the APR process is based on the values provided in the literature by Cortright et al. The heat dissipation into the cooling system was assumed to be at a low temperature level and thus non-recoverable. Other liquid phase reactions were neglected. since it was assumed that the soluble organic compounds thus formed would be converted to synthesis gas during subsequent passes of the recycle stream through the reactor. the compression of the synthesis gas up to the methanol synthesis pressure. The reaction takes place at 225 ◦ C and 50 bar. For reasons of brevity.chemical engineering research and design 8 7 ( 2 0 0 9 ) 1328–1339 1333 Fig.. thus reducing the amount of biomass needed for this purpose. 6 – Gasification process with methanol synthesis. 2002. The recycle flow could be ascertained using the specified inlet concentration of the APR reactor of 1% m/m Table 2 – Product composition after aqueous-phase reforming. By-product formation and the resulting purification of the raw methanol that would be necessary were not considered.39CO2 + 0.05. C6 H12 O6 + 1. which in practice in almost achieved with the help of a recycle stream (Fiedler et al.1:0. further details of the process and the heat exchange networks will not be presented in detail. the coke and tars formed would be burnt. It was further assumed that the feedstock is entirely converted to synthesis gas in the gasification. the methanol synthesis and the cooling of the final product stream. The carbon dioxide separation is not explicitly modelled in the energy balance.92CO + 2. as in the processing of methane from biogas plants (Kapdi et al. (1992) can probably be considered representative for atmospheric pressure steam gasification processes. the energy demand for CO2 removal using mixtures of secondary and tertiary amines in a two stage absorber is estimated to be around 30 MJ/kmol CO2 . The level of conversion of glucose to gaseous products was set at 50%.69CH4 0 HR = +446 kJ/mol (10) For purposes of comparison with this gasification process. the results for the steam gasification described by Herguido et al. The aqueous reforming (1) and methanation (2) reactions were taken into consideration. thus fulfilling the overall reaction equation. the CO2 removal process. This assumption is justified. The energy balance for the compression assumed an isentropic process with an estimated efficiency of 72%. As an indication of the expected product distribution for atmospheric gasification at 800 ◦ C the results of Bridgewater (1994). showing a ratio of Gas:Chars:Tars = 0. the product gas composition from an operational technicalscale process employing a fast internal circulating bed (FICFB) biomass gasification in a power station at Güssing. An overall conversion of 100% was assumed. The overall energy balance of the gasification process considers the feedstock heating and evaporation. It is assumed that the energy requirements for this step are similar in both processes and thus cancel one another out. 3.

For the methanol synthesis and all other unit operations the same conditions and assumptions were employed as in the high temperature gasification process described previously. The assumption of ignoring the adsorption/desorption enthalpies in the retro-water-gas shift (RWGS) reactor can be justified briefly as follows: in comparison to the adsorption enthalpy released ( HR Ads = −75 kJ/mol. They attribute this phenomenon Table 3 – Mass balances.04CO2 + 0. It can be seen that for the APR + RWGS-process more glucose must be provided for the same amount of methanol. continuous operation of the RWGS was assumed. and thus the overall adsorptive reaction process is only mildly exothermic. The energy required for compression during the regenerative cycle of the RWGS reactor was not taken into account. the driving force for desorption is the depressurisation (e.. to improve process economics by reducing equipment dimensions. Nevertheless. This is a consequence of the larger amount of methane formed as a by-product in the APR reaction. 1996) the endothermic reaction enthalpy of RWGS is lower ( HR RWGS = +41 kJ/mol). which require the same period for adsorption and desorption. (2002). (11) 4. In order to obtain results consistent with the reaction system given above. which in practice would be realised by tandem operation of at least two reactors in parallel. In our model we have assumed two RWGS reactors operated in The solution of the mass balance equations for the processes presented in the previous sections yielded the results given in Table 3. glucose. as it is anticipated that it would be consumed regeneratively during the subsequent adsorbent regeneration through decompression. Davda and Dumesic (2004) and Davda et al. These two reactors are treated as a single unit operation and therefore in our model only the overall external heat input needed to cover the reaction enthalpy is supplied. It would be desirable to cut the recycle flow rate in the APR reactor by operating at higher glucose concentrations. The assumed composition of the synthesis gas generated is given in Table 2.16H2 + 5. the regeneratively stored heat is then consumed by the desorption process. Carvill et al. from 50 bar to atmosphere pressure). However. the heat for the RWGS reaction still of course has to be provided regardless of this regenerative heat exchange process. which is based on the measurements of Cortright et al.g. Gasification process Stream Water Glucose APR + RWGS-process Stream Water Glucose Inlet [kg/h] 328 1925 Inlet [kg/h] 4504 2068 Gasification process Stream CO2 MeOH Off-gas APR + RWGS-process Stream Condensed water CO2 RWGS-water MeOH Off-gas Outlet [kg/h] 1124 1000 129 Outlet [kg/h] 3662 1171 562 1000 177 . that largely reappears as condensate product. For this modest amount of heat. the values were modified slightly. 7 – APR + RWGS + MeOH-synthesis process. The temperature excursions associated with such internal regenerative heat recovery can be minimised by incorporating additional thermal ballast in the fixed-bed or by using phase change materials to enhance isothermal heat storage capacities. In the desorptive phase. (2005) report that the hydrogen selectivity diminishes dramatically and hydrocarbon levels rise when 10% m/m glucose feed concentration is used. The flowsheet is depicted in Fig.08H2 O 8. The reverse water-gas shift reaction (3) achieves a carbon dioxide conversion of nearly 100% during the reaction/adsorption phase (Carvill et al. but nevertheless slightly higher in the APR process because the H2 /CO2 ratio in the synthesis gas formed is somewhat less than twice the H2 /CO ratio in the high temperature gasification process. One thus obtains the following overall reaction for the APR (11): C6 H12 O6 + 4. the adsorptive RWGS reactor was modelled as a normal stoichiometric reactor with subsequent water vapor removal.1334 chemical engineering research and design 8 7 ( 2 0 0 9 ) 1328–1339 Fig. since it is almost negligible by virtue of the low volumetric flows involved. Results As a simplification. Assuming only minor temperature changes during cyclic operation. 1996). For the simulation. 1999). The amount of carbon dioxide purged from both processes is similar. 7. The heat of adsorption has been neglected in the calculations. it is anticipated that the fixed-bed can serve as a regenerative heat store over the reactive-desorptive cycle (Nieken and Watzenberger..96CH4 0 HR = +385 kJ/mol parallel. Furthermore the much greater water feed to the APR process is apparent.

91 −14.56 3.97 −3. However. APR + RWGS-process Stream Inlet water Inlet glucose APR reactor inlet APR reactor outlet RWGS reactor inlet RWGS reactor outlet gas RWGS reactor outlet H2 O MeOH-reactor outlet Off-gas MeOH ˙ m [kg/h] 4504 2068 287110 287110 1740 1177 562 1177 177 1000 Vapor fraction 0 0 0 0.26 3.47 −4.75 2.06 4.88 −8.48 T [K] 25 ◦ C 25 ◦ C 225 ◦ C 225 ◦ C 250 ◦ C 250 ◦ C 250 ◦ C 250 ◦ C 25 ◦ C 25 ◦ C Gasification process Stream Inlet water Inlet glucose Gasification inlet Gasification outlet MeOH-reactor inlet MeOH-reactor outlet Off-gas MeOH ˙ m [kg/h] 328 1925 2253 2253 1129 1129 119 1000 Vapor fraction 0 0 1 1 1 1 1 0 Cp [kJ/kg K] 4.92 2.31 −7.20 −6. For the reaction temperature level of 800 ◦ C.01 −14.65 −2. using the ASPEN PinchTM software.023 1 1 0 1 1 0 Cp [kJ/kg K] 4. In the composite curves for the gasification shown in Fig. it is apparent that the heat of reaction must be supplied externally.45 2.51 2.89 −5.20 −14. 1983).70 −7.06 2. the methanol reactor could supply roughly 70% of the heat needed for the APR reaction.87 −6. This apparent contradiction is due to the evaporation of water within the reactor. Overall the APR reactor consumes 1268 kW for the endothermic reaction and 1589 kW for water evaporation. The most important thermal properties and streams for both processes can be found in Table 5.48 T [K] 25 ◦ C 25 ◦ C 800 ◦ C 800 ◦ C 250 ◦ C 250 ◦ C 25 ◦ C 25 ◦ C . albeit much less than for the APR reactor. Calculation of the composite curves was done by the method presented from Lindhoff (Linnhoff and Hindmarsh.82 5. Gasification process Unit HeatEx3 Gasification APR + RWGS-process Unit HeatEx1 APR HeatEx2 RWGS reactor Cold streams [kW] 1783 1385 Cold streams [kW] 1444 2857 279 337 Gasification process Unit HeatEx4. It can be seen that.25 2. without this latent heat effect.79 2.39 2.26 3. it must be remembered that heat input is also required for the RWGS reactor. 8.61 2. although the reaction enthalpy for the APR is somewhat lower.88 −8.5 bar). combustion Table 5 – Thermal properties. but the fraction of water vapor in the gas following phase separation in nevertheless about 56%.84 4. The pressure of the APR process (50 bar) lies well above the boiling pressure at the prevailing temperature of 225 ◦ C (25. A pinch analysis was carried out for both processes. assuming a minimal temperature difference of 10 ◦ C between hot and cold streams in heat exchangers. When one considers the heat and energy consumptions of the two processes given in Table 4 one is struck by the higher heat energy requirement of the APR reactor compared to the high temperature gasification.90 −5. MeOH-reactor Product cooler (3) APR + RWGS-process Unit Condenser (1) MeOH-reactor Product cooler (2) Hot streams [kW] 994 884 438 Hot streams [kW] 3064 886 437 Gasification process Unit Compressor 1 Compressor 2 APR + RWGS-process Unit Pump Electrical power [kW] 263 465 Electrical power [kW] 27 to undesirable liquid phase reactions and propose the hydrogenation of glucose to sorbitol in an additional upstream reactor to counteract this difficulty.25 2. since sorbitol exhibits higher hydrogen selectivities at higher inlet concentrations in the APR. due to the high vapor pressure of water at this temperature.788 H [MJ/kg] −15.72 −4.78 H [MJ/kg] −15.chemical engineering research and design 8 7 ( 2 0 0 9 ) 1328–1339 1335 Table 4 – Heat exchange and energy demands.72 −4.

9) it should be noted. the RWGS reactor must be externally heated. the improvement in the thermal balance at higher pressure must be set off against the increased alkane concentrations in the mass balance. From a general point of view only relatively little poorly utilisable thermal energy arises in this process. In practice the relatively high temperature level of 250 ◦ C would certainly make it an attractive proposition for alternative thermal applications in the biorefinery. 8 – Composite curves—gasification process. is the only suitable process which can cover this requirement. 9 – Composite curves—APR + RWGS-process at 50 bar. this amount of heat is entirely inadequate to meet all the thermal needs of the APR. However. This measure is still energetically attractive when the electrical power is weighted 2. Determining overall energy requirement in this manner (i. 10. since the flue gases containing a large portion of the heat of combustion will leave the combustion reactor and only some .1336 chemical engineering research and design 8 7 ( 2 0 0 9 ) 1328–1339 Fig. However. 3790 kW). A comparison of the two processes reveals that under the prevailing conditions the APR process has a higher external heat demand than the gasification process. This cuts the external heat input necessary by roughly 40% (816 kW) in comparison to the gasification. since too much water is being evaporated in the APR reactor. thermal + electrical power inputs) manifests a clear advantage for the APR process over the gasification (2442 kW vs. In actual operation. Increasing the liquid feed pumping power to realise this would probably present little difficulty. The pinch temperature for this process has a value of 245 ◦ C. as a consequence. for example biomass solubilisation. about 50% of APR heat demand can now be covered by the heat from the methanol synthesis.e. The intended effect of saving thermal inputs cannot be achieved. In the mass balance for the high temperature gasification it was assumed that the process was externally heated. since no other heat source is available for this purpose. However. and. that the entire heat production in the methanol synthesis can be consumed in the APR reaction. It is clear that in this case only a relatively small part of the heat requirement of the APR reactor arises due to evaporative water losses with the product gases. For the composites curves of the APR process (Fig. synthesis gas from the high temperature gasification process requires a much greater power input than feeding the glucose solution into the pressurised APR system. This would most likely entail considerable equipment costs and detract from the simple elegance of the APR process. An alternative solution might be to try and recover the heat of condensation from the water vapor lost with the gas by some form of vapor recompression. Davda et al. Since the internal process heat source has been exhausted. despite the thermal coupling with the methanol synthesis. Fig. (2005) report an increase in hydrogenation activity at higher pressures. the heat supply to the gasification is obtained from combustion of part of the biomass feedstock or other fuel. For the case in hand 354 kg/h of dry glucose must be burnt to cover the heat demand of the gasification (neglecting heat transfer losses). The true amount required will be considerably higher. The waste heat from the methanol synthesis is only partially utilised in the process considered. examining the electrical power requirements leads one to revise this evaluation somewhat. with the result that selectivities tend to shift from hydrogen to alkanes. 10 – Composite curves—APR at 100 bar + RWGS-process. Assuming a power station efficiency of 40% for electrical power generation means that the electrical energy must be weighted by a factor of 2.5 higher than the thermal energy. In practice. The evaporation of water in the APR reactor leads on one hand to a substantial increase in the external heat requirement and on the other necessitates an almost equally large increase in the cooling capacity. whilst the pump power required increases from 27 to 41 kW. even allowing for the increased cooling capacity for the former. The pinch temperature in this case is 220 ◦ C. Ignoring this chemical effect and assuming the same gas composition as before leads to the composite curves for operation at 100 bar shown in Fig. In order to suppress the evaporation of water in the APR one could employ higher operating pressures in the APR reactor. Unfortunately we are unaware of any literature providing reliable data on gas composition for APR at 100 bar. reflecting the efficiency of electrical power generation. since only a small fraction of the heat of condensation can be effectively utilised within the process.5 times more than thermal power. The compression of the Fig.

the condensate was recycled as water feed. because it was assumed that most waste heat could be used elsewhere within the biorefinery (for example. Nevertheless. The costs for cooling were neglected. the largest contribution to the simplified operating costs comes from the biomass feedstock in both cases. An alternative would be an autothermal oxygen-blown gasification under pressure. a point which seems to have been overlooked in the past. in the hydrolysis of cellulose and hemicellulose). The balance of the carbon is present in the form of the by-product methane. On the other hand the immense costs needed for the large compressors in the gasification can be saved. and the need for at least two adsorptive RWGS reactors will increase the investment costs still further. the . With theses assumptions. is incomplete it is difficult to provide a reliable assessment of this technology. The carbon balance could be improved dramatically if hydrogen could be introduced directly to adjust the synthesis gas composition. but by no means impossible hurdle (Freihling et al. on long-term catalyst performance with closed recycle loops for example. such as solar or wind energy. This leads to a slight edge over the gasification with respect to the operating costs for the test case considered here. this would only make sense if the hydrogen was derived from non-fossil. The advantage of the APR process in this instance would be that the RWGS reactor is already present and just needs to be enlarged to accommodate a larger throughput.chemical engineering research and design 8 7 ( 2 0 0 9 ) 1328–1339 1337 of the heat of combustion will thus be imparted to the heat transport medium. 2005). elegantly circumventing the need for air separation processes (Dietenberger and Anderson. 2006). It is therefore not the thermal integration that leads to the advantage of the proposed APR scheme. For the indirectly heated steam gasification with circulating fluidised bed and an additional combustion chamber (e. it should be clearly recognised. 39% of the carbon fed to the APR process is lost in the form of carbon dioxide. The carbon balance of both processes studied is poor. (2002) give the energy demand for cryogenic oxygen recovery (99% O2 ) as 1100 kW h/tO2 . 5. whereas for the gasification this step must be grafted on. it would especially favour the oxygen-blown gasification. For the gasification it was assumed that the enthalpy for the reaction would be supplied by the combustion of 354 kg/h glucose. Carbon dioxide could then be completely converted to synthesis gas using RWGS and the costs for its separation could be avoided. If the energy demand of our gasification example were to be met by internal combustion with oxygen. i. In the APR process. Only when water evaporation is suppressed at higher operating pressure do the advantages of thermal coupling between the methanol synthesis and APR emerge. the APR process appears to have a slight economic edge over the gasification option with costs of (305 D /(h tMeOH )) against (324 D /(h tMeOH )). such as the methanol synthesis. 2007). The oxygen thus introduced must be eliminated as CO2 . In terms of the technical risk. if any. Electric energy was priced at 10 Eurocent/kW h and thermal energy at 4 Eurocent/kW h. Failure to resolve this issue means that APR offers little advantage thermally over a conventional gasification. the APR process has the advantage that it is able to furnish the operating pressure for the methanol synthesis more favourably through pumping liquids. Discussion The process proposed here for the generation of bio-syngas envisages the production of synthesis gas in a biorefinery at much lower temperature levels than conventional high temperature gasification processes and would permit thermal integration with exothermic downstream processes. with that of the compression of the synthesis gas from an atmospheric gasification. of course. by the liquefaction of air for example. 2007). renewable energy sources. which requires less electrical energy than compressing gases. When one considers the entire energy demand. such as sand. The carbon ‘loss’ is mainly a consequence of the fact that one must add water in the reforming step to attain the syngas ratio of C:H:O = 1:4:1 needed for methanol. Ecologically. The second most important contribution differs for the two processes. be used elsewhere in the biorefinery. Should such a hydrogen source be available. Up to 70% of the heat of reaction needed for the APR could be met with heat released from the methanol synthesis. As expected. however: heating costs for the APR process and compression outlays for the gasification process. Furthermore. since the oxygen from the electrolytic hydrogen generation could be fed directly to the gasification. the resultant energy requirement for oxygen production would be 415 kW h/tMeOH ) as opposed to a compression energy of 728 kW h/tMeOH for atmospheric operation. The introduction of the biomass feedstock into the pressurised reactor represents a difficult. The price for glucose from lignocellulose was set at 10 Eurocent/kg (Huber et al. On one hand the APR reactors will be much larger than those for gasification.. but rather achieving the system pressure by pumping liquids in place of more energetically extravagant gas compression. a saving of 43%. but is lost as far as the gasification is concerned. of course. One possibility of overcoming the disadvantage of high compression costs in the gasification process would be to operate the gasification under pressure in the range of the pressure required for the downstream synthesis. The cost of the water feed was taken as 1 D /t. Even if the technical problems of an oxygen-blown pressurised gasification can be overcome. For a rough estimate of the variable operating costs (energy and raw materials) for the APR process at 50 bar and gasification with methanol synthesis under the conditions given. which seems a distant prospect at present. 2002). and this rises to 49% for the high temperature gasification. it would still necessary to compare the energy requirements for generating pressurised oxygen. as is being presently studied in the CHRISGAS project (Albertazzi et al. reference prices for the energy and material inputs must be defined.g. the well known and industrially applied gasification processes have a clear lead when it comes to questions of scale-up and similar issues. The residual heat in the flue gases can.. Bisio et al. industrial experience with APR or adsorptive RWGS reactors and since the data available. at which water evaporation is suppressed. In order to assess to process economics more objectively one needs to consider the investment costs for the two processes as well. In the case studied here the operating costs would drop to 258 D /(h tMeOH ) for APR operation at 100 bar. The benefit of thermal integration only becomes apparent at higher operating pressure. due to the inherently slower reaction kinetics. For the APR process only 45% of the carbon in the biomass feedstock is to be found in the methanol product and for the gasification only 41%. the FICFB process) the technical challenges for an operation at higher pressure have not yet been surmounted and an implementation in the foreseeable future is unlikely (Ciferno and Marano. As there is little. that the heat balance for this process is very adversely affected by the high energy demand imposed by water evaporation in the APR reactor..e.

The APR process. Reaktoren für die Fischer–Tropsch-Synthese.. where the broad product spectrum is less of an issue.. The APR process presented can of course be used for thermal integration in conjunction with the Fischer–Tropsch process.A.B. Superior space-time yields represent a clear advantage of the APR process over competing biological process that is unlikely to be endangered. 46(26): 8863–8874.V. p. 2007). 326 Ciferno. because the conditions in the APR are insufficient to achieve its conversion. (London. G... Chemical processes are able to treat a broader spectrum of feedstocks and do it more rapidly. However.R.R. 106(1–4): 297–300. in Ullmann’s Encyclopedia of Industrial Chemistry. Shabaker. It has even proved possible to combine the APR and FTS steps in a single reactor providing excellent thermal integration (Simonetti et al.D.N. 79(5): 531–543. There are developments underway to improve matters. and Marano. Bridgewater. Chemical Communications.S.. Kunz. T. and Dumesic. In view of this. 2006). Vision of the US biofuel future: a case for hydrogen-enriched biomass gasification.gov Cortright.. (Dekker. 2002.D. the overall energy efficiency of the lignin combustion could probably be enhanced. which could then make a larger contribution to heat integration.. J. and development potential. T. 2007).E.. J. W. 2007. F. J. G. When one considers the feasible feedstocks for the APR and gasification processes. 29(11): 1743–1771. A prerequisite for the large-scale implementation of such technology is further research to clarify the considerable risks still posed by the long-term operation of the APR and the cyclic operation of a RWGS reactor. H. The low energy demand and the direct production of a chemical (e.W. since evolution has compelled the microorganisms involved to maximise the energy yield available from such reactions. G. The investigation of APR processes under higher pressure would seem to offer a particularly promising avenue for research. Dietenberger.. Applied Catalysis B: Environmental. E. 344 Carvill. et al. but yields and reaction rates are still very low (Jeffries. (1): 36–37. J.-H.. R. (Wiley-VCH. (Blackie Academic and Professional.. Whilst the heat of combustion of the lignin separated in a biorefinery must be used directly at high temperatures for the gasification process.A. Biological systems may nevertheless indicate the asymptotic carbon efficiencies which may be achieved..P..R. (2002). D..R. R. Production of FT transportation fuels from biomass. (1994). it is obvious that APR is more suitable for biomass with a higher moisture. Hydrogen-production from the low-temperature water-gas shift reaction—kinetics and simulation of the industrial reactor. New York). 2000. Industrial & Engineering Chemistry Research. Spath and Dayton (2003) and Hamelinck et al. This would be particularly interesting for the production of gasolines for the transport sector.doe. 56(1–2): 171–186. .. and Sircar. 418(6901): 964–967. P. APR is to some extent in direct competition to biotechnological fermentation processes. R. Davda. Renewable hydrogen by aqueous-phase reforming of glucose. Davda. p. and Koch. Catalysis Today. The technical feasibility of biomass gasification for hydrogen production. M. A. and Witte. can tolerate biomass of any moisture content. Cortright. Energy.P. R. AIChE Journal. 2005. 1189–1192.W.C. Germany. .. (U. J.A. A.B. (2004) report that the price for biomass-based FTS-diesel is 40–50% higher than that for methanol or hydrogen from renewable feedstocks. 2004. Güttel. even when the changes necessary to the present distribution infrastructure and the power trains of existing automobiles are taken into consideration. Ullmann. Fermentation processes often suffer from the extreme substrate selectivity of the microorganisms and low space-time yields. Faaij.. National Energy Technology Laboratory).J. Weiss.netl. Petersen. Chemicals and Hydrogen Production. pp. Schuster et al. B. 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