J.

of Supercritical Fluids 47 (2009) 391399

Contents lists available at ScienceDirect

The Journal of Supercritical Fluids

journal homepage: www.elsevier.com/locate/supflu

Review

Hydrothermal biomass gasication

Andrea Kruse
ITC-CPV, Forschungszentrum Karlsruhe, Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany

a r t i c l e

i n f o

a b s t r a c t
Different hydrothermal biomass gasication processes are under development. In contrast to biomass gasication processes without water, biomass with the natural water content (green biomass) can be converted completely and energetically efciently to gases. Depending on the reaction conditions, methane or hydrogen is the burnable gas produced. Some processes use catalysts. In recent years, significant progress was achieved in the development of various hydrothermal biomass gasication processes. However, some challenges still exist and technical solutions are needed before large-scale production facilities can be built. 2008 Elsevier B.V. All rights reserved.

Article history: Received 8 July 2008 Received in revised form 6 October 2008 Accepted 6 October 2008 Keywords: Methane Hydrogen Gasication Wet gasication Hydrothermal biomass gasication

Contents 1. 2. 3. 4. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Accomplishments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Challenges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Future opportunities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 391 392 396 397 398 398

1. Introduction The main idea of hydrothermal biomass gasication is to benet from the special properties of near- and supercritical water as solvent and its presence as reaction partner. Relatively fast hydrolysis of biomass in sub- and supercritical water leads to a rapid degradation of the polymeric structure of biomass. Consecutive reactions also are rather fast, as a result of which the gas is formed at low temperatures compared to dry processes. High solubility of the intermediates in the reaction medium, especially in water under supercritical conditions, signicantly inhibits tar and coke formation: the reactive species originating from biomass are diluted by solvation in water and consequently, the reaction rate of polymerization to unwanted products like tar and coke is reduced. Altogether, this leads to high gas yields of hydrothermal gasication processes at relatively low temperatures.

The goal consists in achieving special gas compositions in addition to high gas yields. For example, thermochemical formation of methane is possible only by the hydrothermal route, because the reactivity of biomass under dry conditions is too low at the low temperature needed for the formation of methane in high yields (Fig. 1 [1]). Depending on the reaction conditions and main product gases desired, hydrothermal biomass gasication processes can be divided into three main types: I. Aqueous phase reforming (APR) [25]: compounds originating from biomass (glucose, sorbitol, glycerol, methanol, and glycol) are gasied at around 215265 C to mainly hydrogen as burnable gas and carbon dioxide in the presence of a heterogeneous catalyst (Pt, later also: Ni, Ru, Rh, Pd, Ir). II. Catalyzed near-critical gasication to methane at either around 350 C in the liquid phase or around 400 C in the supercritical state [5,6]: biomass or organic compounds are gasied to mainly methane as burnable gas and carbon dioxide in the presence of an added heterogeneous catalyst.

Tel.: +49 7247 82 3388; fax: +49 7247 82 2244. E-mail addresses: andrea.kruse@itc-cpv.fzk.de, andrea.kruse2@gmx.net. 0896-8446/$ see front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.supu.2008.10.009

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Fig. 1. Equilibrium gas yields in the reactor as a function of temperature for biomass gasication of wood sawdust (CH1.35 O0.617 ) at 25 MPa with 5% (g/g) dry biomass content. Reprint from [1] with kind permission of Elsevier.

III. Supercritical water gasication (SCWG): biomass or organic compounds are gasied to mainly hydrogen as burnable gas and carbon dioxide without the addition of a solid catalyst [7] or in the presence of carbon or other solid catalysts [5,8]. Fig. 1 shows the temperature dependence of gas composition, Fig. 2 the concentration dependence: it is obvious that methane as desired product (type II above) needs lower temperatures than hydrogen (type III). In addition, hydrogen is the thermodynamically preferred product at low concentration and at lower temperatures (type I). Subcritical or near-critical processes in the presence of a catalyst have the clear advantage of a lower temperature. This means much lower investment costs, because the alloys suitable for supercritical gasication at around 600700 C are very costly [9]. On the other hand, catalyst stability in the sub- and near-critical hydrothermal gasication processes is a challenge, as will be discussed below. Apart from a high gas yield and low tar/coke formation at relatively low temperatures, another advantage of hydrothermal gasication compared to dry processes is the possibility to convert biomass with a natural water content of more than 80% (g/g). Green or fresh biomass consists mainly of water. Drying to less than 10% water content, as necessary for dry biomass conver-

sion processes, requires a lot of energy that is difcult to recover. This drying is not necessary for hydrothermal processing, which makes hydrothermal gasication interesting for biomass residues, e.g. from food production or paper industry and sewage sludge. According to the high oxygen content of biomass, gasication leads to high amounts of carbon dioxide. After the reaction and cooling, this carbon dioxide is mainly dissolved in the water, due to its high solubility. The pressurized gas phase separated from the aqueous phase has a relatively low CO2 content and, hence, a high heating value. No additional pressurization, which usually is costly, is necessary for storing this fuel gas. In the dry process, presence of inorganic compounds like chloride in the gas phase leads to severe corrosion problems. In hydrothermal gasication, inorganic compounds are found in the aqueous product phase. This means less cleaning efforts and less corrosion problems with the product gases during further processing. On the other hand, the question arises how these inorganic compounds can be isolated in an inexpensive way to close the nutrition cycle. The most important disadvantage of hydrothermal gasication might be the fact that so much water has to be heated up. The heat necessary to reach, e.g. 600 C may exceed the energy content of the biomass at a water content higher than 80% (g/g). This means that a heat exchanger is required and that the efciency of this heat exchanger is crucial to the overall energy efciency of the process. Fortunately, high-pressure heat exchangers are compact and relatively efcient. This can be explained theoretically and was veried experimentally at the bench-scale plant VERENA (German acronym for experimental facility for the energetic exploitation of agricultural matter) operating with a 100 kg/h sludge throughput [7]. In fact, the major drawback is the high investment costs needed because of the high pressure. This particularly applies to supercritical water gasication that requires the use of special materials because of the combination of high pressure and temperatures of 600 C or above. Recently, four reviews of hydrothermal biomass gasication were published: Elliott and van Rossum et al. [5,10] give an overview of hydrothermal gasication processes with heterogeneous catalysts and Kruse [7] without such catalysts. Less in detail, review [6] by Peterson et al. covers all types of hydrothermal gasication processes. These papers, together with previous reviews [8,11,12], contain a lot of information. Consequently, this article will provide a very short summary and focus on the challenges to overcome and the experience gained from advanced continuous plants. 2. Accomplishments Research in the eld of hydrothermal biomass gasication is based on the work of Modell et al. [1315] and on early work relating to the conversion of carbohydrates and biomass for the formation of useful products or for understanding the formation of coal [16,17]. An overview of the knowledge of the chemistry of hydrothermal biomass gasication gained so far is given in the articles [57,10]. Many of the studies reported deal with model compounds, in most cases, glucose. Biomass is a very heterogeneous feedstock and represents a complex mixture of various, also inorganic, constituents. Therefore, understanding of chemical processes during the conversion of real biomass is difcult. With the help of model substances that have the same functional groups as biomasses, but, unlike them, are pure substances and possess a much simpler structure, the effect of process-relevant parameters, such as temperature, pressure, concentration, heating rates, and others, is studied and the main reaction pathways are identied. The same types of reactions, with the same dependence of reaction parameters, are assumed to apply to biomass conversion. With

Fig. 2. Equilibrium gas yields in the reactor as a function of dry biomass content for biomass gasication of wood sawdust (CH1.35 O0.617 ) at 25 MPa, 873 K. Reprint from [1] with kind permission of Elsevier.

A. Kruse / J. of Supercritical Fluids 47 (2009) 391399 Table 1 Results of aqueous phase reforming of oxygenates at 1% (g/g) initial concentration (taken from [2]). Compound Reaction conditions ( C) Glucose Sorbitol Glycerol Ethylene glycol Methanol 216 255 216 255 216 255 216 255 216 255

393

Gasication efciency Carbon in the gas phase % (mol/mol) 50 80 61 90 83 99 90 99 94 94

Main products in the gas phase H2 % (mol/mol) 51 46 61 54 65 57 70 69 75 75 CO2 % (mol/mol) 43 42 35 36 30 32 29 29 25 25 CH4 % (mol/mol) 4.0 7.0 2.5 6.0 4.2 8.3 0.8 2.0 0.4 0.6

p (MPa) 29 56 29 56 29 56 29 56 29 56

this approach, a better understanding of hydrothermal gasication processes is achieved. Under the conditions of aqueous phase reforming (type I) at relatively low temperatures below 300 C, methane is expected thermodynamically as the main product, except for very low concentrations (Figs. 1 and 2). In the presence of Pt/Al2 O3 as catalyst, oxygenates of a very low concentration of 1% (g/g) were transformed to gas with a high hydrogen yield. Table 1 summarizes the results. It has to be pointed out that components with a higher hydrogen content exhibit an increased gas formation, here expressed by the carbon content in the gas (Table 1). At an increased initial concentration, the gas yield decreases. In the case of ethylene glycol of 10% (g/g) initial concentration, a conversion rate of up to 62% was reached [2]. Different catalysts [4] were tested for ethylene glycol gasication, leading to the following activity sequence (total carbon gasication relative to the amount of catalytic metal, 210 C): Ru Pt > Rh Ni > Pd [5]. According to thermodynamic calculation, the yield of methane after gasication near the critical point of water (374 C, 22.1 MPa) and at a reasonable dry matter content of 1020% (g/g) is supposed to be rather high (near-critical gasication to methane, type II). In fact, this also is the temperature range for hydrothermal liquefaction, and the gas yield without the addition of a catalyst is rather low [5]. Formation of methane from biomass is a hydrogenation process. Consequently, it is reasonable to try hydrogenation catalysts like nickel, platinum, or palladium [18,19]. Early studies of Modell et al. [14] do not indicate any catalytic effect of nickel containing mixed catalysts (as oxides) on biomass gasication. Likely, the catalyst was not active, because Elliott et

al. subsequently reported an increase of the gas yield in the presence of a nickel catalyst (reduced form) at temperatures between 350400 C [5]. In addition and as shown in Table 2, the presence of a nickel catalyst leads to high methane yields for the gasication of wet biomass. To avoid poisoning of the heterogeneous catalyst by carbon deposition and to support gas formation, alkali salts were added as co-catalyst in many studies [5]. Unfortunately, the early catalysts were hardly stable in the long term. This was a drawback with respect to process development. Investigations of the stability of support materials in hot water by Elliott et al. [5,19,20] represented a big step forward. They found useful support materials, e.g. carbon, mono-clinic zirconia or titania, and -alumina. Elliott et al. reported that only nickel in the reduced form had a signicant effect on hydrothermal gasication. Nickel catalysts were investigated by various groups and some of them revealed promising results in terms activity and catalytic lifetime ([2124]). Ruthenium catalysts of various formulations were also investigated. Some were found to be promising with regard to the two parameters above. Often, the catalyst lifetime was increased compared to Ni [5,12]. At the Pacic Northwest Lab., Elliott et al. demonstrated successfully the continuous gasication of biomass to methane-rich product gas. The initial problem of plugging of the catalyst bed by the biomass was solved by a liquefaction step in a CSTR prior to gasication by the catalyst bed reactor [5,25]. Fig. 3 shows the scheme of the mobile scaled-up reactor system with a throughput of 2 L/h (350 C, 24 MPa). The reactor unit is mounted in a ve-wheeled trailer unit [25]. The demonstration unit worked well, but some poisoning of the catalyst was observed.

Table 2 Catalytic hydrothermal gasication of wet biomass by a nickel catalyst (alumino-silica-supported nickel catalyst, 10% (g/g) dry mass, 15 min at 400 C in a batch reactor, taken from [5,20]). Biomass Cellulosea Sorghum Sunower Napier grass Corn stoverb Water hyacinth Kelp Douglas rb Grape pomace Spent grain Potato wasteb
a b

Gasication efciency C in the gas phase % (mol/mol) 97.6 94.6 87.8 100.8 72.9 73.1 78.8 49.8 44.5 55.7 46.4

Gas composition % (mol/mol) H2 CH4 3.9 9.5 5.0 6.9 20.1 11.3 7.1 21.6 9.6 9.6 27.6 43.2 38.4 45.7 40.6 16.3 35.9 41.9 29.0 40.2 43.1 20.4

CO2 47.8 50.5 45.5 51.1 62.0 49.6 48.4 47.6 47.7 44.2 50.2

CO 0 0 0 0 0 0.8 0 0 0 0 0

C2 + 3.7 1.6 2.4 1.4 1.3 0.9 1.5 1.8 1.0 1.4 1.8

380 C. Sodium carbonate co-catalyst with lower (1/10) nickel loading.

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Fig. 3. Schematic representation of a mobile scaled-up reactor system and auxiliaries for subcritical biomass gasication to methane. Reprinted with permission from [25]. Copyright 1999 American Chemical Society.

At a reasonable dry matter content (1020% (g/g)), rather high temperatures are necessary to reach high hydrogen yields (supercritical water gasication, type III). According to the early studies of Antal and coworkers, the gasication yield decreases at a higher glucose concentration [26]. This was a major obstacle to be overcome in technical development. The group started to develop carbon catalysts, which were very effective. For example, complete conversion of glucose (22% g/g dry matter) to a hydrogen-rich synthesis gas (2.24 mol hydrogen/mol glucose) was achieved at a weight hourly space velocity (WHSV) of 22.2 h1 in supercritical water at 600 C and 34.5 MPa using a coconut shell activated carbon catalyst [26]. Also with sewage sludge biomass, total gasication to a hydrogen-rich gas was achieved [26,27]. A drawback of this process was the plugging of the catalyst solid bed due to the accumulation of ash originating from the biomass and the small amount of coke produced [8]. These studies of carbon-catalyzed SCWG were continued by Matsumura and coworkers [28]: In a pilot plant (0.76 l/min

throughput, see Fig. 4), a suspended carbon catalyst was fed in together with the biomass (ow 1, Fig. 4) instead of using a solid bed that might be plugged as indicated above. The feedstock was chicken manure. After mixing, the aqueous suspension of activated carbon and biomass was fed into the rst heat exchanger HX 1, heated up, and entered the heated liquidizing reactor (180 C, 1.2 MPa, 26.7 min reaction time). Here, the solid biomass particles were converted to oil. After cooling in heat exchanger HX 1, the mixture was compressed by a high-pressure pump and passed on to the second heat exchanger HX 2. In the downstream heater, temperature was increased further to the value needed for conversion in the heated gasication reactor (600 C, 25 MPa, 1.7 min reaction time). The product mixture was cooled down to room temperature in heat exchanger HX 2 and the cooler. Then, the pressure was reduced to normal conditions and the mixture was separated into a gas phase (ow 2, Fig. 4) and an aqueous suspension (ow 3, Fig. 4). To heat the heater and the gasication and liquidizing reactor, a propane burner was used. Comparisons of runs with and

Fig. 4. Scheme of a pilot plant for SCWG with a suspended carbon catalyst (adapted from [28]).

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395

Fig. 5. Scheme of the bench-scale plant VERENA (process modication I, adapted from [33]).

without a carbon catalyst show that the gas yield is doubled by the catalyst. Complete gasication of chicken manure (10% (g/g)) was achieved when increasing the carbon catalyst content to 5% (g/g). The product suspension separated into an ash-containing and a carbon catalyst-containing layer [28]. In addition to the carbon catalysts, noble metal catalysts were tested successfully for supercritical water gasication of higher concentrations (<5% (g/g) and 10% (g/g)) of glucose to hydrogen at higher temperatures of 600700 C [5,2931]. Sometimes, the inner surface of the reactor was used as the catalyst. This was the case for the SCWG of methanol [32]. The catalytic effect of the wall was increased by corrosion and inhibited by poisoning caused by some feedstocks [8]. Even though the use of, e.g. a carbon catalyst has obvious advantages in terms of the formation of hydrogen-rich gas, research groups of the Karlsruhe Research Center, Germany, focus on supercritical gasication of biomass without adding heterogeneous catalysts. (For the discussion of whether the reactor wall may be a heterogeneous catalyst, see [7].) The main reason is that the use of heterogeneous catalyst beds may be associated with the risk of plugging by salts originating from the biomass, which would be a major obstacle to technical application. At Karlsruhe, the largest plant for hydrothermal biomass gasication, with a throughput of 100 kg/h slurry (usually, up to 20% (g/g) dry matter, depending on the nature of biomass), was built. After some teething troubles in the beginning of operation (plugging, problems concerning feeding in the biomass), various biomass feedstocks, e.g. corn silage, were successfully converted to gas. The conceptual design of the VERENA test facility is shown in Fig. 5. It is designed for about 700 C and 35 MPa at the maximum. The components exposed to high temperature are made of a nickel-based alloy. Biomass is crushed, water content is adjusted to the desired dry matter content, subjected to pressure using membrane pumps, and heated up by a tubein-tube heat exchanger having an efciency higher than 80%. In a so-called pre-heater, the temperature of the aqueous ow is further increased prior to gasication (Fig. 5). Conversion mainly takes place downstream in the reactor. The pre-heater and reactor are heated by hot ue gas from a propane burner. Following the reaction, the product mixture is cooled down in the heat exchanger and an additional cooler. The gas phase is separated from the liquid phase still under pressure. In this way, a large part of the CO2 remains dissolved in the aqueous phase. Afterwards, the hydrogenrich gas phase is CO2 -depleted in a scrubber. The product gas can be

expanded and burnt in a are or lled into pressurized gas cylinders for further use by, e.g. a directly coupled gas motor or fuel cells. First experiments revealed a CO2 depletion from 11.5 to 0.05 vol.% downstream of the phase separator and scrubbing column [3335]. The aqueous phase is expanded to normal pressure, with the dissolved CO2 being released. Also at the Karlsruhe Research Center, inuence of different ingredients of biomass on the gasication process is investigated. A main result is that the alkali salts in the biomass increase the hydrogen yield [36]. The reason is the catalysis of the watergas shift reaction by alkali salts that increase the yield of hydrogen and decrease the yield of CO. Other reaction pathways are inuenced indirectly by this effect, because the active hydrogen formed inhibits unwanted side reactions. Such side reactions decrease the gas yield. Watergas shift reaction : CO + H2 O CO2 + H2 (1)

In contrast to alkali salts, other biomass components like proteins reduce the gas yield [37,38]. SCWG is considered to be an environmentally friendly process. This is conrmed by a life cycle assessment by Gasa et al. [39], which included a comparison with other biomass conversion technologies. Sewage sludge was assumed to be the feedstock. In the study, the sewage sludge disposal options of use in agriculture and landscaping as well as combustion were considered. The basic data of the SCWG process were taken from experiments at the VERENA plant described above. Overall, the assessment of the SCWG process in terms of consumption of resources, acidication, particle emission, and eutrophication was very positive. Only for the consumption of resources was the SCWG process rated worse than the other sewage sludge treatment processes. This is due to the relatively high consumption of gas for heating as a result of the still lacking optimization [39]. It must be noted that the VERENA plant was built to demonstrate SCWG, but it is not optimized in terms of energy consumption. In this study energy input is not only necessary in order to run the SCWG process but also to produce fertilizer in an external process. This was incorporated to compensate differences of the considered biomass conversion processes, producing fertilizer or not. Therefore in this study, the separation of salt during SCWG and its use as fertilizer would also reduce the energy consumption. Based on thermodynamic considerations, SCWG was evaluated. The approaches used for this purpose varied by SCWG process fea-

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tures and assumptions. Without considering the low-temperature heat of the products, the calculated energy efciencies of the different approaches and process designs varied between 44 and 65%. Exergy efciencies published were in the range of 4152% [1,4043]. These values were good enough to start to develop the biomass conversion process. An evaluation of supercritical water gasication in comparison with biomethanation for wet biomass utilization in Japan was presented by Matsumura [43]. Energy efciency of SCWG was calculated to be 64.8%, which is higher than that calculated for biomethanation. On the other hand, the costs of the product gas produced by SCWG were 1.86 times higher than the price of city gas in Tokyo (1.64 yen/MJ) in the year 2002 [43]. Any thermodynamic calculation stresses the effect of the heat exchanger. Its improvements will therefore have a major effect on energy efciency. Another life cycle evaluation focusing on a comparison of the efciency and overall CO2 emission of cars driven by energy from biomass conversion technologies, including SCWG, was presented by Yoshida et al. [44]. Such types of energy used by cars are electricity, biogas, methanol, hydrogen, and others. The process chain, including SCWG, for gas- and electricity-driven cars was found to be most energetically efcient for biomass with a high water content (>30% and >40% water). As regards the costs, other biomass conversion processes are more attractive today. But this may change, if the costs of fuel cells decrease. It was pointed out by Yoshida et al. that an improvement of heat exchange and a reduction of capital costs would enhance the position of SCWG [44]. 3. Challenges Universal challenges in hydrothermal biomass gasication are corrosion and problems with salts, which are of variable importance to the process. In SCWG, hydrogen is formed, which is known to be able to change the mechanical stability of metals. Hydrogen formation does not seem to be problematic for autoclave materials used under these conditions. In SCWG experiments with methanol, for example, the reactor tube (nickel-based alloy 625) was used for more than 1000 h [45,46]. However, corrosion of the reactor material was observed in SCWG experiments. The experience gained with respect to corrosion varies from research group to research group, because different feedstocks and reactor materials were applied and operation times of the reactors were of variable duration. Irrespective of this fact, biomass may include many different components. In CSTR experiments with protein-containing biomass, severe corrosion was found, likely because of the sulfur in the biomass [38]. Use of glucose with K2 CO3 was also found to result in products of weak corrosion (Ni, Cr, Mo particles in the outow) [47]. Corrosion was also observed when converting corn silage (SCWG without solid catalyst; [48]) and different feedstocks by carboncatalyzed SCWG [8]. However, a solution of the severe corrosion problem in supercritical water oxidation was found [4951]; and it will also be possible to solve the problem of the relatively weak corrosion in SCWG. The biomass has to pass pumps to reach the high pressure needed. The type of pump (membrane, piston, etc.) and in particular the pump valves have to be selected carefully. The biomass must be conditioned to a pumpable slurry, dispersion or aqueous solution. On the other hand, a high dry matter content leads to a high output of gas. The still pumpable dry matter content depends very much on the type of biomass and its pre-treatment. For example, sewage sludge can be pumped up to 40% dry mass content [52]. In any case, the dry matter content should be high enough to ensure that the energy content of the feedstock is higher than the energy loss of the processing plant. At the VERENA plant (see Fig. 5) which is

not energetically optimized, roughly 10 wt.% dry matter are needed [35]. Antal et al. studied the feeding of sawdust suspended in starch gel via a cement pump. Matsumura et al. successfully applied a hydrothermal pre-treatment (150200 C, 30 min) for feeding their plant with cabbage. Detailed investigations revealed that the hemicellulose was dissolved and the cell structure of the biomass was destroyed [7]. Liquefaction before feeding [43] or the use of dissolved feedstock (e.g. by biochemical treatment) facilitates pumping. In addition, other types of hot water treatment like steam explosion or electroporation can be applied. These types of pre-treatment are common in fermentation to improve the materials availability for biochemical conversion [53,54]. At the VERENA plant, various types of biomass can be treated just by reducing the particle size in different mills and crushers [34,35,55]. As the plant is larger than lab-scale equipment, larger biomass particles can be used. The type of pre-treatment applied depends on the nature of the biomass and the plant scale. In addition to these universal challenges, the three types of hydrothermal biomass gasication have their own special obstacles to overcome. In aqueous phase reforming, high hydrogen yields were achieved for hydrogen-rich compounds at low concentrations only. Gasication of high concentrations of glucose and of biomass was not successful. It was suggested to design a two-step process with two reactors: rst, a low-temperature reactor for hydrogenation of glucose, followed by a high-temperature reactor for reforming. Some lab-scale experiments are promising [3], but still far away from application. The main question is whether it will be possible to convert reasonable concentrations of real biomass by this process. The major challenge faced in catalyzed near-critical hydrothermal gasication to methane (type II) is the poisoning of the heterogeneous catalysts by the salts fed in with the biomass [56]. Both the process of poisoning [57] and the behavior of salts [58] were investigated to develop a process suitable for technical application. It is required to conceive a process that separates the salts before they get into contact with the heterogeneous catalyst. Elliott [5] studied mineral capture in the preheating step using two representative biorenery residues, which is a signicant step forwards. Other catalyst poisons are nitrogen-containing compounds [59] and sulfur [56,60]. It is promising that regeneration of a noble metal catalyst poisoned by sulfur in subcritical water was reported as well [61]. Under supercritical conditions, solubility of salts is reduced. Consequently, solids occur in supercritical gasication processes, which may lead to plugging. This is problematic especially if the tube diameters are small, crystals are large or sticky, and ow velocity is low. In supercritical water gasication with a carbon xed-bed catalyst, plugging by salts is a great challenge. As mentioned earlier, transportation of the catalyst in the form of a suspension through the whole process is one of the solutions investigated. A very interesting approach is supercritical water gasication in a uidized carbon-catalyzed bed. Basic investigations in this eld are very promising [62,63]. Plugging by salts mainly is a problem of supercritical gasication with solid catalysts [8]. In supercritical water gasication without catalysts, the free diameter is larger. As mentioned above, salts are also useful as catalyst for the watergas shift reaction. On the other hand, they may also cause plugging in SCWG without catalyst beds. In this connection, salt concentration of the biomass, the nature of the salts and, hence, the kinetics of seed crystal formation and crystal growth are important. Alkali salts like carbonates may usually be passed easily through a tube, other salts not [58,64].

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397

Fig. 6. Scheme of the modied bench-scale plant VERENA (process modication II, adapted from [33]).

Especially in combination with char, plugging may occur in parts of the equipment having a smaller diameter or at low ow velocity. The presence of salts in biomass seems to result in challenges in all types of hydrothermal gasication, but the quality of these challenges is different. In aqueous phase reforming, solubility of salts is high and the inuence on the catalyst under real biomass conditions is unknown. In subcritical gasication for methane formation, solubility is still high, but the salts lead to a poisoning of the catalyst. In supercritical gasication processes, salts precipitate, which causes major plugging problems in processes with xed catalyst beds and minor problems in processes without. In all cases, salt separation is of interest for use as a fertilizer. After hydrothermal gasication processes without salt separation, the salts are found mainly in the aqueous efuent. It would be useful to separate or concentrate the salts in order to bring them back to the elds, thus closing the nutrition cycle of the biomass. To optimize the process, challenges connected with the energy efciency of the process have to be overcome. Importance of this aspect increases from hydrothermal gasication type I to type III, because the temperature increases. A very important point is the efciency of heat exchange in the whole process. Without a heat exchanger, the SCWG process would not make sense from the energy point of view. On the other hand, the heating rate of the feedstock should be high, higher than achieved by a heat exchanger. As shown by different research groups, low heating rates lead to unwanted reaction products like tars and reduce the gas yield [65,47]. As a solution, only water can be heated by the heat exchanger [1], which is then mixed with the biomass. In this case, the biomass feedstock should have a high dry mass content, which may cause pumping difculties, if the biomass is not pretreated or liqueed. Such a process modication was tested successfully at the VERENA plant (Fig. 6). The biomass was heated to subcritical temperature only and then mixed with water of supercritical temperature. Here, gas composition was changed compared to the original process: the hydrogen content was higher and the methane content lower [33]. As observed by, e.g. DJesus et al. [66] and earlier by Antal and coworkers [26], the relative gas yield decreases with initial concentration/dry matter content of the feedstock. This is a drawback in technical process development, because a high absolute hydrogen yield will reduce the relative production costs that are nearly independent of the dry matter content. Kruse and Faquir pointed

out that back-mixing reduces the parasitic side reaction to higher molecular weight compounds [67]. The reason is assumed to be the presence of active hydrogen that suppresses polymerization by the hydrogenation of early and reactive intermediates, which then are no longer able to polymerize. This is conrmed by the comparison of results obtained in a CSTR with results from tubular reactors and batch reactors without back-mixing. Only with back-mixing is the late hydrogen product able to react with early intermediates. An alternative solution is to feed in a component that forms active hydrogen during the reaction [67]. The challenge now consists in implementing such a concept on the technical scale without losing energy efciency or increasing costs. 4. Future opportunities The question of how large the plant should be is very important. Transportation of biomass with a high water content would be very expensive and energy-consuming. But the higher the process temperature is, the larger the plant should be, because the relative energy loss expected increases with temperature, but decreases with volume. Hence, different hydrothermal biomass gasication processes may be suitable for different types of application and different plant sizes. The approach pursued by the Karlsruhe Research Center is that SCWG should be part of a larger plant, such as a winery, that produces biomass to be gasied. In this case, energy management may be improved: the heat needed for SCWG may be generated by another part of the plant or by a high-temperature fuel cell that processes the fuel gas from SCWG. At the moment, the Karlsruhe Research Center is planning to scale the VERENA concept up in cooperation with industry. Carbon-catalyzed SCWG process approaches still remain to prove their applicability on the technical scale. When using the suspended carbon catalyst, recycling is very important and still needs to be demonstrated. In the case of a uidized-bed, carboncatalyzed SCWG, scale-up from the very small lab equipment still remains to be accomplished. If these obstacles will be overcome, both processes will be very interesting for technical application. The idea of a transportable plant is very attractive [56,68], which is especially true for catalyzed near-critical gasication to methane. As an example, the concept of a farm-scale hydrothermal gasication system to treat swine manure is shown in Fig. 7. This concept includes units to process mineral matter and reduced sulfur (in

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Fig. 7. Process owchart of the farm-scale, conceptual wet gasication unit. Reprinted with permission from [56]. Copyright 2007 American Chemical Society.

proteins), which are under development at the Pacic Northwest Laboratories [56]. Aqueous phase reforming is interesting for the small-scale production of hydrogen, e.g. for PEM fuel cells. The advantage is the rather low temperature compared with other hydrothermal gasication processes. A drawback has been the low concentration of feedstock up to now. Mobile application of aqueous phase reforming with PEM fuel cells would lead to a high weight due to the large amount of water. In addition, the range of feedstocks that have been gasied successfully so far is small. The future of this process will depend on whether the limitations in terms of concentration and nature of the feedstock will be overcome. This will require further research and development. In recent years, production of fuels or high-value products using enzymes or microorganisms met with increasing interest. In particular, production of ethanol fuel presently is of high economic importance. Usually, such processes are conducted in an aqueous solution and associated with the production of wet residues, as it is impossible to use the complete plant from the eld. In bioethanol production, for instance, biomass is separated rst into the main components of cellulose, hemicellulose, and lignin. Only carbohydrates can be converted to sugar and further to ethanol. Lignin cannot be converted and remains. In other cases, conversions are not complete. In biogas production, for example, the whole biomass is fed into the reactor, but conversion to gas is incomplete. In both cases, combination with thermochemical conversion reactions in water, such as the hydrothermal gasication process presented here, leads to synergies in terms of a biorenery, because the wet residues of the bioprocess can be converted to useful products without drying. Recently, the formation of platform chemicals from sugar or lignin under hydrothermal conditions also yielded very promising results [6972]. Again, the combination with gasication may lead to synergies and closed loops in a biorenery. Acknowledgements The helpful comments of Erdogan Kiran, Nicolaus Dahmen and Maike Schrder during the genesis of this article are gratefully acknowledged.

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